Document Detail


Enantiomerically pure trans-beta-lactams from alpha-amino acids via compact fluorescent light (CFL) continuous-flow photolysis.
MedLine Citation:
PMID:  20698705     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Photolysis of alpha-diazo-N-methoxy-N-methyl (Weinreb) beta-ketoamides derived from enantiomerically pure (EP) alpha-amino acids affords the corresponding EP beta-lactams via an intramolecular Wolff rearrangement. The photochemistry is promoted with either standard UV irradiation or through the use of a 100 W compact fluorescent light; the latter affords a safe and environmentally friendly alternative to standard photolysis conditions. A continuous-flow photochemical reactor made from inexpensive laboratory equipment reduced reaction times and was amenable to scale-up. The diastereoselectivity (cis or trans) of the product beta-lactams has been shown to vary from modest to nearly complete. An extremely facile, atom-economical method for the epimerization of the product mixture to the trans isomer, which is generally highly crystalline, has been developed. Evidence for C3 epimerization of Weinreb amide structures via a nonbasic, purely thermal route is presented. Subsequent transformations of both the Weinreb amide at C3 (beta-lactam numbering) and the amino acid side chain at C4 are well-tolerated, allowing for a versatile approach to diverse beta-lactam structures. The technology is showcased in the synthesis of a common intermediate used toward several carbapenem-derived structures starting from unfunctionalized aspartic acid.
Authors:
Yvette S Mimieux Vaske; Maximillian E Mahoney; Joseph P Konopelski; David L Rogow; William J McDonald
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  132     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2010 Aug 
Date Detail:
Created Date:  2010-08-11     Completed Date:  2010-11-30     Revised Date:  2013-05-29    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  11379-85     Citation Subset:  IM    
Affiliation:
Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, USA.
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MeSH Terms
Descriptor/Qualifier:
Amino Acids / chemistry*
Lactams / chemistry*
Lighting / methods*
Photolysis*
Stereoisomerism
Substrate Specificity
Grant Support
ID/Acronym/Agency:
R25 GM058903-12/GM/NIGMS NIH HHS; R25GM58903/GM/NIGMS NIH HHS; S10RR019918/RR/NCRR NIH HHS
Chemical
Reg. No./Substance:
0/Amino Acids; 0/Lactams
Comments/Corrections

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