Work

Regioselective Electrochemical Borylation of Oxygenated Allylic Electrophiles: Method Development and Synthetic Applications

Year: 2025

Type: article

Abstract: Allylboronic esters are highly versatile intermediates in organic synthesis. In this work, we report a general and scalable strategy for the regioselective deoxygenative borylation of allylic alcohols, enals, enones, and acrylates, upgrading these abundant functional groups in feedstock chemicals and natural products into value-added borylated synthetic handles. This method achieves efficient C-O bond activation under mild electroreductive conditions, and the effective control of regioselectivity was made possible by optimizing the borylating agent and supporting electrolyte. The utility of this approach was further demonstrated in a series of telescoped synthetic sequences, enabling alcohol and carbonyl transposition, formal cross-coupling of alcohols and aldehydes, allylic amination, and vinylogous homologation. This electrosynthetic protocol offers a broadly applicable, modular route to complex allylboron compounds from simple and readily available starting materials, including terpenoid natural products.

Source: ACS Central Science

DOI: 10.1021/acscentsci.5c01074

Authors: Wan-Chen Cindy Lee, Pierre-Louis Lagueux-Tremblay, Zongbin Jia, Song Lin

Institution: Cornell University

Language: English

Topic: Organoboron and organosilicon chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: diamond

Funders: Camille and Henry Dreyfus Foundation, National Institutes of Health, National Institute of General Medical Sciences

Award: G4580980826