Catalytic protodeboronation of pinacol boronic esters: formal anti-Markovnikov hydromethylation of alkenes

Chemical Science
Florian ClausenArmido Studer

Abstract

Pinacol boronic esters are highly valuable building blocks in organic synthesis. In contrast to the many protocols available on the functionalizing deboronation of alkyl boronic esters, protodeboronation is not well developed. Herein we report catalytic protodeboronation of 1°, 2° and 3° alkyl boronic esters utilizing a radical approach. Paired with a Matteson-CH2-homologation, our protocol allows for formal anti-Markovnikov alkene hydromethylation, a valuable but unknown transformation. The hydromethylation sequence was applied to methoxy protected (-)-Δ8-THC and cholesterol. The protodeboronation was further used in the formal total synthesis of δ-(R)-coniceine and indolizidine 209B.

References

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Citations

Dec 6, 2019·Chemical Communications : Chem Comm·Nivesh KumarAhmad Masarwa
Jul 3, 2020·Advanced Synthesis & Catalysis·Marvin KischkewitzArmido Studer
Apr 20, 2021·Angewandte Chemie·James A LawJames H Frederich
Dec 22, 2020·Journal of the American Chemical Society·Yangyang YangTian Qin
Aug 29, 2019·Journal of the American Chemical Society·Daniel KaiserVarinder K Aggarwal
Aug 22, 2020·Organic Letters·Florian Clausen, Armido Studer
Aug 31, 2021·Journal of the American Chemical Society·Hannah L D HayesGuy C Lloyd-Jones

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