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Media type:
E-Article
Title:
New Insights on the Mechanism of the Transition‐Metal Stereoselective Olefin Cyclopropanation
Contributor:
Soriano, Elena;
Marco‐Contelles, José
Published:
Wiley, 2008
Published in:
Chemistry – A European Journal, 14 (2008) 22, Seite 6771-6779
Language:
English
DOI:
10.1002/chem.200800305
ISSN:
0947-6539;
1521-3765
Origination:
Footnote:
Description:
AbstractWe have carried out a theoretical analysis of the intermolecular cyclopropanation of propargylic esters with alkenes. DFT calculations allow us to propose a reaction mechanism, and provide explanations for the reasons behind the difference between the inter‐ and intramolecular versions of this process. The results strongly suggest that the entropic effects could modulate the operative mechanism and account for the mechanistic discrepancy. The calculated model also justifies the experimental stereoselectivity on the basis of intra‐ and intermolecular interactions. In addition, we have taken into account other transformations of propargylic carboxylates catalyzed by late transition metals, and the results rationalize the accumulated experimental observations.