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Updated: Sep 16, 2025

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Electrochemical phosphorylation of α,β-unsaturated carboxylic acids via decarboxylative cross-coupling reaction
Zhaoqi Zhang1, Yirui Shen2, Yufen Zhao1,3
1Institute of Drug Discovery Technology, Ningbo University, Zhejiang, China. wuju@nbu.edu.cn.
Abstract:
DABCO-mediated electrochemical decarboxylative coupling reaction of Ph2P(O)H with alkenyl acids has been developed. A range of (E)-alkenylphosphine oxides were obtained with broad substrate scope and excellent regioselectivity under metal-free and ambient conditions. Mechanistic studies suggested that the phosphinyl radical was generated through a hydrogen atom transfer (HAT) process mediated by DABCO+˙. Moreover, Cp2Fe-mediated electrochemical synthesis of alkynylphosphine oxides has been established.
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As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...

