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Formation of ?-chiral centers by asymmetric ?-C(sp3)-H arylation, alkenylation, and alkynylation.

ABSTRACT: The enzymatic ?-C-H hydroxylation of the feedstock chemical isobutyric acid has enabled the asymmetric synthesis of a wide variety of polyketides. The analogous transition metal-catalyzed enantioselective ?-C-H functionalization of isobutyric acid-derived substrates should provide a versatile method for constructing useful building blocks with enantioenriched ?-chiral centers from this abundant C-4 skeleton. However, the desymmetrization of ubiquitous isopropyl moieties by organometallic catalysts has remained an unanswered challenge. Herein, we report the design of chiral mono-protected aminomethyl oxazoline ligands that enable desymmetrization of isopropyl groups via palladium insertion into the C(sp3)-H bonds of one of the prochiral methyl groups. We detail the enantioselective ?-arylation, -alkenylation, and -alkynylation of isobutyric acid/2-aminoisobutyric acid derivatives, which may serve as a platform for the construction of ?-chiral centers.

SUBMITTER: Wu QF 

PROVIDER: S-EPMC5480404 | biostudies-other | 2017 Feb

REPOSITORIES: biostudies-other

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Formation of α-chiral centers by asymmetric β-C(sp3)-H arylation, alkenylation, and alkynylation.

Wu Qing-Feng QF   Shen Peng-Xiang PX   He Jian J   Wang Xiao-Bing XB   Zhang Forrest F   Shao Qian Q   Zhu Ru-Yi RY   Mapelli Claudio C   Qiao Jennifer X JX   Poss Michael A MA   Yu Jin-Quan JQ  

Science (New York, N.Y.) 20170201 6324

The enzymatic β-C-H hydroxylation of the feedstock chemical isobutyric acid has enabled the asymmetric synthesis of a wide variety of polyketides. The analogous transition metal-catalyzed enantioselective β-C-H functionalization of isobutyric acid-derived substrates should provide a versatile method for constructing useful building blocks with enantioenriched α-chiral centers from this abundant C-4 skeleton. However, the desymmetrization of ubiquitous isopropyl moieties by organometallic catalys  ...[more]

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