Irradiation of Methyl Diazomalonate in Solution. Reactions of Singlet and Triplet Carbenes with Carbon-Carbon Double Bonds

Maitland Jones, Wataru Ando, Michael E. Hendrick, Anthony Kulczycki, Peter M. Howley, Karl F. Hummel, Donald S. Malament

Research output: Contribution to journalArticlepeer-review

129 Scopus citations

Abstract

Direct and sensitized irradiation of methyl diazomalonate gives singlet and triplet biscarbomethoxycarbene, respectively. The reactions of these species with carbon–carbon double bonds are described. Cyclopropanes are formed with substantial retention of stereochemistry from the singlet but with complete loss from the triplet. Additions to aliene, norbornadiene, and benzene are also achieved. The reactions of several triplet carbenes with dienes are reported, but even in systems thought to be favorable to 1,4 addition, only the normal cyclopropanes could be found. Reactions with carbon-hydrogen single bonds are also described. Singlet carbene reacts by direct insertion, but the triplet abstracts hydrogen to give radical pairs which undergo recombination and disproportionation.

Original languageEnglish
Pages (from-to)7469-7479
Number of pages11
JournalJournal of the American Chemical Society
Volume94
Issue number21
DOIs
StatePublished - Oct 1 1972

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