spin-dependent diastereoselectivity in the photocycloaddition of aldehydes to 2,2-dimethyl-2,3-dihydrofuranspin-dependent photocycloaddition选择性很大的醛,2-dimethyl-2 3-dihydrofuran.pdfVIP

Vol. 07 INTERNATIONAL JOURNAL OF PHOTOENERGY 2005 Spin-dependent diastereoselectivity in the photocycloaddition of aldehydes to 2,2-dimethyl-2,3-dihydrofuran Samir Bondock1,2 and Axel G. Griesbeck2,† 1 Department of Chemistry, University of Mansoura, Egypt 2 Institute of Organic Chemistry, University of Cologne, Greinstr. 4, D-50939 Köln, Germany Abstract. The simple (non-induced) diastereoselectivity of the photocycloaddition of aliphatic as well as aromatic aldehydes to 2,2-dimethyl-2,3-dihydrofuran (1) was analyzed as a function of the substrate concentration (spin mapping) and rationalized in terms of optimal spin-orbit coupling controlled triplet biradical geometries. 1. INTRODUCTION product is inverted when going from the triplet excited mesitylaldehyde to the singlet excited naph- The technique of “spin-mapping” of diastereoselec- thaldehyde as substrate. Two structural features tivities of bimolecular photochemical reactions is of made the conformational analysis of spin-inversion special relevance in reactions of electronically excited geometries straightforward: the two sites of the molecules and decisive in controlling and manipulating alkene part were strongly