Photoreactions of γ,δ-Unsaturated Chromium Carbene Complexes

A number of functionalized γ,δ-unsaturated chromium carbene complexes were synthesized, and their photochemistry was studied. Photolysis of carbene complexes 5 and 17 induced intramolecular [2 + 2] cycloaddition to afford cyclobutanones 6 and 18, respectively. If the photoreactions were not run in t...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 118; no. 34; pp. 7873 - 7880
Main Authors Moser, William H, Hegedus, Louis S
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 28.08.1996
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
AROMATIC ALCOHOLS
KETENES
SALTS
CYCLOADDITIONS
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Summary:A number of functionalized γ,δ-unsaturated chromium carbene complexes were synthesized, and their photochemistry was studied. Photolysis of carbene complexes 5 and 17 induced intramolecular [2 + 2] cycloaddition to afford cyclobutanones 6 and 18, respectively. If the photoreactions were not run in thoroughly degassed solvents, small amounts of lactones 7 and 19 were obtained as well. Cyclobutanones 6 and 18 were stable once isolated, but underwent an acid-catalyzed Pinacol rearrangement/hydrolysis transformation in acidic solution to afford novel α-hydroxy-substituted bicyclo[3.1.0]hexanone compounds 20 and 21. Photolysis of cyclopropyl carbene complex 28 induced a vinylcyclopropyl rearrangement involving the photogenerated ketene moiety to provide α-alkoxy cyclopentenone 29.
Bibliography:Abstract published in Advance ACS Abstracts, August 1, 1996.
istex:F1C50C95285037FE8FB8B78F6EF8F070710FA575
ark:/67375/TPS-XKC8FL8T-P
ISSN:0002-7863
1520-5126
DOI:10.1021/ja9537585