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

Publication ,  Journal Article
Harris, RJ; Carden, RG; Duncan, AN; Widenhoefer, RA
Published in: 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 catalytically active mixtures. These data are consistent with a mechanism involving endergonic conversion of (IPr)AuOTf and 1 to the cationic gold π-allene complex (IPr)Au[n2-H2C=C=CMe2][OTf] (5·OTf), which undergoes outer-sphere addition of 2 followed by rapid protodemetalation to form 1-(3-methyl-2-butenyloxy)propyl)benzene (3a) as the kinetic product. The microscopic rate constants associated with the formation and consumption of 5·OTf are of similar magnitude, such that the kinetic behavior of catalytic hydroalkoxylation changes as a function of the relative and absolute concentrations of allene and alcohol.

Duke Scholars

Published In

ACS Catalysis

DOI

EISSN

2155-5435

Publication Date

September 7, 2018

Volume

8

Issue

9

Start / End Page

8941 / 8952

Related Subject Headings

  • 3406 Physical chemistry
  • 3405 Organic chemistry
  • 3106 Industrial biotechnology
  • 0904 Chemical Engineering
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry
 

Citation

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Harris, R. J., Carden, R. G., Duncan, A. N., & Widenhoefer, R. A. (2018). Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols. ACS Catalysis, 8(9), 8941–8952. https://doi.org/10.1021/acscatal.8b02211
Harris, R. J., R. G. Carden, A. N. Duncan, and R. A. Widenhoefer. “Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols.” ACS Catalysis 8, no. 9 (September 7, 2018): 8941–52. https://doi.org/10.1021/acscatal.8b02211.
Harris RJ, Carden RG, Duncan AN, Widenhoefer RA. Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols. ACS Catalysis. 2018 Sep 7;8(9):8941–52.
Harris, R. J., et al. “Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols.” ACS Catalysis, vol. 8, no. 9, Sept. 2018, pp. 8941–52. Scopus, doi:10.1021/acscatal.8b02211.
Harris RJ, Carden RG, Duncan AN, Widenhoefer RA. Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols. ACS Catalysis. 2018 Sep 7;8(9):8941–8952.
Journal cover image

Published In

ACS Catalysis

DOI

EISSN

2155-5435

Publication Date

September 7, 2018

Volume

8

Issue

9

Start / End Page

8941 / 8952

Related Subject Headings

  • 3406 Physical chemistry
  • 3405 Organic chemistry
  • 3106 Industrial biotechnology
  • 0904 Chemical Engineering
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry