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2000 Alfred Bader Award Lecture - In the footsteps of Pasteur: asymmetric induction in the photochemistry of crystalline ammonium carboxylate salts

Title2000 Alfred Bader Award Lecture - In the footsteps of Pasteur: asymmetric induction in the photochemistry of crystalline ammonium carboxylate salts
Publication TypeJournal Article
Year of Publication2001
AuthorsScheffer, JR
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume79
Pagination349-357
Date PublishedApr
Type of ArticleArticle
ISBN Number0008-4042
KeywordsABSOLUTE-CONFIGURATION CORRELATION, ACID-DERIVATIVES, asymmetric synthesis, chiral auxiliaries, crystal structure-reactivity relationships, di-pi-methane, GEOMETRIC REQUIREMENTS, II REACTION, ionic chiral auxiliaries, ORGANIC-PHOTOCHEMISTRY, PHOTOCHEMISTRY, solid state, SOLID-STATE PHOTOCHEMISTRY, STRUCTURE-REACTIVITY RELATIONSHIPS, YANG PHOTOCYCLIZATION REACTION
Abstract

This review describes the development of a new, synthetically useful method of asymmetric synthesis in organic photochemistry. Similar in many ways to the Pasteur procedure for resolving racemic carboxylic acids and organic amines, the method relies on the use of crystalline organic salts in which the enantioselectivity of a photochemical reaction of an achiral organic ion (for example, a carboxylate anion) is governed in the solid state by the presence of an optically pure counterion (for example, an optically active ammonium ion). Such optically pure counterions are termed ionic chiral auxiliaries. Salts containing ionic chiral auxiliaries are required to crystallize in chiral space groups, which provide the asymmetric environment necessary for chiral induction. Using this methodology, we have obtained near-quantitative optical yields in a wide variety of photochemical reactions.

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