US EPA

8711889 

Journal Article 

Highly Selective Nonenzymatic Chiral Induction into 3-Methylglutaric Acid and cis-4-Cyclohexen-l,2-ylenebis(acetic acid) Utilizing a Functional Five-Membered Heterocycle 4(R)-MCTT 

Nagao, Y; Ikeda, T; Inoue, T; Yagi, M; Shiro, M; Fujita, E 

1985 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

50 

21 

4072-4080 

English 

10.1021/jo00221a022 

Diamide 8, prepared by treatment of 3-methylglutaric acid (1) with 4(R)-MCTT (5) in the presence of DCC in pyridine, was subjected to aminolysis with 1 equiv of piperidine in CH2C12 at -30 °C to give a mixture of diastereomers 9a and 10a in a 88:12 ratio. Compound 9a, separated by silica gel column chromatography, was treated with various nucleophiles to give optically pure bifunctional synthons 11a-k in high yields. Highly selective chiral induction into ci's-4-cyclohexen-1,2-ylenebis(acetic acid) (4) was also performed. Aminolysis of 19 with 1 mol equiv of piperidine gave a mixture of 20 and 21 with 94% selectivity of the former. Similar chiral induction into cis-cyclohexan-1,2-ylenebis(acetic acid) (23) was tried. Aminolysis of its 4(R)-MCTT diamide (24) with piperidine gave 25 and 26 in a 89:11 ratio; the opposite selectivity was obtained with 19. The conformations of 19 and 24 in a solvent, the relationship between the susceptibility of their conformations and environmental temperature, and the diastereoselectivity of the reaction are discussed on the basis of the 400-MHz NMR 1H spectra. 1985, American Chemical Society. All rights reserved.