Issue 8, 2014

Hypervalent iodine(iii)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions

Abstract

Hypervalent iodine(III)-mediated dioxygenation and diamination of alkenes have been previously developed. In this study, the potential application of hypervalent iodine(III) reagent was successfully extended to the dialkylation and cyclopropa(e)nation of unsaturated alkenes and alkynes. The reactions of alkenes with malononitrile and other active methylene compounds as the carbon nucleophiles give access to multisubstituted cyclopropane derivatives in moderate to excellent yields. Both electron-rich and electron-deficient alkenes are suitable substrates. Alkynes, no matter terminal or internal alkynes, work well, affording the corresponding highly functionalized cyclopropenes efficiently. A plausible mechanism of iodo(III)cyclopropanation, ring opening attack by the carbon-nucleophile, and recyclization was proposed for the cyclopropanation of trans-alkene substrates. The cyclopropenation was thought to proceed via iodo(III)cyclopropanation, ring-opening attack by the carbon-nucleophile, recyclization into a four-membered iodo(III)cyclobutene and final reductive elimination. The protocol might provide a complementary route to cyclopropanation/cyclopropenation.

Graphical abstract: Hypervalent iodine(iii)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions

Supplementary files

Article information

Article type
Paper
Submitted
25 Oct 2013
Accepted
19 Dec 2013
First published
19 Dec 2013

Org. Biomol. Chem., 2014,12, 1341-1350

Hypervalent iodine(III)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions

S. Lin, M. Li, Z. Dong, F. Liang and J. Zhang, Org. Biomol. Chem., 2014, 12, 1341 DOI: 10.1039/C3OB42123F

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