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Scientific article
English

Rh(II)-Catalyzed Isomerizations of Cyclopropenes Evidence for Rh(II)-Complexed Vinylcarbene Intermediates

Published inHelvetica Chimica Acta, vol. 73, no. 5, p. 1233-1241
Publication date1990
Abstract

The thermocatalytic rearrangements of cyclopropenes 1-4 have been investigated in the presence of Rh(IT) perfiuorobutyrate. 1, 2, 3-Triphenylcyclopropene (1a) undergoes rearrangement lo diphenylindene 5a or, with alkoxycyclopropene derivatives, to α, β-unsaturated ketone 6. Furan formation occurs with 2, 3-diphenylcyclo-propenecarboxylate 2, but the diethyl counterpart 3 rearranges to dienoate 8. 2-Alkylcyclopropenecarboxylates 4 afforded (E)-methylidenecyclopentane derivatives 9 as the only isolable product in yields of ca. 35 %. A mechanism involving regio- and stereospecific cyclopropene ring opening to a Rh-complexed vinylcarbene and insertion of the latter into the C-H bond to give 9 is proposed. An analogous mechanism should account for the rearrangement products of 1 to 3.

Funding
  • Swiss National Science Foundation - 2.602-0.87
Citation (ISO format)
MULLER, Paul et al. Rh(II)-Catalyzed Isomerizations of Cyclopropenes Evidence for Rh(II)-Complexed Vinylcarbene Intermediates. In: Helvetica Chimica Acta, 1990, vol. 73, n° 5, p. 1233–1241. doi: 10.1002/hlca.19900730513
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ISSN of the journal0018-019X
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