Inclusion crystals enantioselective photochemical

Reviews of general interest in this area highlights microreactors that can be used for a variety of photochemical reactions such as the synthesis of large ring ketones. Interest in the control that can be exercised on the outcome of photochemical reactions in constrained environments continues to increase and reviews dealing with the enantioselective photoreactions of achiral compounds in chiral crystals and inclusion crystals have been published. ... 

Enantioselective photodimerization of coumarin (97) was accomplished in the inclusion complex (100) with 12a. For example, irradiation of the 1 1 inclusion compound of 97 with 12a gave the anti-head-to-head dimer (—)-98 of 96% ee in 96% yield [52], This photochemical reaction of 100 to the complex (101) of 98 was also found to proceed by a single-crystal to single-crystal manner. However, 1 2 inclusion compound of 11 and 97 gave the. vw-head-to-head dimer (99) upon irradiation in 75% yield [53],... 

Since photochemical reactions in inclusion compounds have been described in one chapter of the previous book [1], enantioselective (3-lactam formation reactions are summarized in this present chapter as a typical application of the inclusion technique for enantioselective photosynthesis. In addition, as a representative enantioselective single-crystal-to-single-crystal photoreaction, the photodimerization reactions of coumarin and thiocoumarin in their inclusion compound with a chiral host are also described. Furthermore, a host-catalyzed photodimerization reaction of chalcone and 2-pyridone in the solid state is also added to this chapter as a unique example of the application of inclusion techniques to selective photoreaction. 

Scheme 8. Enantioselective Photoreactions in TADDOL Inclusion Compounds with a Cou-marin, a Methacryl Anilide, and an Oxocyclohexenyl-carboxamide. In the first case, the packing of the coumarin molecules in the mixed crystal is such that the double bonds are predisposed for the (2+2) cycloaddition. In the second example, a photochemical electrocychc reaction is followed by a sigmatropic H shift. The third reaction is an intramolecular (2+2) cycloaddition with dia- and enantioselective formation of three new stereogenic centers. There are several more reactions of this type, described in the literature [54], and the Toda group has determined the crystal structures of a number of inclusion compounds to show the correlation between the crystal packing and the configuration of the photoproducts. EMastereoselective solid-phase reactions of chiral guests in TADDOL-host lattices have also been described by the...

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