Scholars@Duke
Ross A. Widenhoefer

Ross A. Widenhoefer

Professor of Chemistry
Chemistry
ross.widenhoefer@duke.edu
Box 90346, Durham, NC 27708-0346
124 Science Drive, 2101 French Science Center, Durham, NC 27708
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Selected Publications

Cationic Bis(Gold) Indenyl Complexes.

Journal Article ChemPlusChem · June 2024 Reaction of (P)AuOTf [P=P(t-Bu)2o-biphenyl] with indenyl- or 3-methylindenyl lithium led to isolation of gold η1-indenyl complexes (P)Au(η1-inden-1-yl) (1 a) and (P)Au(η1-3-methylinden-1-yl) (1 b), respectively, ... Full text Cite

Modulating Transition Metal Reactivity with Force

Journal Article ChemCatChem · March 8, 2024 The reactivity and selectivity of a transition metal catalyst is intimately related to its ligand-sphere geometry, and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another. F ... Full text Cite

Force-Modulated C-C Reductive Elimination from Nickel Bis(polyfluorophenyl) Complexes

Journal Article Organometallics · August 14, 2023 We have analyzed the rate of C(sp2)-C(sp2) reductive elimination from nickel(II) bis(2,4,6-trifluorophenyl) complexes (P-P)Ni(2,4,6-C6H2F3)2 containing either MeOBiPhep (3a) or a macrocyclic bisphosphine ligand (3b-3e) as a function of force applied to the ... Full text Cite

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis.

Journal Article Nature communications · August 2023 Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplore ... Full text Cite

Force-Modulated Selectivity of the Rhodium-Catalyzed Hydroformylation of 1-Alkenes

Journal Article ACS Catalysis · November 18, 2022 Here we quantify the regio- chemo-, and enantioselectivity of the hydroformylation of 1-alkenes catalyzed by Rh(I) complexes containing chiral macrocyclic biaryl bis(phosphine) ligands as a function of mechanical force applied to the biaryl backbone of the ... Full text Cite

Kinetics and Mechanisms of the Gold-Catalyzed Hydroamination of Axially Chiral 1-Aryl-1,2-butadienes with Aniline

Journal Article Organometallics · October 10, 2022 The mechanisms of the hydroamination of enantiomerically enriched, axially chiral (R)-1-aryl-1,2-butadienes (R)-(4-C6H4R)C(H)=C=C(H)Me [R = Ph (1a), OMe (1b)] with aniline catalyzed by (IPr)AuOTf have been investigated employing a combination of kinetic an ... Full text Cite

Substituent Effects and the Mechanism of Gold to Alkene Benzylidene Transfer Employing a Gold Sulfonium Benzylide Complex

Journal Article Organometallics · May 9, 2022 Aliphatic and aromatic alkenes react rapidly and efficiently with the gold sulfonium benzylide complex [(P)- AuCHPh(SPh2)]+ {B [3,5-CF3C6H3]4}- [P = P (t-Bu)2o-biphenyl; 1] at room temperature via the cationic two-coordinate gold benzylidene complex [(P)Au ... Full text Cite

Force-modulated reductive elimination from platinum(ii) diaryl complexes.

Journal Article Chemical science · August 2021 Coupled mechanical forces are known to drive a range of covalent chemical reactions, but the effect of mechanical force applied to a spectator ligand on transition metal reactivity is relatively unexplored. Here we quantify the rate of C(sp2)-C( ... Full text Cite

Kinetics and Mechanism of the Gold-Catalyzed Hydroamination of 1,1-Dimethylallene with N-Methylaniline.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · July 2021 The mechanism of the intermolecular hydroamination of 3-methylbuta-1,2-diene (1) with N-methylaniline (2) catalyzed by (IPr)AuOTf has been studied by employing a combination of kinetic analysis, deuterium labelling studies, and in situ spectral analysis of ... Full text Cite

Mechanism of the Stereomutation of an Azaplatinacyclobutane Complex

Journal Article Organometallics · April 26, 2021 The diastereomerically pure azaplatinacyclobutane complex, bearing a single deuterium atom at Cα, undergoes stereomutation about the Cα-Cβ bond of the azaplatinacyclobutane moiety at 30 °C with a half-life of 3.0 h. Kinetic analysis of the stereomutation o ... Full text Cite

Mechanochemical Regulation of Oxidative Addition to a Palladium(0) Bisphosphine Complex.

Journal Article Journal of the American Chemical Society · October 2020 Featured Publication Here, we report the effect of force applied to the biaryl backbone of a bisphosphine ligand on the rate of oxidative addition of bromobenzene to a ligand-coordinated palladium center. Local compressive and tensile forces on the order of 100 pN were generat ... Full text Cite

Formation of Cyclopropanes via Activation of (γ-Methoxy)alkyl Gold(I) Complexes with Lewis Acids

Journal Article Organometallics · September 14, 2020 Featured Publication Treatment of the gold 3-methoxy-3-phenylpropyl complex (P)AuCH2CH2CH(OMe)Ph [P = P(t-Bu)2o-biphenyl] with AlCl3 at -78 °C led to the immediate (≤5 min) formation of a 4:1 mixture of phenylcyclopropane and (1-methoxypropyl)benzene in 86 ± 5% combined yield. ... Full text Cite

Synthesis, Structure, and Reactivity of Gold(I) α-Oxo Carbenoid Complexes

Journal Article Organometallics · April 27, 2020 Featured Publication The trifluoromethanesulfonate α-oxo carbenoid complexes (IPr)AuCH(OTf)COR [R = OEt (1a), p-tolyl (1b)] were isolated from reactions of (IPr)Au(OTf) with the corresponding α-diazo carbonyl compounds. The pyridinium α-oxo carbenoid complexes [(IPr)AuCH(4-MeC ... Full text Cite

Kinetics and Mechanism of the Platinum(II)-Catalyzed Hydroarylation of Vinyl Arenes with 1,2-Dimethylindole

Journal Article Israel Journal of Chemistry · March 1, 2020 The mechanism of the intermolecular hydroarylation of vinyl arenes (1) with 1,2-dimethylindole (2) catalyzed by PtCl2 has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and stereochemical analysis. The results of thes ... Full text Cite

Synthesis of gold allyloxysulfonium complexes and elimination to form an α,β-unsaturated aldehyde.

Journal Article Chemical communications (Cambridge, England) · November 2019 Treatment of the gold vinyl carbene/allylic cation complex (E)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf- with sulfoxides at -95 °C formed the corresponding gold allyloxysulfonium complexes [(IPr)AuC(H)(OSR2)C(H)[double bond, length as m-dash]C(4-C6H4OMe)2]+ OTf ... Full text Cite

Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · August 2019 The gold sulfonium benzylide complexes [(P1)AuCHPh(SR1 R2 )]+  {B[3,5-CF3 C6 H3 ]4 }- [P1=P(tBu)2 o-biphenyl; R1 , R2 =-(CH2 ... Full text Cite

Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.

Journal Article Chemical science · June 2019 Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf- {L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P( ... Full text Cite

Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols

Journal Article ACS Catalysis · September 7, 2018 The mechanism of the hydroalkoxylation of 3-methyl-1,2-butadiene (1) with 1-phenylpropan-1-ol (2) catalyzed by (IPr)AuOTf in toluene has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and in situ spectral analysis of ... Full text Cite

Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes.

Journal Article Angewandte Chemie (International ed. in English) · April 2018 Methoxide abstraction from gold acetylide complexes of the form (L)Au[η1 -C≡CC(OMe)ArAr'] (L=IPr, P(t Bu)2 (ortho-biphenyl); Ar/Ar'=C6 H4 X where X=H, Cl, Me, OMe) with trimethylsilyl trifluoromethanes ... Full text Cite

Cationic Bis(Gold) Indenyl Complexes.

Journal Article ChemPlusChem · June 2024 Reaction of (P)AuOTf [P=P(t-Bu)2o-biphenyl] with indenyl- or 3-methylindenyl lithium led to isolation of gold η1-indenyl complexes (P)Au(η1-inden-1-yl) (1 a) and (P)Au(η1-3-methylinden-1-yl) (1 b), respectively, ... Full text Cite

Modulating Transition Metal Reactivity with Force

Journal Article ChemCatChem · March 8, 2024 The reactivity and selectivity of a transition metal catalyst is intimately related to its ligand-sphere geometry, and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another. F ... Full text Cite

Force-Modulated C-C Reductive Elimination from Nickel Bis(polyfluorophenyl) Complexes

Journal Article Organometallics · August 14, 2023 We have analyzed the rate of C(sp2)-C(sp2) reductive elimination from nickel(II) bis(2,4,6-trifluorophenyl) complexes (P-P)Ni(2,4,6-C6H2F3)2 containing either MeOBiPhep (3a) or a macrocyclic bisphosphine ligand (3b-3e) as a function of force applied to the ... Full text Cite

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis.

Journal Article Nature communications · August 2023 Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplore ... Full text Cite

Force-Modulated Selectivity of the Rhodium-Catalyzed Hydroformylation of 1-Alkenes

Journal Article ACS Catalysis · November 18, 2022 Here we quantify the regio- chemo-, and enantioselectivity of the hydroformylation of 1-alkenes catalyzed by Rh(I) complexes containing chiral macrocyclic biaryl bis(phosphine) ligands as a function of mechanical force applied to the biaryl backbone of the ... Full text Cite

Kinetics and Mechanisms of the Gold-Catalyzed Hydroamination of Axially Chiral 1-Aryl-1,2-butadienes with Aniline

Journal Article Organometallics · October 10, 2022 The mechanisms of the hydroamination of enantiomerically enriched, axially chiral (R)-1-aryl-1,2-butadienes (R)-(4-C6H4R)C(H)=C=C(H)Me [R = Ph (1a), OMe (1b)] with aniline catalyzed by (IPr)AuOTf have been investigated employing a combination of kinetic an ... Full text Cite

Substituent Effects and the Mechanism of Gold to Alkene Benzylidene Transfer Employing a Gold Sulfonium Benzylide Complex

Journal Article Organometallics · May 9, 2022 Aliphatic and aromatic alkenes react rapidly and efficiently with the gold sulfonium benzylide complex [(P)- AuCHPh(SPh2)]+ {B [3,5-CF3C6H3]4}- [P = P (t-Bu)2o-biphenyl; 1] at room temperature via the cationic two-coordinate gold benzylidene complex [(P)Au ... Full text Cite

Force-modulated reductive elimination from platinum(ii) diaryl complexes.

Journal Article Chemical science · August 2021 Coupled mechanical forces are known to drive a range of covalent chemical reactions, but the effect of mechanical force applied to a spectator ligand on transition metal reactivity is relatively unexplored. Here we quantify the rate of C(sp2)-C( ... Full text Cite

Kinetics and Mechanism of the Gold-Catalyzed Hydroamination of 1,1-Dimethylallene with N-Methylaniline.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · July 2021 The mechanism of the intermolecular hydroamination of 3-methylbuta-1,2-diene (1) with N-methylaniline (2) catalyzed by (IPr)AuOTf has been studied by employing a combination of kinetic analysis, deuterium labelling studies, and in situ spectral analysis of ... Full text Cite

Mechanism of the Stereomutation of an Azaplatinacyclobutane Complex

Journal Article Organometallics · April 26, 2021 The diastereomerically pure azaplatinacyclobutane complex, bearing a single deuterium atom at Cα, undergoes stereomutation about the Cα-Cβ bond of the azaplatinacyclobutane moiety at 30 °C with a half-life of 3.0 h. Kinetic analysis of the stereomutation o ... Full text Cite

Mechanochemical Regulation of Oxidative Addition to a Palladium(0) Bisphosphine Complex.

Journal Article Journal of the American Chemical Society · October 2020 Featured Publication Here, we report the effect of force applied to the biaryl backbone of a bisphosphine ligand on the rate of oxidative addition of bromobenzene to a ligand-coordinated palladium center. Local compressive and tensile forces on the order of 100 pN were generat ... Full text Cite

Formation of Cyclopropanes via Activation of (γ-Methoxy)alkyl Gold(I) Complexes with Lewis Acids

Journal Article Organometallics · September 14, 2020 Featured Publication Treatment of the gold 3-methoxy-3-phenylpropyl complex (P)AuCH2CH2CH(OMe)Ph [P = P(t-Bu)2o-biphenyl] with AlCl3 at -78 °C led to the immediate (≤5 min) formation of a 4:1 mixture of phenylcyclopropane and (1-methoxypropyl)benzene in 86 ± 5% combined yield. ... Full text Cite

Synthesis, Structure, and Reactivity of Gold(I) α-Oxo Carbenoid Complexes

Journal Article Organometallics · April 27, 2020 Featured Publication The trifluoromethanesulfonate α-oxo carbenoid complexes (IPr)AuCH(OTf)COR [R = OEt (1a), p-tolyl (1b)] were isolated from reactions of (IPr)Au(OTf) with the corresponding α-diazo carbonyl compounds. The pyridinium α-oxo carbenoid complexes [(IPr)AuCH(4-MeC ... Full text Cite

Kinetics and Mechanism of the Platinum(II)-Catalyzed Hydroarylation of Vinyl Arenes with 1,2-Dimethylindole

Journal Article Israel Journal of Chemistry · March 1, 2020 The mechanism of the intermolecular hydroarylation of vinyl arenes (1) with 1,2-dimethylindole (2) catalyzed by PtCl2 has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and stereochemical analysis. The results of thes ... Full text Cite

Synthesis of gold allyloxysulfonium complexes and elimination to form an α,β-unsaturated aldehyde.

Journal Article Chemical communications (Cambridge, England) · November 2019 Treatment of the gold vinyl carbene/allylic cation complex (E)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf- with sulfoxides at -95 °C formed the corresponding gold allyloxysulfonium complexes [(IPr)AuC(H)(OSR2)C(H)[double bond, length as m-dash]C(4-C6H4OMe)2]+ OTf ... Full text Cite

Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · August 2019 The gold sulfonium benzylide complexes [(P1)AuCHPh(SR1 R2 )]+  {B[3,5-CF3 C6 H3 ]4 }- [P1=P(tBu)2 o-biphenyl; R1 , R2 =-(CH2 ... Full text Cite

Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.

Journal Article Chemical science · June 2019 Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf- {L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P( ... Full text Cite

Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols

Journal Article ACS Catalysis · September 7, 2018 The mechanism of the hydroalkoxylation of 3-methyl-1,2-butadiene (1) with 1-phenylpropan-1-ol (2) catalyzed by (IPr)AuOTf in toluene has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and in situ spectral analysis of ... Full text Cite

Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes.

Journal Article Angewandte Chemie (International ed. in English) · April 2018 Methoxide abstraction from gold acetylide complexes of the form (L)Au[η1 -C≡CC(OMe)ArAr'] (L=IPr, P(t Bu)2 (ortho-biphenyl); Ar/Ar'=C6 H4 X where X=H, Cl, Me, OMe) with trimethylsilyl trifluoromethanes ... Full text Cite

Experimental Evaluation of (L)Au Electron-Donor Ability in Cationic Gold Carbene Complexes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · December 2017 29 Si NMR spectroscopy was employed to evaluate the electron donor properties of the (L)Au fragments in the cationic gold (β,β-disilyl)vinylidene complexes [(L)Au=C=CSi(Me)2 CH2 CH2 Si(Me)2 ]+ Full text Cite

Formal Synthesis of (+)-Laurencin by Gold(I)-Catalyzed Intramolecular Dehydrative Alkoxylation.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · May 2017 8-Membered cyclic ethers are found in a wide range of natural products; however, they are challenging synthetic targets due to enthalpic and entropic barriers. The gold(I)-catalyzed intramolecular dehydrative alkoxylation of ω-hydroxy allylic alcohols was ... Full text Cite

Gold(I)-Catalyzed Intramolecular Hydroamination of Unactivated Terminal and Internal Alkenes with 2-Pyridones.

Journal Article Organic letters · March 2017 The cationic gold phosphine complex [(P1)Au(NCMe)]+SbF6- [P1 = P(t-Bu)2o-biphenyl; 2] catalyzes the intramolecular hydroamination of 6-alkenyl-2-pyridones to form 1,6-carboannulated 2-pyridones in high yield. The ... Full text Cite

Unexpected Skeletal Rearrangement in the Gold(I)/Silver(I)-Catalyzed Conversion of 7-Aryl-1,6-enynes to Bicyclo[3.2.0]hept-6-enes via Hidden Brønsted Acid Catalysis

Journal Article Organometallics · February 13, 2017 Cycloaddition of an isotopically labeled 7-phenyl-1,6-enyne catalyzed by a mixture of LAuCl [L = P(t-Bu)2o-biphenyl)] and AgSbF6 forms the corresponding 6-phenylbicyclo[3.2.0]hept-6-ene with concomitant scrambling of the olefinic CPh (C6) and CH (C7) group ... Full text Cite

Gold-Catalyzed Intermolecular, anti-Markovnikov Hydroarylation of Methylenecyclopropanes with Indoles.

Journal Article Organic letters · October 2016 Cationic gold complexes containing an N-heterocyclic carbene ligand catalyze the intermolecular anti-Markovnikov hydroarylation of monosubstituted and cis- and trans-disubstituted methylenecyclopropanes (MCPs) with N-alkyl and 1,2-dialkyl indoles to form t ... Full text Cite

Gold carbenes, gold-stabilized carbocations, and cationic intermediates relevant to gold-catalysed enyne cycloaddition.

Journal Article Chemical Society reviews · August 2016 Cationic gold complexes in which gold is bound to a formally divalent carbon atom, typically formulated as gold carbenes or α-metallocarbenium ions, have been widely invoked in a range of gold-catalyzed transformations, most notably in the gold-catalyzed c ... Full text Cite

Kinetics and Mechanism of Allene Racemization Catalyzed by a Gold N-Heterocyclic Carbene Complex

Journal Article Organometallics · July 11, 2016 The kinetics of the racemization of 1,3-disubstituted allenes catalyzed by (IPr)AuOTf (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) has been investigated. The rate of gold-catalyzed allene racemization obeyed the following second-order rate law: ... Full text Cite

Effect of Substitution, Ring Size, and Counterion on the Intermediates Generated in the Gold-Catalyzed Intramolecular Hydroalkoxylation of Allenes

Journal Article Organometallics · June 13, 2016 The reaction of 2,2-diphenylhepta-4,5-dien-1-ol (4) with (L)AuOTs [L = P(t-Bu)2o-biphenyl] and the reactions of 2,2-diphenylhepta-5,6-dien-1-ol (10) with either (L)AuOTs or (L)AuCl/AgSbF6 have been investigated. For both substrates, the mono(gold) vinyl co ... Full text Cite

Mechanism of the Platinum(II)-Catalyzed Hydroamination of 4-Pentenylamines

Journal Article Organometallics · January 25, 2016 The mechanism of the platinum(II)-catalyzed intramolecular hydroamination of benzyl 4-pentenylamines has been evaluated under stoichiometric and catalytic conditions. Reaction of a benzyl 2,2-disubstituted 4-pentenylamine with [(PPh3)Pt(μ-Cl)Cl]2 forms a t ... Full text Cite

Gold-Catalyzed Intermolecular anti-Markovnikov Hydroamination of Methylenecyclopropanes with 2-Pyridones

Journal Article Advanced Synthesis and Catalysis · November 16, 2015 The cationic gold phosphine complex [(o-biphenylPCy2)Au(NCMe)]+ SbF6- catalyzes the intermolecular, anti-Markovnikov hydroamination of methylenecyclopropanes (MCPs) with 2-pyridones at 80 C. The transformation was effective for a range of pyridones and for ... Full text Cite

Synthesis and Characterization of a Gold Vinylidene Complex Lacking π-Conjugated Heteroatoms.

Journal Article Angewandte Chemie (International ed. in English) · June 2015 Hydride abstraction from the gold (disilyl)ethylacetylide complex [(P)Au{η(1) -C≡CSi(Me)2CH2CH2SiMe2H}] (P=P(tBu)2o-biphenyl) with triphenylcarbenium tetrakis(pentafluorophenyl)borate at -20 °C formed the cationic gold (β,β-disilyl)vinylidene complex [(P)A ... Full text Cite

Tandem gold/silver-catalyzed cycloaddition/hydroarylation of 7-aryl-1,6-enynes to form 6,6-diarylbicyclo[3.2.0]heptanes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · April 2015 Mixtures of [{PCy2(o-biphenyl)}AuCl] and AgSbF6 catalyze the tandem cycloaddition/hydroarylation of 7-aryl-1,6-enynes with electron-rich arenes to form 6,6-diarylbicyclo[3.2.0]heptanes in good yield under mild conditions. Experimental observations point to ... Full text Cite

Gold-catalyzed intermolecular anti-markovnikov hydroamination of alkylidenecyclopropanes.

Journal Article Angewandte Chemie (International ed. in English) · February 2015 The cationic gold phosphine complex [{PCy2 (o-biphenyl)}Au(NCMe)](+) SbF6 (-) (Cy=cyclohexyl) catalyzes the intermolecular, anti-Markovnikov hydroamination reaction of monosubstituted and cis- and trans-disubstituted alkylidenecyclopropanes (ACPs) with imi ... Full text Cite

Photomechanical actuation of ligand geometry in enantioselective catalysis.

Journal Article Angewandte Chemie (International ed. in English) · December 2014 A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and select ... Full text Cite

Mechanism of 1,3-hydrogen migration in a gold bicyclo[3.2.0]heptene complex: The role of brønsted acid in the gold-catalyzed cycloisomerization of 7-aryl-1,6-enynes

Journal Article Organometallics · November 24, 2014 The gold 7-phenylbicyclo[3.2.0]hept-1(7)-ene complex 1 is generated as an intermediate in the gold-catalyzed cycloisomerization of 7-phenyl 1,6-enyne 2 to 7-phenylbicyclo[3.2.0]hept-1(7)-ene 3. We have investigated the kinetics of the isomerization of 1 vi ... Full text Cite

Enantioselective intramolecular hydroamination of unactivated alkenes catalyzed by mono- and bis(gold) phosphine complexes

Journal Article Advanced Synthesis and Catalysis · October 1, 2014 A 1:2 mixture of (P1)(AuCl)2[P1=(S)-DTBM-MeO-BIPHEP] and silver tetrafluoroborate (AgBF4) in methanol catalyzes the intramolecular hydroamination of unactivated alkenes with carbamates and ureas to form pyrrolidine derivatives with up to 85% ee. ... Full text Cite

Kinetics and mechanism of the racemization of aryl allenes catalyzed by cationic gold(I) phosphine complexes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · September 2014 The kinetics of the racemization of aromatic 1,3-disubstituted allenes catalyzed by gold phosphine complexes has been investigated. The rate of gold-catalyzed allene racemization displayed first-order dependence on allene, and catalyst concentration and ki ... Full text Cite

Synthesis, structure, and reactivity of a gold carbenoid complex that lacks heteroatom stabilization.

Journal Article Angewandte Chemie (International ed. in English) · August 2014 Hydride abstraction from the neutral gold cycloheptatrienyl complex [(P)Au(η(1)-C7H7)] (P=P(tBu)2(o-biphenyl)) with triphenylcarbenium tetrafluoroborate at -80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [(P)Au(η(1)-C7H6)](+ ... Full text Cite

Synthesis and X-ray crystal structure of a cationic gold (I) π-(1,3-diene) complex generated via isomerization of a gold π-allene complex

Journal Article Journal of Organometallic Chemistry · May 15, 2014 The cationic gold tetramethylallene complex {[P(t-Bu)2o- biphenyl]Au(η2-Me2CCCMe2)}+ SbF6- (1) underwent formal 1,3-hydrogen migration in CD2Cl2 solution at or below room temperature in the absence of base to form the 1,3-diene complex {[P(t-Bu)2o-biphenyl ... Full text Cite

Experimental evaluation of the electron donor ability of a gold phosphine fragment in a gold carbene complex.

Journal Article Chemical communications (Cambridge, England) · March 2014 X-ray analysis of the gold cyclopropyl(methoxy)carbene complex [(P)AuC(OMe)(c-Pr)](+) SbF6(-) [P = P(t-Bu)2o-biphenyl] and comparison to extant protonated cyclopropyl ketones indicates that electron donation from the (P)Au fragment to the electron-deficien ... Full text Cite

Cationic, two-coordinate gold π complexes.

Journal Article Angewandte Chemie (International ed. in English) · November 2013 Cationic, two-coordinate gold π complexes that contain a phosphine or N-heterocyclic supporting ligand have attracted considerable attention recently owing to the potential relevance of these species as intermediates in the gold-catalyzed functionalization ... Full text Cite

Synthesis and study of cationic, two-coordinate triphenylphosphine-gold-π complexes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · June 2013 Cationic, two-coordinate triphenylphosphine-gold(I)-π complexes of the form [(PPh₃)Au(π ligand)]⁺SbF₆⁻ (π ligand=4-methylstyrene, 1∙SbF₆), 2-methyl-2-butene (3∙SbF₆), 3-hexyne (6∙SbF₆), 1,3-cyclohexadiene (7∙SbF₆), 3-methyl-1,2-butadiene (8∙SbF₆), and 1,7- ... Full text Cite

The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · March 2013 A 1:1 mixture of [AuCl(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgClO(4) catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ... Full text Cite

Cationic, two-coordinate gold p-complexes containing an N-heterocyclic carbene ligand

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 19, 2012 Link to item Cite

Mechanistic analysis of gold(I)-catalyzed intramolecular allene hydroalkoxylation reveals an off-cycle bis(gold) vinyl species and reversible C-O bond formation.

Journal Article Journal of the American Chemical Society · June 2012 Mechanistic investigation of gold(I)-catalyzed intramolecular allene hydroalkoxylation established a mechanism involving rapid and reversible C-O bond formation followed by turnover-limiting protodeauration from a mono(gold) vinyl complex. This on-cycle pa ... Full text Cite

Structures and dynamic solution behavior of cationic, two-coordinate gold(I)-π-allene complexes.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · May 2012 A family of seven cationic gold complexes that contain both an alkyl substituted π-allene ligand and an electron-rich, sterically hindered supporting ligand was isolated in >90% yield and characterized by spectroscopy and, in three cases, by X-ray crystall ... Full text Cite

Gold(I)-catalyzed stereoconvergent, intermolecular enantioselective hydroamination of allenes.

Journal Article Angewandte Chemie (International ed. in English) · May 2012 Full text Cite

Gold(I)-catalyzed enantioselective intramolecular dehydrative amination of allylic alcohols with carbamates.

Journal Article Angewandte Chemie (International ed. in English) · February 2012 Full text Cite

Synthesis and structure of dicationic, bis(gold) φ-alkene complexes containing a 2,2-bis(phosphino)biphenyl ligand

Journal Article Organometallics · January 23, 2012 The dicationic bis(gold)-biarylphosphine φ-alkene complexes {(PP)[Au(φ-alkene)]2}2+2SbF6 [PP = 2,2-bis(di-tertbutylphosphino) biphenyl; alkene = isobutylene, 1-pentene] were isolated in >95% yield from reaction of alkene with a 1:2 mixture of (PP)- (AuCl)2 ... Full text Cite

Cationic gold(I) π-complexes of terminal alkynes and their conversion to dinuclear σ,π-acetylide complexes

Journal Article Organometallics · November 14, 2011 Treatment of a suspension of (IPr)AuCl [IPr = 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene] and AgSbF6 with terminal arylacetylenes led to the formation of thermally unstable gold π-alkyne complexes of the form [(IPr)Au(η 2-HC≡ CAr)]+SbF 6- in ≥86 ± 5 ... Full text Cite

Platinum(II)-catalyzed intermolecular hydroamination of allenes

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2011 Link to item Cite

Dinuclear gold(I) s,P -acetylide complex formation via gold(I) P -alkyne complexes: Kinetics and mechanism

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2011 Link to item Cite

Gold(I)-catalyzed enantioselective intermolecular hydroamination of unactivated 1-alkenes with cyclic ureas

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2011 Link to item Cite

Stereochemistry and mechanism of the Brønsted acid catalyzed intramolecular hydrofunctionalization of an unactivated cyclic alkene.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · May 2011 Through employment of deuterium-labeled substrates, the triflic acid catalyzed intramolecular exo addition of the X-H(D) (X=N, O) bond of a sulfonamide, alcohol, or carboxylic acid across the C=C bond of a pendant cyclohexene moiety was found to occur, in ... Full text Cite

Gold(I)-Catalyzed Intramolecular Hydroamination of N-Allylic,N'-Aryl Ureas to form Imidazolidin-2-ones.

Journal Article Advanced synthesis & catalysis · April 2011 Treatment of N-allylic,N'-aryl ureas with a catalytic 1:1 mixture of di-tert-butyl-o-biphenylphoshphine gold(I) chloride and silver hexafluorophosphate (1 mol %) in chloroform at room temperature led to 5-exo hydroamination to form the corresponding imidaz ... Full text Cite

Synthesis and equilibrium binding studies of cationic, two-coordinate gold(I) π-alkyne complexes.

Journal Article Journal of organometallic chemistry · March 2011 Reaction of a 1:1 mixture of (L)AuCl [L = P(t-Bu)2o-biphenyl or IPr] and AgSbF6 with internal alkynes led to isolation of the corresponding cationic, two-coordinate gold π-alkyne complexes in ≥ 90% yield. Equilibrium bin ... Full text Cite

Gold(I)-catalyzed intramolecular amination of allylic alcohols with alkylamines.

Journal Article Organic letters · March 2011 A 1:1 mixture of (1)AuCl [1 = P(t-Bu)(2)o-biphenyl] and AgSbF(6) catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino ... Full text Cite

Syntheses, x-ray crystal structures, and solution behavior of cationic, two-coordinate gold(I) η2-diene complexes

Journal Article Organometallics · 2011 A family of cationic gold p-diene complexes of the form {[P(t-Bu) 2o-biphenyl]Au(η2-diene)}+SbF6- were isolated in >80% yield from reaction of various dienes with a mixture of [P(t-Bu)2o-biphenyl]AuCl and AgSbF6 and were characterized by spectroscopy an ... Full text Cite

Solid-state and dynamic solution behavior of a cationic, two-coordinate gold(I) π-allene complex

Journal Article Organometallics · October 11, 2010 The cationic gold π-allene complex {[P(t-Bu)2o-biphenyl] Au[η2-H2C=C=C(CH3)2]} +SbF6- was isolated in 98% yield from reaction of 3-methyl-1,2-butadiene with a mixture of [P(t-Bu)2o-biphenyl]AuCl and AgSbF6 and was characterized by X-ray crystallography and ... Full text Open Access Cite

Intramolecular Diamination and Alkoxyamination of Alkenes with N-Sulfonyl Ureas With N-Iodosuccinimide.

Journal Article Tetrahedron · June 2010 Reaction of N-δ-alkenyl-N'-sulfonyl urea 1 with N-iodosuccinimde (NIS; 2 equiv) and a catalytic amount of AgOTf (20 mol %) at room temperature led to intramolecular alkoxyamination to form bicyclic isourea 2a in 95% isolated yield. In comparison, reaction ... Full text Cite

Mechanistic studies and scrope of gold(I)-catalyzed intermolecular hydroamination of allenes with arylamines

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · March 21, 2010 Link to item Cite

Platinum(II)-catalyzed intermolecular hydroamination of monosubstituted allenes with secondary alkylamines.

Journal Article Chemical communications (Cambridge, England) · March 2010 A 1:1 mixture of (dppf)PtCl(2) and AgOTf (5 mol%) catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines at 80 degrees C to form allylic amines in good yield with selective formation of the E-diastereomer. ... Full text Open Access Cite

Gold(I)-catalyzed amination of allylic alcohols with cyclic ureas and related nucleophiles.

Journal Article Organic letters · March 2010 A 1:1 mixture of [P(t-Bu)(2)-o-biphenyl]AuCl and AgSbF(6) catalyzes the intermolecular amination of allylic alcohols with 1-methylimidazolidin-2-one and related nucleophiles that, in the case of gamma-unsubstituted or gamma-methyl-substituted allylic alcoh ... Full text Open Access Cite

Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes with Arylamines.

Journal Article Synlett : accounts and rapid communications in synthetic organic chemistry · February 2010 A mixture of (3)AuCl [3 = P(t-Bu)(2)o-biphenyl] and AgOTf catalyzes the intermolecular hydroamination of monosubstituted and 1,1- and 1,3-disubstituted allenes with primary and secondary arylamines. ... Full text Cite

Gold(I)-catalyzed intermolecular amination of allylic alcohols with cyclic ureas and related nucleophiles

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · 2010 Cite

Syntheses and X-ray crystal structures of cationic, two-coordinate gold(I) pi-alkene complexes that contain a sterically hindered o-biphenylphosphine ligand.

Journal Article Chemical communications (Cambridge, England) · November 2009 A number of cationic gold pi-alkene complexes of the form {[P(t-Bu)(2)o-biphenyl]Au(pi-alkene)}(+)SbF(6)(-) were isolated and three were analyzed by X-ray crystallography. ... Full text Cite

Unactivated Alkenes

Journal Article · September 16, 2009 Since 2000, a number of transition metal-catalyzed methods for the enantioselective alkylation of arenes with unactivated (non-Michael acceptor) C=C bonds have been reported. Early examples include the enantioselective ortho-alkylation of benzamide with no ... Full text Cite

Gold(I)-catalyzed intramolecular dihydroamination of allenes with N,N'-disubstituted ureas to form bicyclic imidazolidin-2-ones.

Journal Article Organic letters · June 2009 Reaction of N-delta-allenyl urea 1 with a catalytic 1:1 mixture of gold(I) N-heterocyclic carbene complex (5)AuCl [5 = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine] and AgPF(6) at room temperature for 2 h led to isolation of bicyclic imidazolidin-2-one ... Full text Cite

Syntheses, X-ray crystal structures, and solution behavior of monomeric, cationic, two-coordinate gold(I) pi-alkene complexes.

Journal Article Journal of the American Chemical Society · May 2009 Treatment of a suspension of (IPr)AuCl [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine] and AgSbF(6) (1:1) with isobutylene at room temperature for 12 h led to isolation of [(NHC)Au(eta(2)-H(2)C=CMe(2))](+) SbF(6)(-) (1a) in 98% yield, which was ch ... Full text Cite

Gold(I)-Catalyzed Hydration of Allenes.

Journal Article Tetrahedron · February 2009 A gold(I) N-heterocyclic carbene complex catalyzes the intermolecular hydration of allenes to form allylic alcohols in modest yield with selective delivery of water to the terminal carbon atoms of the allenyl moiety. ... Full text Cite

Gold(I)-Catalyzed Hydroarylation of Allenes with Indoles.

Journal Article Journal of organometallic chemistry · February 2009 Reaction of a monosubstituted, 1,3-disubstituted, or tetrasubstituted allene with various indoles catalyzed by a 1:1 mixture of a gold(I) N-heterocyclic carbene complex and AgOTf at room temperature leads to hydroarylation with formation of 3-allyl-indoles ... Full text Cite

A palladium-catalyzed formal (4+1) annulation: a new approach to cyclopentene construction.

Journal Article Angewandte Chemie (International ed. in English) · January 2009 Full text Cite

ORGN 42-Gold(I)-catalyzed dynamic kinetic enantioselective hydroamination

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 17, 2008 Link to item Cite

ORGN 589-Gold(I)-catalyzed intermolecular hydroalkoxylation of allenes

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 17, 2008 Link to item Cite

Intermolecular hydroamination of allenes with N-unsubstituted carbamates catalyzed by a gold(I) N-heterocyclic carbene complex.

Journal Article Organic letters · July 2008 Reaction of 2,3-pentadienyl benzoate with benzyl carbamate catalyzed by a 1:1 mixture of (NHC)AuCl and AgOTf in dioxane at 23 degrees C for 5 h led to isolation of (E)-4-(benzyloxycarbonylamino)-2-pentenyl benzoate in 84% yield as a single regio- and diast ... Full text Cite

Gold(I)-catalyzed intramolecular hydroamination of unactivated C==C bonds with alkyl ammonium salts.

Journal Article Chemical communications (Cambridge, England) · June 2008 A mixture of (5)AuCl [ = PCy2[2-(2,6-C6H3(OMe)2)C6H4]] and AgOTf catalyzes the intramolecular hydroamination of unactivated C==C bonds with primary and secondary ammonium salts. ... Full text Cite

Sterically hindered mono(phosphines) as supporting ligands for the platinum-catalyzed hydroamination of amino alkenes

Journal Article Organometallics · May 26, 2008 In an effort to develop more active catalysts for the intramolecular hydroamination of amino alkenes, we have investigated the application of sterically hindered mono(phosphines) as supporting ligands for platinum-catalyzed hydroamination. Here we demonstr ... Full text Cite

Regio- and stereoselective synthesis of alkyl allylic ethers via gold(I)-catalyzed intermolecular hydroalkoxylation of allenes with alcohols.

Journal Article Organic letters · May 2008 Reaction of 1-phenyl-1,2-butadiene with 2-phenyl-1-ethanol catalyzed by a 1:1 mixture of a gold(I) N-heterocyclic carbene complex and AgOTf at room temperature for 1 h led to isolation of (E)-(3-phenethoxy-1-butenyl)benzene in 96% yield as a single regio- ... Full text Cite

PRES 11-Platinum catalyzed intramolecular hydroamination of unactivated olefines with secondary alkylamines

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · April 6, 2008 Link to item Cite

Recent developments in enantioselective gold(I) catalysis.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · January 2008 The use of gold(I) complexes as catalysts for organic transformations has become increasingly common over the past decade, leading to the development of a number of useful carbon-carbon and carbon-heteroatom bond-forming processes. In contrast, enantiosele ... Full text Cite

Gold(I)-catalyzed dynamic kinetic enantioselective intramolecular hydroamination of allenes.

Journal Article Journal of the American Chemical Society · November 2007 Full text Cite

Platinum-catalyzed hydrofunctionalization of unactivated alkenes with carbon, nitrogen and oxygen nucleophiles.

Journal Article Chemical communications (Cambridge, England) · September 2007 The transition metal-catalyzed addition of the X-H bond of a carbon, nitrogen or oxygen nucleophile across the C[double bond]C bond of an unactivated alkene (hydrofunctionalization) represents an attractive, atom-economical approach to the synthesis of car ... Full text Cite

INOR 555-Gold-catalyzed enantioselective cyclization of allenyl alcohols

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 19, 2007 Link to item Cite

Palladium-mediated cyclization of 6-methyl-1-phenyl-6-hepten-2-one to form 3-methyldiphenylmethane: Carbonyl activation by a neutral palladium(II) complex

Journal Article Organometallics · July 30, 2007 Reaction of 6-methyl-1-phenyl-6-hepten-2-one (4) with a stoichiometric mixture of PdCl 2(CH 3CN) 2 (2) and Me 3SiCl in dioxane at 70 °C formed 3-methyldiphenylmethane (6) in 78% isolated yield. A number of experiments supported a mechanism for the conversi ... Full text Cite

Gold(I)-catalyzed enantioselective hydroamination of N-allenyl carbamates.

Journal Article Organic letters · July 2007 Treatment of the N-4,5-hexadienyl carbamate 2a with a catalytic 1:2 mixture of [(S)-1]Au2Cl2 [(S)-1 = (S)-3,5-t-Bu-4-MeO-MeOBIPHEP] and AgClO4 in m-xylene at -40 degrees C for 24 h led to isolation of 2-vinylpyrrolidine 3a in 97% yield with 81% ee. Gold(I) ... Full text Cite

Gold(I)-catalyzed intramolecular enantioselective hydroarylation of allenes with indoles.

Journal Article Organic letters · May 2007 Treatment of 2-allenyl indole 4 with a catalytic 1:2 mixture of [(S)-2]Au2Cl2 [(S)-2 = (S)-3,5-tBu-4-MeO-MeOBIPHEP] and AgBF4 in toluene at -10 degrees C for 17 h led to isolation of tetrahydrocarbazole 5 in 88% yield with 92% ee. The protocol was effectiv ... Full text Cite

Gold(I)-catalyzed intramolecular enantioselective hydroalkoxylation of allenes.

Journal Article Angewandte Chemie (International ed. in English) · January 2007 Full text Cite

Room temperature hydroamination of N-alkenyl ureas catalyzed by a gold(i) N-heterocyclic carbene complex.

Journal Article Organic letters · November 2006 [Structure: see text] Treatment of an N-4-pentenyl or N-5-hexenyl urea with a catalytic 1:1 mixture of a gold(I) N,N-diaryl imidazol-2-ylidine complex and AgOTf at or near room temperature leads to intramolecular exo-hydroamination to form the correspondin ... Full text Cite

Gold-catalyzed hydroamination of C-C multiple bonds

Journal Article European Journal of Organic Chemistry · October 13, 2006 The development of general and efficient methods for the addition of an N-H bond across a C-C multiple bond (hydroamination) represents a significant challenge in both organic synthesis and homogeneous catalysis. Although a diverse range of transition-meta ... Full text Cite

Gold(I)-catalyzed intramolecular hydroamination of unactivated alkenes with carboxamides.

Journal Article Chemical communications (Cambridge, England) · October 2006 N-Alkenyl carboxamides undergo gold-catalyzed intramolecular exo-hydroamination to form nitrogen heterocycles in excellent yield. ... Full text Cite

ORGN 188-Au(I)-catalyzed intramolecular hydroamination of unactivated olefins with carboxamides

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 10, 2006 Link to item Cite

ORGN 187-Au(I)-catalyzed cyclizations of allenyl alcohols

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 10, 2006 Link to item Cite

INOR 437-Mechanism for the intramolecular hydroamination of unactivated olefins with secondary alkylamines

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 10, 2006 Link to item Cite

ORGN 922-Au(I)-Catalyzed intramolecular hydroamination of allenyl carbamates

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 10, 2006 Link to item Cite

Platinum(II)-catalyzed intermolecular hydroarylation of unactivated alkenes with indoles.

Journal Article Chemical communications (Cambridge, England) · September 2006 Ethylene, alpha-olefins, and vinyl arenes undergo platinum-catalyzed hydroarylation with substituted indoles in moderate to good yield. ... Full text Cite

Platinum-catalyzed intramolecular asymmetric hydroarylation of unactivated alkenes with indoles.

Journal Article Organic letters · August 2006 [reaction: see text] A 1:1 mixture of the platinum bis(phosphine) complex [(S)-4]PtCl2 [(S)-4 = (S)-3,5-t-Bu-4-MeO-MeOBIPHEP] catalyzes the intramolecular asymmetric hydroarylation of 2-(4-pentenyl)indoles in moderate to good yield with up to 90% ee. ... Full text Cite

Highly active Au(I) catalyst for the intramolecular exo-hydrofunctionalization of allenes with carbon, nitrogen, and oxygen nucleophiles.

Journal Article Journal of the American Chemical Society · July 2006 Reaction of benzyl (2,2-diphenyl-4,5-hexadienyl)carbamate (4) with a catalytic 1:1 mixture of Au[P(t-Bu)2(o-biphenyl)]Cl (2) and AgOTf (5 mol %) in dioxane at 25 degrees C for 45 min led to isolation of benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate ... Full text Cite

Rhodium-catalyzed asymmetric cyclization/hydroboration of 1,6-enynes.

Journal Article Organic letters · May 2006 [reaction: see text] Reaction of enyne 1 with catecholborane catalyzed by a 1:1 mixture of [Rh(COD)(2)](+)SbF(6)(-) and (S)-BINAP (5 mol %) followed by Pd-catalyzed arylation with p-IC(6)H(4)CF(3) gave benzylidenecyclopentane 5 in 65% yield with 88% ee. Rh ... Full text Cite

Rhodium-catalyzed asymmetric borylative cyclization of 1,6-enynes

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · March 26, 2006 Link to item Cite

Scope and mechanism of the Pd(II)-catalyzed arylation/carboalkoxylation of unactivated olefins with indoles.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · March 2006 Treatment of 1-methyl-2-(4-pentenyl)indole (5) with a catalytic amount of [PdCl2(MeCN)2] (2; 5 mol %) and a stoichiometric amount of CuCl2 (3 equiv) in methanol under CO (1 atm) at room temperature for 30 min gives methyl (9-methyl-2,3,4,9-tetrahydro-4-car ... Full text Cite

Gold(I)-catalyzed intramolecular hydroamination of alkenyl carbamates.

Journal Article Angewandte Chemie (International ed. in English) · March 2006 Full text Cite

Scope and mechanism of Pd-catalyzed arylation/carboalkoxylation of unactivated olefins with indoles and pyrrols

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2005 Link to item Cite

Intramolecular hydroamination of unactivated olefins with secondary alkylamines

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2005 Link to item Cite

Platinum-catalyzed intermolecular hydroamination of vinyl arenes with carboxamides

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 28, 2005 Link to item Cite

Platinum-catalyzed intermolecular hydroamination of vinyl arenes with carboxamides.

Journal Article Organic letters · June 2005 [reaction: see text] Reaction of benzamide with 4-methylstyrene catalyzed by a 1:2 mixture of [PtCl(2)(H(2)C=CH(2))](2) and P(4-C(6)H(4)CF(3))(3) (5 mol %) in mesitylene at 140 degrees C for 24 h led to the isolation of N-(1-p-tolylethyl)benzamide in 85% y ... Full text Cite

Asymmetric intramolecular alkylation of indoles with unactivated olefins.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · March 13, 2005 Link to item Cite

Platinum-catalyzed intramolecular hydroamination of unactivated olefins with secondary alkylamines.

Journal Article Journal of the American Chemical Society · February 2005 Reaction of benzyl-2,2-diphenyl-4-pentenylamine with a catalytic 1:2 mixture of [PtCl2(H2C=CH2)]2 (2.5 mol %) and PPh3 in dioxane at 120 degrees C for 16 h led to isolation of 1-benzyl-2-methyl-4,4-diphenylpyrrolidine in 75% yield. A number of gamma- and d ... Full text Cite

Development, scope, and mechanism of the palladium-catalyzed intramolecular hydroalkylation of 3-butenyl β-diketones

Journal Article Organometallics · January 17, 2005 Reaction of 7-octene-2,4-dione (3) with a catalytic amount of PdCl 2(CH 3CN) 2 (4) (10 mol %) in dioxane at room temperature for 16 h formed 2-acetylcyclohexanone (5) in 81% yield as a single regioisomer. Byproducts in the conversion of 3 to 5 include 2,4- ... Full text Cite

Platinum(II)/europium(III)-catalyzed intramolecular hydroalkylation of 4-pentenyl β-dicarbonyl compounds

Journal Article Tetrahedron Letters · January 10, 2005 A mixture of [PtCl 2(CH 2CH 2)] 2 (1 mol %), and EuCl 3 (2 mol %) catalyzes the hydroalkylation of 4-pentenyl β-dicarbonyl compounds to form substituted cyclohexanones in moderate to excellent yield with excellent regioselectivity. Reaction of 5,5-dimethyl ... Full text Cite

Palladium-catalyzed intramolecular oxidative alkylation of 4-pentenyl beta-dicarbonyl compounds.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · December 2004 Reaction of 8-nonene-2,4-dione with a catalytic amount of [PdCl2(CH3CN)2] (2; 5 mol %) and a stoichiometric amount of CuCl2 (2.5 equiv) at room temperature for 3 h led to oxidative alkylation and formation of 2-acetyl-3-methyl-2-cyclohexenone in 80 % isola ... Full text Cite

Palladium-catalyzed intramolecular hydroalkylation of alkenyl-beta-keto esters, alpha-aryl ketones, and alkyl ketones in the presence of Me3SiCl or HCl.

Journal Article Chemistry (Weinheim an der Bergstrasse, Germany) · December 2004 Reaction of 3-butenyl beta-keto esters or 3-butenyl alpha-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/CuCl2 in dioxane at 25-70 degrees C formed 2-substituted cyclohexanones in good yield wi ... Full text Cite

Platinum-catalyzed intramolecular alkylation of indoles with unactivated olefins.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 22, 2004 Link to item Cite

Platinum-catalyzed intramolecular hydroalkoxylation of gamma- and delta-hydroxy olefins to form cyclic ethers.

Journal Article Journal of the American Chemical Society · August 2004 Reaction of 2,2-diphenyl-4-penten-1-ol with a catalytic mixture of [PtCl2(H2C=CH2)]2 (1 mol %) and P(4-C6H4CF3)3 (2 mol %) at 70 degrees C for 24 h led to the isolation of 2-methyl-4,4-diphenyltetrahydrofuran in 78% yield. The platinum-catalyzed hydroalkox ... Full text Cite

Palladium-catalyzed cyclization/carboalkoxylation of alkenyl indoles.

Journal Article Journal of the American Chemical Society · August 2004 Reaction of 1-methyl-2-(4-pentenyl)indole with a catalytic amount of PdCl2(CH3CN)2 (5 mol %) and a stoichiometric amount of CuCl2 (3 equiv) in methanol under CO (1 atm) at room temperature for 30 min led to cyclization/carboalkoxylation to form the corresp ... Full text Cite

Mechanism of palladium-catalyzed diene cyclization/hydrosilylation: direct observation of intramolecular carbometalation.

Journal Article Journal of the American Chemical Society · May 2004 The results of kinetic, deuterium-labeling, and low-temperature NMR studies have established a mechanism for the palladium-catalyzed cyclization/hydrosilylation of dimethyl diallylmalonate (1) with triethylsilane involving rapid, irreversible conversion of ... Full text Cite

Platinum-Catalyzed Intermolecular Hydroamination of Unactivated Olefins with Carboxamides

Journal Article Organometallics · April 12, 2004 Reaction of benzamide with a catalytic 1:2 mixture of[PtCl 2(H 2C=CH 2)] 2 (2.5 mol%) and PPh 3 in dioxane at 120°C for 24 h led to isolation of N-ethylbenzamide in 97% yield. A range of primary, acyclic aryl and alkyl carboxamides and secondary cyclic car ... Full text Cite

Palladium(II)- and platinum(II)-catalyzed addition of stabilized carbon nucleophiles to ethylene and propylene.

Journal Article Chemical communications (Cambridge, England) · March 2004 PdCl(2)(CH(3)CN)(2) and [PtCl(2)(H(2)C[double bond]CH(2))](2) catalyze the addition of beta-dicarbonyl compounds to ethylene and propylene. ... Full text Cite

Palladium-catalyzed oxidative alkoxylation of alpha-alkenyl beta-diketones to form functionalized furans.

Journal Article The Journal of organic chemistry · March 2004 Treatment of 4-allyl-2,6-dimethyl-3,5-heptanedione with a catalytic amount of PdCl(2)(CH(3)CN)(2) (5 mol %) and a stoichiometric amount of CuCl(2) (2.2 equiv) in dioxane at 60 degrees C for 12 h formed 3-isobutyryl-2-isopropyl-5-methylfuran in 77% isolated ... Full text Cite

Platinum-catalyzed intramolecular alkylation of indoles with unactivated olefins.

Journal Article Journal of the American Chemical Society · March 2004 Reaction of 1-methy-2-(4-pentenyl)indole (1) with a catalytic amount of PtCl2 (2 mol %) in dioxane that contained a trace of HCl (5 mol %) at 60 degrees C for 24 h led to the isolation of 4,9-dimethyl-2,3,4,9-tetrahydro-1H-carbazole (2) in 92% yield. Plati ... Full text Cite

Palladium-catalyzed alkylation of unactivated olefins

Journal Article Pure and Applied Chemistry · January 1, 2004 Reaction of a 3-butenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experi ... Full text Cite

Effect of terminal substitution on the intramolecular carbometallation of 5-hexenyl palladium chelate complexes.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 1, 2003 Link to item Cite

Palladium-catalyzed intramolecular hydroalkylation of unactivated olefins with dialkyl ketones.

Journal Article Organic letters · July 2003 [reaction: see text] Treatment of 3-butenyl heptyl ketone with substoichiometric amounts of PdCl(2)(CH(3)CN)(2) (10 mol %), HCl (0.1 equiv), and CuCl(2) (0.3 equiv) in dioxane at 70 degrees C for 12 h in a sealed tube formed 2-hexylcyclohexanone in 77% iso ... Full text Cite

Mechanism of the palladium-catalyzed intramolecular hydroalkylation of 7-octene-2,4-dione.

Journal Article Journal of the American Chemical Society · February 2003 Cyclization of (E)-7,8-dideuterio-7-octene-2,4-dione [(E)-1-7,8-d(2)] catalyzed by PdCl(2)(CH(3)CN)(2) (2) formed cis-2-acyl-3,4-dideuteriocyclohexanone (cis-3-3,4-d(2)) in 64% yield as the exclusive isotopomer. This experiment, in conjunction with additio ... Full text Cite

Palladium-catalyzed intramolecular oxidative alkylation of unactivated olefins.

Journal Article Journal of the American Chemical Society · January 2003 Reaction of 5,5-dimethyl-8-nonene-2,4-dione catalyzed by PdCl2(CH3CN)2 (5 mol %) in the presence of CuCl2 (2.5 equiv) at room temperature for 3 h formed 2-acetyl-3,6,6-trimethyl-2-cyclohexenone in 96% isolated yield. Palladium-catalyzed intramolecular oxid ... Full text Cite

Enantioselective cyclization/hydrosilylation of 1,6-enynes catalyzed by a cationic rhodium bis(phosphine) complex.

Journal Article Organic letters · January 2003 [reaction: see text] Reaction of 4,4-dicarbomethoxy-1-octene-6-yne (1) with triethylsilane and a catalytic 1:1 mixture of [Rh(COD)(2)](+) SbF(6)(-) and (R)-BIPHEMP (5 mol %) at 70 degrees C for 90 min gave (Z)-1,1-dicarbomethoxy-3-(1-triethylsilyl)ethylide ... Full text Cite

Cyclization/hydrosilylation of functionalized diynes catalyzed by a cationic rhodium bis(phosphine) complex

Journal Article Organometallics · December 9, 2002 The catalysis of cyclization/hydrosilylation of 5,5-dicarbomethoxy-2,7-nonadiyne and triethylsilane by the cationic rhodium complex [Rh(BINAP)(COD)]+BF4- [BINAP = (±)-2,2′-bis-(diphenylphosphino)binaphthyl] was presented. The (E,Z)-1,1-dicarbomethoxy-3-eth ... Full text Cite

Synthetic and mechanistic studies of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes.

Journal Article Accounts of chemical research · October 2002 This Account describes the development and mechanistic study of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes. These transformations are characterized by good functional group ... Full text Cite

Palladium-catalyzed addition of stabilized carbon nucleophiles to unactivated olefins.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 18, 2002 Link to item Cite

Rh-catalyzed cyclization/hydrosilylation of functionalized enynes.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 18, 2002 Link to item Cite

Cyclization/hydrosilylation of functionalized 1,6-diynes catalyzed by cationic platinum complexes containing bidentate nitrogen ligands.

Journal Article The Journal of organic chemistry · May 2002 A 1:1 mixture of the platinum dimethyl diimine complex [PhN[double bond]C(Me)C(Me)[double bond]NPh]PtMe(2) (4a) and B(C(6)F(5))(3) catalyzed the cyclization/hydrosilylation of dimethyl dipropargylmalonate (1) and HSiEt(3) to form 1,1-dicarbomethoxy-3-methy ... Full text Cite

Palladium-catalyzed intramolecular addition of 1,3-diones to unactivated olefins.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · April 7, 2002 Link to item Cite

Palladium-catalyzed ring-opening cyclization/hydrosilylation of 1-cyclopropyl-1,6-heptadienes to form (E)-1-butenyl cyclopentanes

Journal Article Organometallics · March 4, 2002 The catalysis of a reaction of 4,4-dicarbomethoxy-1-cyclopropyl-1,6-heptadiene and HSiMe2OSiPh2t-Bu by a 1:1 mixture of (phen)Pd(Me)Cl (phen = 1, 10-phenanthroline) and NaBAr4 [Ar = 3, 5-C6H3(CF3)2] in Ch2Cl2 at 0° C for 12 h was presented. The (E)-trans-3 ... Full text Cite

Palladium-catalyzed cyclization of alkenyl beta-keto esters in the presence of chlorotrimethylsilane.

Journal Article Chemical communications (Cambridge, England) · March 2002 PdCl2(CH3CN)2 catalyzed the cyclization of alkenyl beta-keto esters in the presence of a stoichiometric amount of SiMe3Cl to form 2-carboalkoxycyclohexanones in good yield with excellent regioselectivity. ... Full text Cite

Direct observation of the conversion of a palladium 5-hexenyl chelate complex to a palladium cyclopentylmethyl complex

Journal Article Organometallics · December 10, 2001 Warming a solution of {(phen)Pd[η1:η2-CH(CH2SiEt3) CH2C(CO2Me)2CH2CH= CH2]}+[BAr4]- (4) at -41 °C led to first-order decay (κ = (4.7 ± 0.3) × 10-4 M s-1, ΔG‡ = 17.1 ± 0.1 kcal mol-1) with formation of the palladium cyclopentylmethyl complex {(phen)Pd-[CH2 ... Full text Cite

Mechanistic studies of the cycloisomerization of dimethyl diallylmalonate catalyzed by a cationic palladium phenanthroline complex.

Journal Article Journal of the American Chemical Society · November 2001 The mechanism of the cycloisomerization of dimethyl diallylmalonate (1) catalyzed by the cationic palladium phenanthroline complex [(phen)Pd(Me)CNCH(3)](+)[BAr(4)](-) [Ar = 3,5-C(6)H(3)(CF(3))(2)] (2) has been investigated. Heating a solution of 1 and 2 (5 ... Full text Cite

Palladium-catalyzed asymmetric diene cyclization/hydrosilylation employing functionalized silanes and disiloxanes.

Journal Article The Journal of organic chemistry · November 2001 Pentasubstituted disiloxanes and silanes of the form HSiMe(2)CH(x)Ph(3-x)(x = 1 or 2) reacted with dimethyl diallylmalonate (1) and other functionalized 1,6-dienes in the presence of a catalytic 1:1 mixture of (N-N)Pd(Me)Cl [N-N = (R)-(+)-4-isopropyl-2-(2- ... Full text Cite

Palladium-catalyzed intramolecular addition of 1,3-diones to unactivated olefins.

Journal Article Journal of the American Chemical Society · November 2001 Full text Cite

Platinum-catalyzed cyclization/hydrosilylation of functionalized diynes.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 1, 2001 Link to item Cite

Direct observation of the intramolecular carbometallation of a palladium alkyl-olefin chelate complex.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 1, 2001 Link to item Cite

Synthesis of carbobicyclic compounds via palladium-catalyzed cyclization/hydrosilylation: evidence for reversible silylpalladation.

Journal Article The Journal of organic chemistry · March 2001 Cyclization/hydrosilylation of substituted 1-vinyl-1-(3-butenyl)cycloalkanes catalyzed by a 1:1 mixture of (phen)Pd(Me)Cl (1) and NaBAr(4) [phen = 1,10-phenanthroline; Ar = 3,5-C(6)H(3)(CF(3))(2)] formed silylated spirocycles in high yield with excellent r ... Full text Cite

Cyclization/hydrosilylation of functionalized diynes catalyzed by a cationic platinum phenanthroline complex.

Journal Article Organic letters · February 2001 [figure: see text] A 1:1 mixture of the platinum phenanthroline complex (phen)PtMe2 and B(C6F5)3 catalyzed the cyclization/hydrosilylation of functionalized 1,6- and 1,7-diynes to form silylated 1,2-dialkylidenecycloalkanes in good yield and with high Z-se ... Full text Cite

Development, synthetic scope, and mechanistic studies of the palladium-catalyzed cycloisomerization of functionalized 1,6-dienes in the presence of silane

Journal Article Journal of the American Chemical Society · October 18, 2000 A 1:1 mixture of the π-allyl palladium complex (η3-C3H5)Pd(CI)PCy3 (1a) and NaB[3,5-C6H3-(CF3)2]4 in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy-1,2-dimethylcyclopentane (3b) in 98% yie ... Full text Cite

Asymmetric diene cyclization/hydrosilylation/oxidation employing 1-tert-butyl-3,3-dimethyl-1,1-diphenyldisiloxane

Journal Article Tetrahedron Letters · September 30, 2000 A 1:1 mixture of (N-N)Pd(Me)Cl [N-N=(R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline] (1) and NaBAr4 [Ar=3,5-C6H3(CF3)2] catalyzed the asymmetric cyclization/hydrosilylation of functionalized 1,6-dienes with 1-tert-butyl-3,3-dimethyl-1,1-diphenyldisiloxane ... Full text Cite

Enantioselective diene Cyclization/Hydrosilylation catalyzed by optically active palladium bisoxazoline and pyridine-oxazoline complexes.

Journal Article The Journal of organic chemistry · June 2000 A 1:1 mixture of (N-N)Pd(Me)Cl ¿N-N = (S,S)-4,4'-dibenzyl-4,5,4', 5'-tetrahydro-2,2'-bisoxazoline (S,S-4a) and NaBAr(4) ¿Ar = 3, 5-C(6)H(3)(CF(3))(2) (5 mol %) catalyzed the asymmetric cyclization/hydrosilylation of dimethyl diallylmalonate (2) and triethy ... Full text Cite

Use of pentamethyldisiloxane in the palladium-catalyzed cyclization/hydrosilylation of functionalized dienes.

Journal Article Organic letters · May 2000 [reaction--see text] Pentamethyldisiloxane reacts with a range of functionalized dienes in the presence of a catalytic 1:1 mixture of (N-N)Pd(Me)Cl [N-N = 1, 10-phenanthroline or (R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline] and NaBAr(4) [Ar = 3,5-C(6)H ... Full text Cite

An improved catalyst for the cyclization/hydrosilylation of functionalized 1,6-dienes employing dimethylphenylsilane

Journal Article Tetrahedron Letters · December 3, 1999 A 1:1 mixture of (Me4-phen)Pd(Me)Cl [Me4-phen=3,4,7,8-tetramethyl-1,10-phenanthroline] and NaBAr4 [Ar=3,5-C6H3(CF3)2] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes with dimethylphenylsilane within minutes at room temperature to for ... Full text Cite

Cyclization/hydrosilylation of functionalized dienes catalyzed by a cationic palladium phenanthroline complex

Journal Article Journal of Organic Chemistry · November 12, 1999 Mixtures of (phen)PdMe2 (2a) and HBAr'4 (3a) or (phen)PdMe(Cl) (2b) and NaBAr'4 (3b) [phen = 1,10-phenanthroline; Ar' = 3,5-C6H3(CF3)2] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and ... Full text Cite

Cyclization/Hydrogermylation of Functionalized 1,6-Dienes Catalyzed by Cationic Palladium Complexes

Journal Article Organometallics · October 25, 1999 A 1:1 mixture of the palladium phenanthroline complex (phen)Pd(Me)Cl and NaBAr4 (phen = 1,10-phenanthroline; Ar = 3,5-C6H3(CF3)2) catalyzed the reaction of 4,4-disubstituted 1,6-dienes with trialkylgermanes at 80°C in 1,2-dichloroethane (DCE) to form R3GeC ... Full text Cite

Silane-promoted cycloisomerization of functionalized 1,6-dienes catalyzed by a cationic (π-allyl)palladium complex

Journal Article Organic Letters · October 7, 1999 (matrix presented) A 1:1 mixture of the (π-allyl)palladium complex (η3-C3H5)Pd(Cl)PCy3 and NaB[3,5-C6H3(CF3)2]4 in the presence of HSiEt3 catalyzed the cycloisomerization of functionalized 1,6-dienes to form 1,2-disubstituted cyclopentenes in good yield wi ... Full text Cite

Cyclization/hydrosilylation of functionalized 1,7-dienes to form substituted six-membered carbocycles

Journal Article Tetrahedron Letters · February 19, 1999 The cationic palladium complex (phen)Pd(Me)(OEt2)+ BAr4/- [phen = 1,10-phenanthroline; Ar = 3,5-C6H3(CF3)2] catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexanes in good yield and with moderate to good trans- ... Full text Cite

Palladium-catalyzed cyclization of 4-pentenylsilanes to form six-membered silicon heterocycles.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 23, 1998 Link to item Cite

Tandem cyclization/hydrosilylation of functionalized 1,6-dienes catalyzed by a cationic palladium complex.

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 23, 1998 Link to item Cite

Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes

Journal Article Journal of the American Chemical Society · July 8, 1998 Thermal decomposition of the palladium (aryl)neopentoxide complexes [P-P]Pd(Ar)OCH2CMe3 [P-P =Tol-BINAP or BINAP; Ar p-C6H4CHO (1b), p-C6H4COPh (1c), p-C6H4NO2 (1d), o-C6H4NO2 (1e), o-C6H4CN (1F)] possessing substituents on the palladium-bound aryl group s ... Full text Cite

Palladium-catalyzed intramolecular hydrosilylation of alkenylsilanes: Selective formation of six-membered silicon heterocycles

Journal Article Organometallics · January 1, 1998 The cationic palladium complex (phen)Pd(Me)(OEt2)+BAr4- [phen = 1,10-phenanthroline; Ar = 3,5-C6Hs(CF3)2] catalyzed the intramolecular hydrosilylation of 4-pentenylsilanes and 5-hexenylsilanes to form silacyclohexanes in 43-87% isolated yield and with exce ... Full text Cite

Direct observation of C-O reductive elimination from palladium aryl alkoxide complexes to form aryl ethers

Journal Article Journal of the American Chemical Society · July 23, 1997 Reaction of KOCH2CMe3 with [(R)-Tol-BINAP]Pd(p-C6H4CN)Br formed [(R)-Tol-BINAP]Pd(p-C6H4-CN)(OCH2CMe3) (5) in quantitative yield (1H NMR spectroscopy). Thermolysis of 5 in THF-d8 at 47 °C led to C-O reductive elimination with formation of p-neopentoxybenzo ... Full text Cite

Kinetics and Mechanism of the Formation of Palladium Bis(benzylamine) Complexes from Reaction of Benzylamine with Palladium Tri-o-tolylphosphine Mono(amine) Complexes

Journal Article Inorganic Chemistry · January 1, 1997 The kinetics of the conversion of the palladium mono(benzylamine) complex Pd[P(o-tol)3](p-C6H4CMe3)[H 2-NBn]Br (2) to the bis(benzylamine) complex Pd(p-C6H4CMe3[H2NBn]2Br (3) established the second-order rate law: Rate = k1[2][H2NBn], where ΔH‡ = 13.8 ± 0. ... Full text Cite

Formation of palladium bis (amine) complexes from reaction of amine with palladium tris(o-tolyl)phosphine mono(amine) complexes

Journal Article Organometallics · August 6, 1996 Palladium mono(benzylamine) complexes Pd[P(o-tolyl)3](p-C6H4CMe3)[H 2NBn]X (X = Cl (7), Br (8), I (14)) react reversibly with benzylamine in CDCl3 at 25 °C via P(o-tolyl)3 displacement to generate the corresponding bis(amine) derivatives trans-Pd(p-C6H4CMe ... Full text Cite

Synthesis and solution structure of palladium tris(o-tolyl)phosphine mono(amine) complexes

Journal Article Organometallics · June 11, 1996 The complex(es) resulting from a 1:4 mixture Of Pd2(DBA)3 and P(o-tol)3 react with aryl bromides or aryl iodides p-XC6H4R (X = Br, I; R = Me, t-Bu, OMe) to generate the corresponding halide dimers {Pd[P(o-tol)3](p-C6H4R)(μ-X)}2 (X = Br, R = t-Bu (1), Me (2 ... Full text Cite

Halide and amine influence in the equilibrium formation of palladium tris(o-tolyl)phosphine mono(amine) complexes from palladium aryl halide dimers

Journal Article Organometallics · June 11, 1996 The relative binding constants (Kb) for the coordination of amines to the palladium fragment Pd[P(o-tol)3](p-C6H4Me)Cl were determined by 1H NMR spectroscopy and decrease in the order hexylamine > benzylamine ≈ cyclohexylamine ≈ piperidine > dibutylamine ≈ ... Full text Cite

THE SYNTHESIS AND REDUCTIVE ELIMINATION OF PALLADIUM AMINE COMPLEXES

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 20, 1995 Link to item Cite

Reactions of Cp*3Co3(μ2-H)3(μ3-H) with Carbon Dioxide, Carbon Disulfide, and Phenyl Isocyanate

Journal Article Inorganic Chemistry · March 1, 1995 The tetrahydride tricobalt cluster Cp*3Co3(μ2-H)3(μ3-H) (1) reduces CO2 at 120 °C to form the dicobalt dicarbonyl complex [Cp*Co(μ-CO)]2 (2) in 45% yield by 1H NMR. 1 reacted with CS2 at room temperature to form the thiocarbonyl cluster Cp*3Co3(μ3-CS)(μ3-S ... Full text Cite

Kinetics and Mechanism of the Formation of the Bis(ethylidyne) Tricobalt Cluster Cp*3Co3(μ3-CCH3)2 from Reaction of Acetylene with Cp*3Co3(μ2-H)3(μ3-H)

Journal Article Journal of the American Chemical Society · January 1, 1995 The paramagnetic tetrahydride cluster Cp*3Co3(μ2-H)3(μ3-H) (1) reacts with acetylene to ultimately form the bis(ethylidyne) cluster Cp*3Co3(μ3-CCH3)2 (2). Two kinetically formed intermediates were isolated from the reaction: the diamagnetic mono(ethylidyne ... Full text Cite

Kinetics and mechanism of the formation of the bis(ethylidyne) tricobalt cluster Cp*3Co3(μ3-CCH3) 2 from reaction of acetylene with Cp*3Co3(μ2-H)3(μ 3-H)

Journal Article Journal of the American Chemical Society · 1995 The paramagnetic tetrahydride cluster Cp*3Co3(μ2-H)3(μ 3-H) (1) reacts with acetylene to ultimately form the bis(ethylidyne) cluster Cp*3Co3(μ3-CCH3) 2 (2). Two kinetically formed intermediates were isolated from the reaction: the diamagnetic mono(ethylidy ... Cite

Reactions of Cp*3Co3(μ2-H)3(μ 3-H) with carbon dioxide, carbon bisulfide, and phenyl isocyanate

Journal Article Inorganic Chemistry · 1995 The tetrahydride tricobalt cluster Cp*3Co3(μ2-H)3(μ 3-H) (1) reduces CO2 at 120°C to form the dicobalt dicarbonyl complex [Cp*Co(μ-CO)]2 (2) in 45% yield by 1H NMR. 1 reacted with CS2 at room temperature to form the thiocarbonyl cluster Cp*3Co3(μ3-CS)(μ3-S ... Cite

Syntheses, X-ray Crystal Structures, and Fluxional Behavior of the Clusters Cp*3Co3(μ2-CO)(μ3-CO)(μ-H)2, Cp*3Co3(μ2-H)(μ3-η2-HC=NCMe3), and Cp*3Co3(μ2-H)(μ3-η2-HC=NCMe2CH2Me)

Journal Article Organometallics · December 1, 1994 Cp*3Co3(μ2-H)3(μ3-H) (1) reacts with 2 equiv of CO to form the 48-electron dicarbonyl dihydride cluster Cp*3Co3(μ2-CO)(μ3-CO)(μ-H)2 (2), which was studied by X-ray crystallography. 2 consists of an equilateral triangle of cobalt atoms (Co-Co = 2.476(1) Å) ... Full text Cite

Syntheses and X-ray Crystal Structures of the Tricobalt Mono(ethylidyne) Clusters Cp*3Co3(µ3-CCH3)(µ3-CO)(µ2-H), Cp*3Co3(µ3-CCH3)(µ3-CNCMe3)(µ2-H), and Cp*3Co3(µ3-CCH3)(µ3-NO)

Journal Article Inorganic Chemistry · June 1, 1994 Cp*3CO3(µ3-CCH3)(µ3-H) (3) reacted with CO to form the 1:1 carbonyl ethylidyne adduct Cp*3Co3(µ3-CCH3)- (µ3-CO) (µ2-H) (5) in 82% yield. Similarly, tery-butyl isocyanide reacted with 3 to form the 1:1 isocyanide ethylidyne adduct Cp*3Co3(µ3-CCH3)(µ3-CNCMe3 ... Full text Cite

X-ray Crystal Structures of Two (Ethylidyne)tricobalt Clusters: Thermolysis of Cp*Co(H2C=CH2)2 Produces Cp*3Co3(μ3-CCH3)(μ3-H), Not Cp*3Co3(μ3-CCH3)2

Journal Article Organometallics · April 1, 1994 The structures of the μ3-ethylidyne tricobalt clusters Cp*3CO3(μ3-CCH3)2 (2) and Cp*3Co3(μ3-CCH3)(μ3-H) (3) were determined by X-ray crystallography. The 48-electron cluster 2 consists of an equilateral triangle of cobalt atoms (Co‒Co = 2.437(1) Å) symmetr ... Full text Cite

Syntheses, X-ray crystal structures, and fluxional behavior of the clusters Cp*3Co3(μ2CO)(μ3-CO)(μ-H)2, Cp*3Co3(μ2-H) (μ3-η2-HC=NCMe3), and Cp*3Co3(μ2-H)

Journal Article Organometallics · 1994 Cp*3Co3(μ2-H)3(μ3-H) (1) reacts with 2 equiv of CO to form the 48-electron dicarbonyldihydride cluster Cp*3Co3(μ2-CO)(μ3-CO)(μ-H) (2), which was studied by X-ray crystallography. 2 consists of an equilaterial triangle of cobalt atoms capped on each face by ... Cite

X-ray crystal structures of two (ethylidyne)tricobalt clusters. Thermolysis of Cp*Co(H2C=CH2)2 Produces Cp*3Co3(μ3CCH3 (μ3-H), not Cp*3Co3(μ3-CCH3)2

Journal Article Organometallics · 1994 The structures of the μ3-ethylidyne tricobalt clusters Cp*3Co3(μ3-CCH3)2 (2) and Cp*3Co3(μ3-CCH3)-(μ3-H) (3) were determined by X-ray crystallography. The 48-electron cluster 2 consists of an equilateral triangle of cobalt atoms (Co-Co = 2.437(1) A) symmet ... Cite

Syntheses and X-ray crystal structures of the tricobalt mono(ethylidyne) clusters Cp*3Co3(μ3-CCH3)(μ 3-CO)(μ2-H), Cp*3Co3(μ3-CCH3)(μ 3-CNCMe3)(μ2-H), and Cp*3Co3(μ3-CCH3)(μ 3-NO)

Journal Article Inorganic Chemistry · 1994 Cp*3Co3(μ3-CCH 3)(μ3-H) (3) reacted with CO to form the 1:1 carbonyl ethylidyne adduct Cp*3Co3(μ3-CCH3)-(μ 3-CO)(μ2-H) (5) in 82% yield. Similarly, tert-butyl isocyanide reacted with 3 to form the 1:1 isocyanide ethylidyne adduct Cp*3Co3(μ3-CCH3)(μ 3-CNCMe ... Cite

Reaction of CO and tert-butyl isocyanide with the cluster [(C 5Me5)3Co3(μ2-H) 3(μ3-H)] facile hydrogen transfer to isocyanide forms [(C5Me5)3Co3 (μ-H) (μ3-η2-HC=NCMe3)]

Journal Article Journal of the Chemical Society, Chemical Communications · December 1, 1993 The reaction of [(C5Me5)3Co 3(μ-2-H)3(μ3-H)] 1 with 2 equiv. of CO forms the biscarbonyl dihydride cluster [(C5Me5) 3Co3(μ3-CO) (μ2-CO)(μ-H) 2] 2; tert-butyl isocyanide inserts into a Co-H bond of 1 to form the formimidoyl monohydride cluster [(C5Me5) 3Co3 ... Full text Cite

CONVERSION OF ACETYLENE TO A TRIPLE BRIDGED ETHYLIDYNE LIGAND ON THE CLUSTER CP-ASTERISK-3CO3(MU-3-H)(MU-2-H)3

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · August 22, 1993 Link to item Cite

Conversion of Acetylene to a Triple Bridged Ethylidyne Ligand on the Cluster Cp*3Co3(μ2-H)3(μ3-H)

Journal Article Organometallics · January 1, 1993 The paramagnetic tetrahydride cluster, Cp*3-Co3(μ2-H)3(μ3-H) (1) reacts with acetylene to ultimately form the bis(ethylidyne) cluster Cp*3Co3(μ3-CCH3)2 (2). Two intermediates were detected during the course of the reaction: the diamagnetic Cp*3Co3(μ2-H)3(μ ... Full text Cite

Conversion of acetylene to a triple bridged ethylidyne ligand on the cluster Cp*3Co3(μ2-H)3(μ 3-H)

Journal Article Organometallics · 1993 The paramagnetic tetrahydride cluster, Cp*3-Co3(μ2-H)3(μ 3-H) (1) reacts with acetylene to ultimately form the bis(ethylidyne) cluster Cp*3Co3(μ3-CCH3) 2 (2). Two intermediates were detected during the course of the reaction: the diamagnetic Cp*3Co3(μ2-H)3 ... Cite

Phosphine induced cyclopentadienyl ring slippage catalyzes CO insertion into a methyl rhenium compound to produce an acetyl rhenium compound

Journal Article Journal of Organometallic Chemistry · April 28, 1992 The carbonylation of (η5-C5H5)Re(NO)(PMe3)(CH3) (1) to form (η5-C5H5)Re(NO)-(PMe3)(COCH3) (4) under 4.95 atm CO at 90°C is accelerated by a factor of > 25 in the presence of 0.28 M PMe3. Kinetic studies established a third order rate law: Rate = k3 [1] [PM ... Full text Cite

'[Cp*Co=CoCp*]' is a Hydride

Journal Article Angew. Chem. · 1992 Cite

“[Cp*CoCoCp*]” is a Hydride

Journal Article Angewandte Chemie International Edition in English · January 1, 1992 The supposed synthesis of the cobalt complex [Cp*CoCoCp*] was in the spotlight at the end of last year (Angew. Chem. Int. Ed. Engl. 1991, 30, 1124). But the compound described at that time is actually the mixed‐valent cobalt hydride 2. The reaction of the ... Full text Cite