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Enantioconvergent Hydroboration of <i>E</i>/<i>Z</i>-Mixed Trisubstituted Alkenes

Yinwei Bao, Cheng‐Gong Zheng, Kangyu Xiong, Chenke Hu, Peng Lu, Yuwen Wang, Zhan Lu

2024Journal of the American Chemical Society24 citationsDOI

Abstract

The lack of mode for chirality recognition makes it particularly challenging to carry out asymmetric transformations on E / Z -mixed minimally functionalized trisubstituted alkenes. Here, we report a catalytic enantioconvergent hydroboration of minimally functionalized trisubstituted E / Z -mixed alkenes to construct chiral organoboronic esters with excellent enantioselectivity using chiral radical cobalt catalyst. This C(sp 3 )-H borylation protocol showed good functional group tolerance and products could be converted to valuable compounds via C–B derivatizations. The mechanistic studies, which included control experiments, nonlinear effect experiments, deuterated labeling experiments, and X-ray diffraction, demonstrated that the favorable compatibility between the thermodynamically unfavorable isomerization and hydroboration was the key factor in achieving convergent transformation.

Topics & Concepts

ChemistryHydroborationOrganic chemistryStereochemistryCatalysisOrganoboron and organosilicon chemistryAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and Catalysis
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