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

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 catalytically active mixtures. The results of these and additional experiments are consistent with a mechanism for hydroamination involving reversible, endergonic displacement of N-methylaniline from [(IPr)Au(NHMePh)]⁺ (4) by allene to form the cationic gold π-C1,C2-allene complex [(IPr)Au(η² -H₂ C=C=CMe₂ )]⁺ (I), which is in rapid, endergonic equilibrium with the regioisomeric π-C2,C3-allene complex [(IPr)Au(η² -Me₂ C=C=CH₂ )]⁺ (I'). Rapid and reversible outer-sphere addition of 2 to the terminal allene carbon atom of I' to form gold vinyl complex (IPr)Au[C(=CH₂ )CMe₂ NMePh] (II) is superimposed on the slower addition of 2 to the terminal allene carbon atom of I to form gold vinyl complex (IPr)Au[C(=CMe₂ )CH₂ NMePh] (III). Selective protodeauration of III releases N-methyl-N-(3-methylbut-2-en-1-yl)aniline (3 a) with regeneration of 4. At high conversion, gold vinyl complex II is competitively trapped by an (IPr)Au⁺ fragment to form the cationic bis(gold) vinyl complex {[(IPr)Au]₂ [C(=CH₂ )CMe₂ NMePh]}⁺ (6).

Duke Scholars

Author Ross A. Widenhoefer Chemistry