Carbocation-mediated rearrangements within [n.m.1]propellane frameworks

Martin G. Banwell, John H. Ryan, David A Winkler

Research output: Contribution to journalArticleOther

6 Citations (Scopus)

Abstract

Mild thermolysis of the tetracyclic mesylate (6) in the presence of traces of mineral acid afforded a mixture of the rearrangement products (21) and (22) as well the σ-anti- bishomotetralin (20). On treatment with methanesulfonic acid in dichloromethane, compound (20) gives rise to the [5.4.1] propellene (21) which, on prolonged exposure to these reaction conditions, isomerizes to the mesyloxymethyl compound (22). Under the same conditions, the σ-anti- bishomoindan (4) is converted into the [5.3.1] propellene (3) which, in turn, slowly rearranges to the [4.3.1] propellene (23). A mechanistic rationalization of these observations is advanced which also accounts for the formation of the novel by-product (16) observed during Simmons-Smith cyclopropanation of allylic alcohol (15a). 

Original languageEnglish
Pages (from-to)593-611
Number of pages19
JournalAustralian Journal of Chemistry
Volume44
Issue number4
DOIs
Publication statusPublished - 1991
Externally publishedYes

Cite this

Banwell, Martin G. ; Ryan, John H. ; Winkler, David A. / Carbocation-mediated rearrangements within [n.m.1]propellane frameworks. In: Australian Journal of Chemistry. 1991 ; Vol. 44, No. 4. pp. 593-611.
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Carbocation-mediated rearrangements within [n.m.1]propellane frameworks. / Banwell, Martin G.; Ryan, John H.; Winkler, David A.

In: Australian Journal of Chemistry, Vol. 44, No. 4, 1991, p. 593-611.

Research output: Contribution to journalArticleOther

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AU - Ryan, John H.

AU - Winkler, David A

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AB - Mild thermolysis of the tetracyclic mesylate (6) in the presence of traces of mineral acid afforded a mixture of the rearrangement products (21) and (22) as well the σ-anti- bishomotetralin (20). On treatment with methanesulfonic acid in dichloromethane, compound (20) gives rise to the [5.4.1] propellene (21) which, on prolonged exposure to these reaction conditions, isomerizes to the mesyloxymethyl compound (22). Under the same conditions, the σ-anti- bishomoindan (4) is converted into the [5.3.1] propellene (3) which, in turn, slowly rearranges to the [4.3.1] propellene (23). A mechanistic rationalization of these observations is advanced which also accounts for the formation of the novel by-product (16) observed during Simmons-Smith cyclopropanation of allylic alcohol (15a). 

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