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Published on: November 30, 2022
Enantiodivergent Rh-Catalyzed Reductive Hydroformylation of Alkenyl Boronic Esters
Yiteng Yu1, Yuchen Zhang2, Xiao-Song Xue2,3
1State Key Laboratory of Green-Chemical Synthesis and Conversion Technology, the College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang, 310032, China.
Abstract:
We herein report the first enantioselective Rh-catalyzed reductive hydroformylation of alkenyl boronic esters. By employing either "camouflage" or "direct" reductive AHF strategy, enantiodivergent synthesis of chiral γ-boryl alcohols has been developed for the first time in high yields and excellent enantioselectivities with alkene 1,2-diboronic esters or alkenyl boronic esters as the starting materials using rhodium/Ph-BPE as the catalyst. The method has enjoyed high chemo-selectivity, good functional group compatibility, and broad substrate scope. The chiral γ-boryl alcohol or diol products are versatile building blocks applicable to the synthesis of a series of APIs including (S)-tolterodine, (S)-dapoxetine, and (R)-atomaxetine. DFT calculation has revealed the origin of enantiodivergence of Rh-catalyzed reductive AHF of alkenyl boronic esters with Ph-BPE as the chiral ligand. The transformation is promised to provide great synthetic potential in both academia and industry.
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