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Synlett 2011(4): 582-584  
DOI: 10.1055/s-0030-1259529
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

TMSCl-Promoted Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine

Hideo Tanaka*a, Tomotake Yanoa, Kazuma Kobayashia, Syogo Kamenouea, Manabu Kuroboshia, Hiromu Kawakubo*b
a The Graduate School of Natural Science and Technology, Okayama University, Tsushima-Naka 3-1-1, Okayama 700-8530, Japan
Fax: +81(86)2518079; e-Mail: tanaka95@cc.okayama-u.ac.jp;
b API Department, Asahi Kasei Chemicals Corporation, Kanda Jinbocho 1-105, Chiyoda-ku, Tokyo 101-8101, Japan
Further Information

Publication History

Received 23 November 2010
Publication Date:
08 February 2011 (online)

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Abstract

Direct reductive transformation of triphenylphosphine oxide to triphenylphosphine was performed successfully by electrolysis with TMSCl in an acetonitrile/Bu4NBr/(Zn anode)-(Pt cathode)/undivided cell/constant current electrolysis system. A plausible ECEC mechanism involving the formation of silylated phosphorus radical is proposed.

Key words

reduction - electron transfer - phosphorus - silicon

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16

No appreciable difference in chemical shifts between ³¹P NMR spectra of triphenylphosphine oxide 2 (d = 26.2 ppm in MeCN) and that of a mixture of 2 and TMSCl (1:1) was observed, suggesting that any reactions of 2 with TMSCl would not occur before electrochemical reduction of 2.

17

Though the reaction conditions were not optimized yet, other triarylphosphines such as tris(o-toryl)phosphine, tris(m-toryl)phosphine, and tris(p-toryl)phosphine were obtained from the corresponding phosphine oxides in 58%, 74%, and 78% yield, respectively.