Design of Reactions in Crystals

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Several new chiral host compounds were designed. Some of these showed very efficient inclusion and chiral recognition abilities for various kinds of guest compounds. By using the inclusion complexation for racemic guests, optical resolution of the guest has been accomplished very efficiently. Especially, the host which has been derived from chloranile and chiral acetylenic alcohol showed extremely high chiral recognition ability for various guests.Enantioselective photoreactions of prochiral guest compounds in their inclusion crystals with chiral hosts have been investigated, and some very efficient enantioselective photocyclization reactions have been established. One kind of guest compound formed two kinds of inclusion crystals with a chiral host compound in 1 : 1 and 2 : 1 ratios, which upon photoirradiation gave (-) - and (+) -photoreaction products, respectively. In these inclusion complexes, the gusest molecule would be arranged in opposite chiral positions.Some thermal solid state reactions have also been established. Molecular movement from crystal to crystal has been studied by successive measurements of IR spectra in the solid state and by X-ray structure analysis of crystals. We finally found that the molecular movement from crystal to crystal is accerelated in the presence of a small amount of liquid such as liquid paraffin, silicon oil and water. We also established a new method to be also to follow molecular movement and arrangement in a chiral form in crystal by measurement of CD spectra of crystal in Nujol mull.