Rhodium-Catalyzed Intramolecular Cyclopropanation of α-Diazo β-Keto Nitriles Containing an Unsaturated Substituted Cycloalkyl Group

Abstract

Several α-diazo β-keto nitriles bearing trans-2-allyl-, -vinyl-, or -phenylcycloalkyl groups were prepared and their intramolecular cyclopropanation reactions were examined. In the presence of Rh₂(OAc)₄ (1 mol%) as a catalyst, the allyl- and vinyl-substituted precursors were found to undergo cyclopropanation smoothly at ambient temperature to afford novel tricyclic α-keto cyclopropyl nitriles in 47–88% yields with diastereomeric ratios ranging from 79:21 to >99:1. On the other hand, the catalytic reactions of the phenyl-containing analogues did not give any cyclopropyl products, but instead provided functionalized hexa­hydrophenanthrene or tetrahydrocyclopentanaphthalene derivatives in quantitative yields.

Key words

cyclopropanation - rhodium catalysis - diazonitriles - cyclopropyl nitriles - ring opening - polycyclic compounds

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