Supramolecular Photodimerization of Coumarins 英文参考文献.docVIP

Molecules 2012, 17, 1408-1418; doi:10.3390/moleculeOPEN 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 influenced by the multiplicity of the excited states involved [5]. Photoreactions in the solid state are thought to require precise orientation and separation of the two reacting double bonds within the maximum separation distance of 4.2 ?, as postulated by Schmidt, and some successful examples have been reported. Ramamurthy and Venkatesan pioneered the solid state photochemistry of co