ISSN:
0009-2940
Keywords:
Chromium complexes
;
Carbene ligands
;
alkenyl-substituted
;
[2 + 1] Cycloaddition
;
Vinylcyclopropane→cyclopentene rearrangement
;
Cyclopropanes
;
donor-acceptor-substituted
;
Pyrrole derivatives
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Formation of Vinylcyclopropane and Cyclopentene Derivatives from Alkenyl-Substituted Chromium Carbene Complexes: Competition between Formal [2 + 1] and [3 + 2] Cycloadditions.The alkenyl-substituted chromium carbene complexes 1 - 4 were synthesized following the method of Aumann which starts from the corresponding aldehydes. At 80°C the styryl-substituted complex 1 and electron-deficient olefins smoothly provide vinylcyclopropane derivatives 6,8, 10, and 12 in good yields. On the other hand, methyl acrylate and the anisyl- and furyl-substituted vinylcarbene complexes 2 and 3 give mixtures of the expected vinylcyclopropanes and of cyclopentene derivatives. The pyrrolyl-substituted complex 4 and methyl acrylate exclusively afford the cyclopentenes 24a/b which are the result of a hitherto unprecedented formal [3 + 2] cycloaddition of the vinylcarbene complex to the olefin. However, there are strong arguments suggesting the corresponding vinylcyclopropanes as intermediates. The very smooth vinylcyclopropane→cyclopentene rearrangement probably occurs via zwitterionic intermediates that are wellstabilized by donor and acceptor substituents. Hydrolysis of 24a/b to the cyclopentanone derivatives 25a/b demonstrates that this new route to five-membered carbocycles should have synthetic potential.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240441
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