Document Detail


Palladium-Catalyzed Cross-Coupling of Aziridinyl-Metal Species, Generated by Sulfinyl-Magnesium Exchange, with Aryl Bromides: Reaction Optimization, Scope, and Kinetic Investigations.
MedLine Citation:
PMID:  23311879     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
A series of novel, highly substituted N-PMP aziridines have been accessed in high yields by palladium-catalyzed cross-coupling of intact aziridines. The cross-coupling employed aryl bromides and tertiary organometallic aziridines, generated from sulfinyl aziridines by sulfinyl-magnesium exchange and transmetallation to the aziridinyl-zinc with zinc chloride. A wide range of electron rich and electron poor aryl bromides were utilized to afford the functionalized aziridine products as single diastereoisomers with retention of configuration at the reacting center. Assessment of the reaction kinetics showed zero-order in both the aziridine species and the aryl bromide. This indicated that the rate-determining step was reductive elimination from the palladium (II) species bearing both the aziridine and aryl groups, to form the hindered C-C bond. The intermediate aziridinyl zinc species underwent a progressive, background degradation that led to a plateau in yield and afforded reduced yields in substrates with ortho-substituted aryl groups, which are less reactive due to the additional steric demands.
Authors:
Matthew Hughes; Tom Boultwood; Gianfranco Zeppetelli; James A Bull
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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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