Copper-Catalyzed Regioselective Allylic Cyanation of Allylic Compounds with Trimethylsilyl Cyanide

Daisuke Munemori; Hiroaki Tsuji; Kenta Uchida; Tomoaki Suzuki; Kazuki Isa; Maki Minakawa; Motoi Kawatsura

doi:10.1055/s-0034-1378322

Synthesis, Table of Contents

Synthesis 2014; 46(20): 2747-2750
DOI: 10.1055/s-0034-1378322

paper

Copper-Catalyzed Regioselective Allylic Cyanation of Allylic Compounds with Trimethylsilyl Cyanide

Daisuke Munemori

^aDepartment of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan

,

Hiroaki Tsuji

^aDepartment of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan

,

Kenta Uchida

^aDepartment of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan

,

Tomoaki Suzuki

^bDepartment of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan Fax: +81(3)53179740 Email: kawatsur@chs.nihon-u.ac.jp

,

Kazuki Isa

^bDepartment of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan Fax: +81(3)53179740 Email: kawatsur@chs.nihon-u.ac.jp

,

Maki Minakawa

^bDepartment of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan Fax: +81(3)53179740 Email: kawatsur@chs.nihon-u.ac.jp

,

Motoi Kawatsura*

^bDepartment of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan Fax: +81(3)53179740 Email: kawatsur@chs.nihon-u.ac.jp

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Abstract

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Abstract

The copper-catalyzed regioselective allylic cyanation of allylic compounds with trimethylsilyl cyanide (TMSCN) is described. Copper(I) iodide (CuI), copper(I) cyanide (CuCN) and copper(II) chloride (CuCl₂) are shown to effectively catalyze the cyanation of various allylic substrates to afford the corresponding allylic cyanides in good yields and high regioselectivities. The reaction in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) reveals that the cyanation proceeds via a radical pathway.

Key words

copper - catalysis - regioselectivity - radical reaction - nitriles

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References

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