Journal
SYNTHESIS-STUTTGART
Volume 53, Issue 4, Pages 699-712Publisher
GEORG THIEME VERLAG KG
DOI: 10.1055/s-0040-1707322
Keywords
alkynes; carbonyl compounds; cobalt; cycloaddition; 2H-pyrans
Categories
Funding
- National Institutes of Health (NIH) [GM 22479]
- National Science Foundation (NSF) [CHE 0907800]
- University of California at Berkeley
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The article discusses the reaction products of 1,7-octadiyne with acetone under specific conditions, as well as the exploration of the reaction scope, demonstrating the different behaviors of different substrates in the reaction process.
1,7-Octadiyne underwent [2+2+2] cycloaddition to acetone in the presence of eta(5)-cyclopentadienylcobalt(L)(L ') complexes to give (eta(5)-cyclopentadienyl)[(1,4,4a,8a-eta(4))-5,6,7,8-tetrahydro-3,3-dimethyl-3H-2-benzopyran]cobalt, in which the two triple bonds and the carbonyl moiety have combined to engender a 2H-pyran ring complexed to CpCo. The scope of this reaction was explored, including cocyclizations of ynals and ynones with bis(trimethylsilyl)acetylene, as well as all-intramolecular reorganizations of alpha,omega-diynals and -diynones. Two major trajectories were observed in the case of aldehydes, the (often minor) [2+2+2] pathway and a competing trail featuring a formal 1,5-hydride shift that results in CpCo-dienones. The latter is obviated for ketone substrates. Preliminary chemistry of selected complexes uncovered unprecedented reactions, such as acid-catalyzed ring openings and additions of amines, the latter providing access to novel carbon frames.
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