α-Nitro Keto Hydrazone and Keto Imine Dianions. Synthetic Equivalents for the Nitroalkene d3 Synthon

Scott E. Denmark, Jeffrey A. Sternberg, Rainer Lueoend

Research output: Contribution to journalArticlepeer-review

Abstract

A general method for the preparation of 3-substituted nitrocycloalkenes has been developed. 2-Nitrocyclo-alkanones are transformed into either α-nitro N,N-dimethylhydrazones or α-nitro cyclohexylimines, which exist exclusively in the oci-nitro form. Double deprotonation of these materials with sec-BuLi produces highly reactive dianions which can be alkylated with methyl, allyl, n-butyl, isopropyl, or 4-hexenyl iodides in excellent yields. The alkylation occurred uniformly next to the hydrazone or imine function. The alkylated α-nitro hydrazones are converted to nitroalkenes by reduction with NaBH4 followed by elimination induced by heating (120 °C) with acetic anhydride. The alkylated ?-nitro imines undergo facile reduction-elimination with NaBH4/CeCl3at room temperature. The overall yield for 2-nitro ketone to nitroalkene transformation ranged from 35% to 44% for the hydrazone method and from 19% to 39% for the imine method.

Original languageEnglish (US)
Pages (from-to)1251-1263
Number of pages13
JournalJournal of Organic Chemistry
Volume53
Issue number6
DOIs
StatePublished - Mar 1 1988

ASJC Scopus subject areas

  • Organic Chemistry

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