Document Detail


Origins of 1,6-stereoinduction in torquoselective 6π electrocyclizations.
MedLine Citation:
PMID:  23448287     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
A novel stereoselective electrocyclization developed for the total synthesis of reserpine has been explored by both experiment and theory. A stereocenter six atoms away from the newly forming chiral center is responsible for the diastereoselectivity of the ring closure. This stereogenic center, lying at the junction of two six-membered rings, defines the conformation of the substrates' fused ring skeleton that ultimately distinguishes between the two allowed, disrotatory triene geometries at the transition state. The presence of allylic strain in the disfavored transition state results in a torquoselective ring closure (dr up to 15.7:1).
Authors:
Ashay Patel; Gregg A Barcan; Ohyun Kwon; K N Houk
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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.     Date:  2013-03-18
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  135     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2013 Mar 
Date Detail:
Created Date:  2013-03-27     Completed Date:  2013-09-09     Revised Date:  2014-03-28    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  4878-83     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Antihypertensive Agents / chemical synthesis*
Cyclization
Electrons
Models, Molecular
Reserpine / chemical synthesis*
Stereoisomerism
Grant Support
ID/Acronym/Agency:
GM-36700/GM/NIGMS NIH HHS; R01 GM036700/GM/NIGMS NIH HHS; R01GM071779/GM/NIGMS NIH HHS; T32 GM 008496/GM/NIGMS NIH HHS; T32 GM008496/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Antihypertensive Agents; 8B1QWR724A/Reserpine
Comments/Corrections

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