Stereochemistry of Carbenic 1,2-Vinyl Shifts

Stereochemistry of Carbenic 1,2-Vinyl Shifts

Various 1-phenylbut-3-enylidenes, (Ph)CCR2CHCHR‘, were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R‘CHCHC(Ph)CR2, were found to predominate over γ-C−H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramol...

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Veröffentlicht in:Journal of organic chemistry 1998-02, Vol.63 (4), p.1178-1184
Hauptverfasser: Kirmse, Wolfgang, Kopannia, Siegfried
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Kopannia, Siegfried
description Various 1-phenylbut-3-enylidenes, (Ph)CCR2CHCHR‘, were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R‘CHCHC(Ph)CR2, were found to predominate over γ-C−H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R‘ = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R‘ = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point to vinyl migration in the singlet manifold. Benzophenone-sensitized generation of the carbenes led to partial stereomutation but did not provide conclusive evidence for a triplet rearrangement (isomerization of the diene products could not be avoided under these conditions).
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Org. Chem</addtitle><date>1998-02-20</date><risdate>1998</risdate><volume>63</volume><issue>4</issue><spage>1178</spage><epage>1184</epage><pages>1178-1184</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>Various 1-phenylbut-3-enylidenes, (Ph)CCR2CHCHR‘, were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R‘CHCHC(Ph)CR2, were found to predominate over γ-C−H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R‘ = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R‘ = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point to vinyl migration in the singlet manifold. 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title Stereochemistry of Carbenic 1,2-Vinyl Shifts
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