Direct Catalytic Enantioselective C(sp <sup>2</sup> )–H Allylation of Acrylic Acids: Modular Access to Chiral 1,4-Skipped Dienes

The direct enantioselective C-H functionalization of carboxylic acids represents a formidable yet highly appealing goal in synthesis, offering efficient access to chiral molecules from abundant feedstocks. Herein, we disclose a chiral Cp<sup>x</sup>Rh(III)-catalyzed strategy for the enantioselective alkenyl C-H allylation of acrylic acids. This transformation achieves a unique asymmetric C(sp<sup>2</sup>)-C(sp<sup>3</sup>) cross-coupling between two olefin coupling partners─acrylic acids and allyl acetates─delivering valuable enantioenriched 1,4-dienes with high efficiency and excellent enantioselectivity. This transformation exhibits a broad substrate scope and high functional group tolerance, with its synthetic utility demonstrated through scalable synthesis and diverse downstream derivatizations. This strategy establishes a versatile and practical approach to asymmetric alkenyl C-H functionalization for the convenient synthesis of valuable enantioenriched architectures.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-12-17
DOI
https://doi.org/10.1021/jacs.5c17825
Primary Topic
Catalytic C–H Functionalization Methods
Type
article
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article

Direct Catalytic Enantioselective C(sp 2 )–H Allylation of Acrylic Acids: Modular Access to Chiral 1,4-Skipped Dienes

Mupeng Luo, Qiang Zhou, Juanjuan Wang, Shouguo Wang
Journal of the American Chemical Society
Catalytic C–H Functionalization Methods
article

Direct Catalytic Enantioselective C(sp 2 )–H Allylation of Acrylic Acids: Modular Access to Chiral 1,4-Skipped Dienes

Mupeng Luo, Qiang Zhou, Juanjuan Wang, Shouguo Wang
article en

Abstract

The direct enantioselective C-H functionalization of carboxylic acids represents a formidable yet highly appealing goal in synthesis, offering efficient access to chiral molecules from abundant feedstocks. Herein, we disclose a chiral Cp<sup>x</sup>Rh(III)-catalyzed strategy for the enantioselective alkenyl C-H allylation of acrylic acids. This transformation achieves a unique asymmetric C(sp<sup>2</sup>)-C(sp<sup>3</sup>) cross-coupling between two olefin coupling partners─acrylic acids and allyl acetates─delivering valuable enantioenriched 1,4-dienes with high efficiency and excellent enantioselectivity. This transformation exhibits a broad substrate scope and high functional group tolerance, with its synthetic utility demonstrated through scalable synthesis and diverse downstream derivatizations. This strategy establishes a versatile and practical approach to asymmetric alkenyl C-H functionalization for the convenient synthesis of valuable enantioenriched architectures.

Journal of the American Chemical SocietyVol. 147(52)
Shenzhen University (CN)
Openalex Percentile: Top 69%
Catalytic C–H Functionalization Methods
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