Palladium-Catalyzed Atroposelective Kinetic C-H Olefination and Allylation for the Synthesis of C-B Axial Chirality

Jie Xu; Weihua Qiu; Xu Zhang; Zhihan Wu; Zhen Zhang; Kai Yang; Qiuling Song

doi:10.1002/anie.202313388

Palladium-Catalyzed Atroposelective Kinetic C-H Olefination and Allylation for the Synthesis of C-B Axial Chirality

Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202313388. doi: 10.1002/anie.202313388. Epub 2023 Oct 25.

Authors

Jie Xu¹, Weihua Qiu¹, Xu Zhang¹, Zhihan Wu¹, Zhen Zhang¹, Kai Yang¹, Qiuling Song^{1

2}

Affiliations

¹ Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.
² School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, China.

PMID: 37840007
DOI: 10.1002/anie.202313388

Abstract

The direct C-H functionalization of 1,2-benzazaborines, especially asymmetric version, remains a great challenge. Here we report a palladium-catalyzed enantioselective C-H olefination and allylation reactions of 1,2-benzazaborines. This asymmetric approach is a kinetic resolution (KR), providing various C-B axially chiral 2-aryl-1,2-benzazaborines and 3-substituted 2-aryl-1,2-benzazaborines in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). The synthetic potential of this reaction is showcased by late-stage modification of complex molecules, scale-up reaction, and applications.

Keywords: Axial Chirality; Azaborine; C−H Functionalization; Kinetic Resolution; Palladium.

Abstract

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