Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction.

Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction. Research Abstract Details 

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Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction. Abstract Text:

Julius T Su,Richmond Sarpong,Brian M Stoltz,William A Goddard,

The substrate scope for a ketene-assisted Cope (tandem Wolff-Cope) reaction is elucidated from first-principles quantum mechanics. An alternate pathway (trans) leading to an undesired and unstable product lies perilously close ( approximately 2.5 kcal/mol) to the primary (cis) reaction pathway; this near-degeneracy arises from preferential ketene stabilization of a radicaloid trans transition state over an aromatic cis transition state. Normally, substitution at "forbidden" sites causes the alternate pathway to be favored and the reaction to fail, but using simple conformational analysis principles we design substrates that defy this rule.

Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction. Publishing Authors By Initials

JT Su,R Sarpong,BM Stoltz,WA Goddard,

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Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 126

Page Numbers: 24-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 14

MONTH: Jan

YEAR: 2004

Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction. Information

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LANGUAGE: eng

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Grant and Affiliation Information for Substituent effects and nearly degenerate transition states: rational design of substrates for the tandem Wolff-Cope reaction.

AFFILIATION: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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