supramolecular photodimerization of coumarins超分子的香豆素类光二聚.pdfVIP

Molecules 2012, 17, 1408-1418; doi:10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Review Supramolecular Photodimerization of Coumarins Koichi Tanaka Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan; E-Mail: ktanaka@kansai-u.ac.jp; Tel.: +81-06-6368-0861; Fax: +81-06-6339-4026 Received: 10 January 2012; in revised form: 31 January 2012 / Accepted: 1 February 2012 / Published: 3 February 2012 Abstract: Stereoselective photodimerization of coumarin and its derivatives in supra- molecular systems is reviewed. The enantioselective photodimerization of coumarin and thiocoumarin in inclusion crystals with optically active host compounds is also described. Keywords: photodimerization; coumarin; stereoselective reaction; supramolecular system 1. Introduction Photodimerization of coumarin and its derivatives has been studied extensively [1–5]. However, it is usually difficult to control the regio- and stereoselective [2+2] photodimerization of coumarins both in solution and in the solid state (Scheme 1). For example, the direct photoirradiation of coumarin in benzene afforded a mixture of syn–head–head 2, anti–head–head 3, syn–head–tail 4 and anti–head–tail 5 in the ratio 2.3:91.2:2.3:4.2, albeit in a low conversion of only 9% [4]. In contrast, photodimerization in 1,2-ethanediol gave a mixture of 2, 3, 4 and 5 in the ratio 59:22:19:0 in higher conversion (39%). The product ratio is also influenc