TMSCl-Promoted Electroreduction
of Triphenylphosphine Oxide to Triphenylphosphine

Hideo Tanaka; Tomotake Yano; Kazuma Kobayashi; Syogo Kamenoue; Manabu Kuroboshi; Hiromu Kawakubo

doi:10.1055/s-0030-1259529

LETTER

TMSCl-Promoted Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine

Hideo Tanaka*^a, Tomotake Yano^a, Kazuma Kobayashi^a, Syogo Kamenoue^a, Manabu Kuroboshi^a, 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

Abstract

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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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References

References and Notes

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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.

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.