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Pure Appl. Chem., 2013, Vol. 85, No. 4, pp. 785-799

Published online 2012-12-07

Highly selective introduction of heteroatom groups to isocyanides and its application to electrocyclic reactions

Akiya Ogawa*, Taichi Tamai, Takenori Mitamura and Akihiro Nomoto

Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan

Abstract: Photoinduced cyclization of o-alkenylaryl isocyanides with (PhS)2 in the presence of (PhTe)2 affords the corresponding bisthiolated indene derivatives in good yields via radical cyclization process by thio radical. The procedure can be applied to the construction of tetracyclic systems by using bis(o-aminophenyl) disulfides in place of (PhS)2. In sharp contrast, when o-alkynylaryl isocyanides are employed as the substrates, novel electrocyclic reactions take place upon photoirradiation or heating at 40~80 °C to generate quinoline 2,4‑biradical species, which are trapped with organic diselenides, ditellurides, and molecular iodine to give the corresponding 2,4-diseleno-, ditelluro-, and diiodo-quinoline derivatives, respectively, in good yields. The obtained quinoline derivatives are useful synthetic intermediates; for example, cross-coupling reactions using 2,4-diiodoquinolines lead to the preparation of functionalized quinoline derivatives.