**7. References**

76 Advances in Crystallization Processes

effectively transferred to the products. The THF solution of (*S*,a*R*)-**20** containing methacrylonitrile was irradiated with a high-pressure mercury lamp for 2 hrs until the starting amide was consumed. When the reaction was performed at 20°C, two 2 + 2 adducts, major (1*S*,2a*R*,8b*R*)-**23** and minor (1*R*,2a*S*,8b*S*)-**23** were obtained in 99% yield. As expected, epimerization was strongly controlled at this temperature, and a high *de* of 89% was achieved. Even at low temperature, the reaction proceeded effectively, and after decreasing the temperature, the *de* values improved; the best *de* of 98% was obtained in the reaction at -80°C. The axial chirality evoked by crystallization directed the course of the approach of the reacting molecules, and a fully controlled diastereoselective intermolecular

New aspects of chemistry are deployed by effectively utilizing the unique nature of crystals. In this chapter, a new approach to asymmetric chemistry using chiral crystals found in our research groups is introduced. We succeeded in transferring the chirality expressed by chiral crystallization of achiral substrate to products in a variety of reactions in homogeneous systems. Stereoselective reaction using chiral crystals was limited to the topochemical solidstate photoreaction, and the reactions expanded in a homogeneous system were able to achieve the highly stereoselective asymmetric reaction. Some readers may think that chiral molecules possessing memory effects introduced in this chapter are like acrobats using a very narrow energy band. Figure 19 shows an energy diagram for racemization of chiral molecules that express chirality by spontaneous crystallization or by Crystallization-Induced Enantiomer Transformation (CIET). We can effectively use molecules with

Fig. 19. Energy diagram for racemization of axially chiral and achiral materials available for

asymmetric synthesis via spontaneous chiral crystallization

photocycloaddition reaction was performed.

**6. Prospects for new asymmetric reaction using crystal** 


Asymmetric Reaction Using Molecular Chirality Controlled by Spontaneous Crystallization 79

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**Section 2** 

**Crystallization of Amorphous** 

**and Glassy Materials** 

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