Chiral templates glucose

K. Kakinuma, Y. Iihama, I. Takagi, K. Ozawa, N. Yamauchi, N. Imamura, Y. Esumi, and M. Uramoto, Diacetone glucose architecture as a chirality template. II. Versatile synthon for the chiral deuterium labelling and synthesis of all diastereomers of chirally monodeuterated glycerol, Tetrahedron 48 3163 (1992). 

Eguchi, T., Koudate, T., Kakinuma, K. Diacetone glucose architecture as a chirality template. III. The Overman rearrangement on a diacetone-D-glucose template kinetic and theoretical studies on the chirality transcription. Tetrahedron 1993, 49, 4527-4540. 

A novel series of chiral grass herbicides based on the benzyloxy substituted tetrahydrofuran ring system has been prepared. These compounds are readily accessible synthetically from diacetone-D-glucose which serves as a chiral template possessing the appropriate stereochemistry for elaboration to the active herbicides. The degree of herbicidal activity is related to the molecular shape of these compounds and especially to the orientation of the substituents around the tetrahydrofuran ring. The chemistry and empirical structure-activity relationships of these compounds will be discussed. 

In another paper from the Kakinuma group, further result on the chirality s transfer realized using the diacetone-D-glucose template was described [41]. 

A [2,3]- Wittig rearrangement carried out on a carbohydrate template has been used in a route to 3-alkyl malic acids, as indicated in Scheme 24. The product of opposite chirality at C-3 could be obtained from the cis-alkene, and transition-state models were proposed to rationalize the results.93 Somewhat similar intermediates were used in a synthesis of the stereospecifically-deuteriated ester (llO), required as a standard in a study of enzyme stereospeciflcity in this case C-3 of D-glucose became C-1 of the carbojqrlic acid by oxidative cleavage.94... 

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