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. 2018 Jul 25;140(29):9087-9090.
doi: 10.1021/jacs.8b05683. Epub 2018 Jul 10.

Hydroamination versus Allylic Amination in Iridium-Catalyzed Reactions of Allylic Acetates with Amines: 1,3-Aminoalcohols via Ester-Directed Regioselectivity

Seung Wook Kim  1 , Thomas Wurm  1 , Gilmar A Brito  1 , Woo-Ok Jung  1 , Jason R Zbieg  2 , Craig E Stivala  2 , Michael J Krische  1
Affiliations

Hydroamination versus Allylic Amination in Iridium-Catalyzed Reactions of Allylic Acetates with Amines: 1,3-Aminoalcohols via Ester-Directed Regioselectivity

Seung Wook Kim et al. J Am Chem Soc. .

Abstract

In the presence of a neutral dppf-modified iridium catalyst and Cs2CO3, linear allylic acetates react with primary amines to form products of hydroamination with complete 1,3-regioselectivity. The collective data, including deuterium labeling studies, corroborate a catalytic mechanism involving rapid, reversible acetate-directed aminoiridation with inner-sphere/outer-sphere crossover followed by turnover-limiting proto-demetalation mediated by amine.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Cationic vs neutral iridium catalysts promote Tsuji-Trost allylic amination and hydroamination, respectively.
Scheme 1.
Scheme 1.
Deuterium labelling experiments. aReactants and products characterized by 1H NMR, 2H NMR and HRMS. See Supporting Information for further experimental details.
Scheme 2.
Scheme 2.
General catalytic mechanism for iridium catalyzed hydroamination of linear allylic acetates, as corroborated by deuterium labeling.
See this image and copyright information in PMC

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