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. 2015 Jul 8;137(26):8392-5.
doi: 10.1021/jacs.5b05200. Epub 2015 Jun 29.

Rhodium-Catalyzed Enantioselective Hydroamination of Alkynes with Indolines

Qing-An Chen  1 , Zhiwei Chen  1 , Vy M Dong  1
Affiliations

Rhodium-Catalyzed Enantioselective Hydroamination of Alkynes with Indolines

Qing-An Chen et al. J Am Chem Soc. .

Abstract

The hydroamination of internal alkynes via tandem rhodium catalysis gives branched N-allylic indolines with high regio- and enantioselectivity. An acid switch provides access to the linear isomer in preference to the branched isomer by an isomerization mechanism. Mechanistic studies suggest formation of an allene intermediate, which undergoes hydroamination to generate allylic amines instead of the enamine or imine products typically observed in alkyne hydroaminations.

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Figures

Figure 1
Figure 1
Allylic Aminations versus Alkyne Hydroaminations
Figure 2
Figure 2
Tandem Rh-Catalysis: Proposed Mechanism for Hydroamination of Alkynes
Figure 3
Figure 3
Acid-Promoted Isomerization Study
See this image and copyright information in PMC

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