Intramolecular absolute asymmetric solid state

Since the concept of topochemically controlled reactions was established, various approaches to asymmetric synthesis using a solid-state reaction have been attempted, most actively by the research group at the Weismann Institute. Their studies have been concerned with the bimolecular reactions of chiral crystals in the solid state. In these studies, successful absolute asymmetric synthesis has been performed by using topochemically controlled four-centered photocyclodimerizations of a series of unsymmetrically substituted diolefin crystals. Research on reactivity in the crystalline state has been extended in recent years to a variety of new systems, and many absolute asymmetric syntheses have been provided. Successful examples of absolute asymmetric synthesis using chiral crystals are listed in Tables 2 to 4, which are divided into three categories intermolecular photoreaction in the solid state (Table 2), intramolecular photoreaction in the solid state (Table 3, A-D), and asymmetric induction in the solid-gas and homogeneous reactions (Table 4). 

Kohmoto et al. reported a fine example of absolute asymmetric synthesis involving the intramolecular [4 4- 4] photocycloaddition of 9-anthryl-Af-(naph-thylcarbonyl)carboxamide derivatives 42a-g in the solid state (Scheme 20) [26]. Out of seven carboxamides examined, 42a, 42e7 rid 42g showed intramolecular photocycloaddition in the solid state to give the [4 + 4] cycloadducts 43a, 43e, and 43g in almost quantitative yields after complete conversion and 42f gave 43f in 9% yield (Table 9). However, 42b, 42c, and 42d were unreactive. The crystals... 

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