Vinylidene Homologation of Boronic Esters and its Application to the Synthesis of the Proposed Structure of Machillene

Angewandte Chemie
James M FordhamVarinder K Aggarwal

Abstract

Alkenyl boronic esters are important reagents in organic synthesis. Herein, we report that these valuable products can be accessed by the homologation of boronic esters with lithiated epoxysilanes. Aliphatic and electron-rich aromatic boronic esters provided vinylidene boronic esters in moderate to high yields, while electron-deficient aromatic and vinyl boronic esters were found to give the corresponding vinyl silane products. Through DFT calculations, this divergence in mechanistic pathway has been rationalized by considering the stabilization of negative charge in the C-Si and C-B bond breaking transition states. This vinylidene homologation was used in a short six-step stereoselective synthesis of the proposed structure of machillene, however, synthetic and reported data were found to be inconsistent.

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Citations

Nov 20, 2019·Angewandte Chemie·Ruben MartinYangyang Shen
Feb 19, 2020·Chemistry : a European Journal·Yannick LinneMarkus Kalesse
Aug 31, 2020·Chemistry : a European Journal·Lidia A MaslovskayaCraig M Williams
Jun 17, 2020·Chemical Communications : Chem Comm·Rodney A FernandesPriyanka Choudhary

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