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Photochemistry of 9-methylbicyclo[3.3.1]nonyl aryl ketones - A novel 1,5-disproportionation of 1,4-hydroxy biradicals and asymmetric induction using the solid-state ionic chiral auxiliary method

TitlePhotochemistry of 9-methylbicyclo[3.3.1]nonyl aryl ketones - A novel 1,5-disproportionation of 1,4-hydroxy biradicals and asymmetric induction using the solid-state ionic chiral auxiliary method
Publication TypeJournal Article
Year of Publication2005
AuthorsChen, S, Patrick, BO, Scheffer, JR
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume83
Pagination1460-1472
Date PublishedSep
Type of ArticleArticle
ISBN Number0008-4042
Keywords1, 4-hydroxy biradical, asymmetric, BEHAVIOR, CRYSTAL-STRUCTURE, disproportionation, HYDROGEN-BOND, INDUCTION, ionic chiral auxiliary, PHOTOCHEMISTRY, PHOTOCYCLIZATION, reaction, REACTIVITY CORRELATIONS, SALTS, single crystal-to-single crystal
Abstract

A novel 1.5-disproportionation reaction has been discovered for 1,4-hydroxy biradicals derived from the photolysis of 9-methylbicyclo[3.3.1]nonyl phenyl ketones (1), which undergo mainly Yang cyclization both in Solution and the solid state. By applying the solid-state ionic chiral auxiliary method of asymmetric synthesis to the Yang cyclization, enantiomeric excesses as high as 95% were achieved at high reaction conversions. The origin of the reaction selectivity is discussed with the help of X-ray crystallography. In addition, the solid-state photoreaction of ketone 1b was found to occur in a single crystal-to-single crystal fashion.

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