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. 2016 Dec 14;138(49):15877-15880.
doi: 10.1021/jacs.6b11367. Epub 2016 Nov 30.

Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer

Eiji Yamamoto  1 , Margaret J Hilton  1 , Manuel Orlandi  1 , Vaneet Saini  1 , F Dean Toste  2 , Matthew S Sigman  1
Affiliations

Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer

Eiji Yamamoto et al. J Am Chem Soc. .

Abstract

Enantioselective 1,1-diarylation of terminal alkenes enabled by the combination of Pd catalysis with a chiral anion phase transfer (CAPT) strategy is reported herein. The reaction of substituted benzyl acrylates with aryldiazonium salts and arylboronic acids gave the corresponding 3,3-diarylpropanoates in moderate to good yields with high enantioselectivies (up to 98:2 er). Substituents on the benzyl acrylate and CAPT catalyst significantly affect the enantioselectivity, and multidimensional parametrization identified correlations suggesting structural origins for the high stereocontrol.

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Figures

Figure 1
Figure 1
Multidimensional Correlation of Chiral Anion Parameters with Enantioselectivity.
Figure 2
Figure 2
Evaluation and Correlation of Benzyl Acrylate Substituent Effects on Enantioselectivity.
Scheme 1
Scheme 1
Relevance and overview of the enantioselective 1,1-difunctionalization of alkenes
See this image and copyright information in PMC

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