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ASYMMETRIC INDUCTION IN THE PHOTOCHEMISTRY OF CRYSTALLINE SALTS - STRUCTURE-REACTIVITY CORRELATIONS

TitleASYMMETRIC INDUCTION IN THE PHOTOCHEMISTRY OF CRYSTALLINE SALTS - STRUCTURE-REACTIVITY CORRELATIONS
Publication TypeJournal Article
Year of Publication1994
AuthorsGudmundsdottir, AD, Li, WN, Scheffer, JR, Rettig, S, Trotter, J
JournalMolecular Crystals and Liquid Crystals Science and Technology Section a-Molecular Crystals and Liquid Crystals
Volume240
Pagination81-88
Type of ArticleProceedings Paper
ISBN Number1058-725X
KeywordsPHOTOREARRANGEMENT
Abstract

The enantioselectivity of the di-pi-methane photorearrangement was studied in chiral crystals. Achiral dibenzobarrelene acids 1 and 2 were forced to crystallize as chiral crystals by salt formation with chiral amines. Photolysis of these salts in the solid state yielded photoproducts in > 95% enantiomeric excess. The absolute configurations of the salts and their photoproducts were determined. This allowed the absolute steric course of the di-pi-methane reaction to be mapped and the structural features that control the enantioselectivity to be identified. In contrast to the solid state photolyses, irradiations in solutions give only racemic photoproducts, presumably because the salts dissociated.

URL<Go to ISI>://A1994PU17000010