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. 2015 Dec 4:11:2444-50.
doi: 10.3762/bjoc.11.265. eCollection 2015.

Copper-catalyzed stereoselective conjugate addition of alkylboranes to alkynoates

Takamichi Wakamatsu  1 , Kazunori Nagao  1 , Hirohisa Ohmiya  1 , Masaya Sawamura  1
Affiliations

Copper-catalyzed stereoselective conjugate addition of alkylboranes to alkynoates

Takamichi Wakamatsu et al. Beilstein J Org Chem. .

Abstract

A copper-catalyzed conjugate addition of alkylboron compounds (alkyl-9-BBN, prepared by hydroboration of alkenes with 9-BBN-H) to alkynoates to form β-disubstituted acrylates is reported. The addition occurred in a formal syn-hydroalkylation mode. The syn stereoselectivity was excellent regardless of the substrate structure. A variety of functional groups were compatible with the conjugate addition.

Keywords: alkylborane; alkynoate; conjugate addition; copper; multisubstituted alkene.

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Figures

Scheme 1
Scheme 1
Conjugate addition of alkylborane 2a to alkynoate 3a.
Scheme 2
Scheme 2
Synthesis of five membered carbocycle.
Scheme 3
Scheme 3
Deuterium-labeling experiment.
Figure 1
Figure 1
Possible mechanism.
Figure 2
Figure 2
Isomerization of the alkenylcopper intermediates.
See this image and copyright information in PMC

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