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    
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.
Matthew Hughes; Tom Boultwood; Gianfranco Zeppetelli; James A Bull
Related Documents :
23403109 - Plant-mediated synthesis of platinum nanoparticles and its bioreductive mechanism.
25065789 - Electrochemical degradation of nitrobenzene by anodic oxidation on the constructed tio2...
24099509 - Antifungal dimeric chalcone derivative kamalachalcone e from mallotus philippinensis.
24347049 - Direct amine-functionalisation of γ-fe2o3 nanoparticles.
25000199 - Kinetics and mechanisms of cylindrospermopsin destruction by sulfate radical-based adva...
23190249 - Coumarins from free ortho-hydroxy cinnamates by heck-matsuda arylations: a scalable tot...
2276139 - Synthesis of the enantiomers of 6-epicastanospermine and 1,6-diepicastanospermine from ...
25265819 - Design and synthesis of novel thiophenes bearing biologically active aniline, aminopyri...
20689409 - Is nitrous oxide use appropriate in neurosurgical and neurologically at-risk patients?
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:  -    
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

Previous Document:  Amplified and In Situ Detection of Redox-Active Metabolite Using a Bio-based Redox-Capacitor.
Next Document:  Organization and dynamics of the N-terminal domain of chemokine receptor CXCR1 in reverse micelles: ...