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. 2019 Jun 5;141(22):8708-8711.
doi: 10.1021/jacs.9b03438. Epub 2019 May 24.

Enantioselective Markovnikov Addition of Carbamates to Allylic Alcohols for the Construction of α-Secondary and α-Tertiary Amines

Ana Bahamonde  1 , Buthainah Al Rifaie  1 , Victor Martín-Heras  1 , Jamie R Allen  1 , Matthew S Sigman  1
Affiliations

Enantioselective Markovnikov Addition of Carbamates to Allylic Alcohols for the Construction of α-Secondary and α-Tertiary Amines

Ana Bahamonde et al. J Am Chem Soc. .

Abstract

Herein we describe the development of a Pd-catalyzed enantioselective Markovnikov addition of carbamates to allylic alcohols for the construction of α-tertiary and α-secondary amines. The reaction affords a range of β-amino alcohols, after reduction of the aldehyde in situ, which contain a variety of functional groups in moderate yields and moderate to good enantioselectivities. These products can be readily oxidized to β-amino acids, valuable building blocks for the synthesis of biologically active compounds. Mechanistic studies indicate that the C-N bond formation occurs via a syn amino-palladation mechanism, an insight which may guide future reaction development given the limited number of enantioselective syntheses of α-tertiary amines.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Figure 1
Figure 1
Enantioselective coupling of amines to olefins.
Figure 2
Figure 2
Aminopalladation mechanistic studies
See this image and copyright information in PMC

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