Synlett 2017; 28(12): 1467-1472
DOI: 10.1055/s-0036-1588174
letter
© Georg Thieme Verlag Stuttgart · New York

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

Jia-Liang Zhu*, Yung-Peng Wu
  • Department of Chemistry, National DongHwa University, No. 1, Sec. 2, Da Hsueh Rd. Shoufeng, Hualien 97401, Taiwan, ROC   Email: jlzhu@gms.ndhu.edu.tw
Supported by: Ministry of Science and Technology of Taiwan (MOST 104-2113-M-259-001)
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Publication History

Received: 13 February 2017

Accepted after revision: 19 March 2017

Publication Date:
07 April 2017 (eFirst)

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.

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