The solvomercuration, bromination, and related reactions of 1,5-dimethyl-6-methylenetricyclo(3.2.1.02,7)oct-3-en-8-one and its related compounds.

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概要

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• The solvomercuration-demercuration reactions of 1,5-dimethyl-6-methylenetricyclo[3.2.1.0<SUP>2,7</SUP>]oct-3-en-8-one (<B>1</B>), its corresponding alcohol, and 5,8-dimethyl-9-methylenetricyclo[3.3.1.0<SUP>2,8</SUP>]non-3-en-7-one (<B>2</B>) were investigated. In all cases, the solvent was stereospecifically incorporated on the exomethylene group, and the original tricyclic skeleton did not undergo rearrangement. Similarly, <B>1</B> and <B>2</B> underwent a stereospecific bromination on the exomethylene group by means of the reaction with pyridinium tribromide. These results suggest the stabilization of the formal cyclopropylcarbinyl cation intermediates by the adjacent acetoxymercury moiety or the bromine atom. On the other hand, the reaction of NBS–MeOH or NBS–H<SUB>2</SUB>O with <B>1</B> afforded an addition product on the exomethylene group, and 1,4-addition originated from the cleavage of the cyclopropane ring, while with <B>2</B> the reaction afforded only an addition product on the exomethylene group. The difference in this reaction mode is discussed on the basis of the solvent effect and the ring strain of <B>1</B>.

• 公益社団法人 日本化学会の論文

著者

• Nitta Makoto

  Department Of Applied Pharmacology Toyama Medical And Pharmaceutical University

• Sugiyama Hiroshi

  Department Of Chemistry Faculty Of Science

• Omata Akihiko

  Department of Chemistry, School of Science and Engineering, Waseda University

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