Asymmetric Photocatalytic C(sp3)–H Bond Addition to α‑Substituted Acrylates

Asymmetric functionalization of inert C­(sp3)–H bonds is a straightforward approach to realize versatile bond-forming events, allowing the precise assembly of molecular complexity with minimal functional manipulations. Here, we describe an asymmetric photocatalytic C­(sp3)–H bond addition to α-subst...

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Bibliographic Details
Published in:Organic letters 2021-04, Vol.23 (8), p.3157-3161
Main Authors: Dai, Zhen-Yao, Nong, Zhong-Sheng, Song, Shun, Wang, Pu-Sheng
Format: Article
Language:English
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Summary:Asymmetric functionalization of inert C­(sp3)–H bonds is a straightforward approach to realize versatile bond-forming events, allowing the precise assembly of molecular complexity with minimal functional manipulations. Here, we describe an asymmetric photocatalytic C­(sp3)–H bond addition to α-substituted acrylates by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst and chiral phosphoric acid as a chiral proton-transfer shuttle. This protocol is supposed to occur via a radical/ionic relay process, including a TBADT-mediated HAT to cleave the inert C­(sp3)–H bond, a 1,4-radical addition, a back hydrogen abstraction, and an enantioselective protonation. A variety of inert C–H bond patterns and α-substituted acrylates are well tolerated to enable the rapid synthesis of enantioenriched α-stereogenic esters from simple raw materials.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.1c00801