Document Detail


Theoretical Support for the Involvement of a Radical Pathway in the Formation of Allenylzincs from Propargyl Iodides and Dialkylzincs. Influence of Zinc Coordination.
MedLine Citation:
PMID:  23311748     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Propargyl iodides are good precursors for allenylzincs via reaction with diethylzinc, even in non-degassed medium. These reactions proceed via zinc/iodine exchange. Owing to the previously reported detection of propargyl radical by ESR experiments in this process a radical mechanism was suspected. Calculations of the C-Zn BDEs in allenyl- and propargylzinc species were performed with the CBS-QB3 method to demonstrate that propargyl radicals could undergo homolytic substitution at zinc. The stabilization of allenylzinc derivatives by chelation, made possible by the selection of appropriate ortho-substituted 3-phenylalkynyl iodides as precursors, was shown to influence the regioselectivity of their addition to aldehydes and ketones. The more stabilized is the chelated allenylzinc intermediate, the higher is the ratio of homopropargylic alcohols.
Authors:
Suribabu Jammi; Dominique Mouysset; Didier Siri; Michèle P Bertrand; Laurence Feray
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-13
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  -     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-14     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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