Journal article

Publication year: 2012

Pages: 3800-3807

Journal: The Journal of Organic Chemistry

Volume number: 77

Issue number: 8

ISSN: 0022-3263

DOI Link: https://doi.org/10.1021/jo3001035

Publisher: American Chemical Society

Abstract: 

Bicyclo[3.2.1]oct-6-en-8-ylidene (1) can assume either the conformation of “classical” carbene 1a or that of foiled carbene 1b in which the divalent carbon bends toward the double bond. Oxadiazoline precursors for the generation of 1
were prepared, followed by photochemical and thermal decomposition as
well as flash vacuum pyrolysis (FVP) of a tosyl hydrazone sodium salt
precursor, to give a number of rearrangement products. Matrix isolation
experiments demonstrate the presence of a diazo intermediate and methyl
acetate in all photochemical and thermal precursor reactions. The major
product from rearrangements of “classical” bridged carbene 1a is
bicyclo[3.3.0]octa-1,3-diene as a result of an alkyl shift, while
dihydrosemibullvalene formed from a 1,3-C–H insertion. In contrast, thus
far unknown strained bicyclo[4.2.0]octa-1,7-diene formed by a vinyl
shift in foiled carbene 1b. The experimental results are corroborated by density functional theory (DFT), MP2, and G4 computations.

Harvard Citation style: Brinker, U., Bespokoev, A., Reisenauer, H. and Schreiner, P. (2012) Conformations and Reactions of Bicyclo[3.2.1]oct-6-en-8-ylidene, The Journal of Organic Chemistry, 77(8), pp. 3800-3807. https://doi.org/10.1021/jo3001035

APA Citation style: Brinker, U., Bespokoev, A., Reisenauer, H., & Schreiner, P. (2012). Conformations and Reactions of Bicyclo[3.2.1]oct-6-en-8-ylidene. The Journal of Organic Chemistry. 77(8), 3800-3807. https://doi.org/10.1021/jo3001035