Enantioselective Syntheses of (-)- and (+)-Homocitric Acid Lactones.
Highly enantioselective syntheses of enantiomers of homocitric acid lactones (R)-5a and (S)-5b are described. Thermal Diels-Alder cycloadditions of 2a and 2b to 1,3-butadiene produced adducts 3a and 3b, respectively. Oxidative ozonolysis of latter adducts gave products 4a and 4b which after acid treatment afforded a mixture with 5a and 5b as major component. Acid lactones 5a and 5b were converted into their dimethyl esters 6a and 6b which were purified by chromatography. After saponification, the products obtained were crystallized to yield (-)- and (+)-homocitric acid lactones ((R)-5a and (S)-5b). Diastereomeric excess (de) of Diels-Alder adducts 3a and 3b was determined by means of Mosher esters of glycols 8a, 8b, and racemic 8. Diels-Alder cycloaddition products of lactones 2a and 2b to 1,3-butadiene showed a diastereoselectivity of 96%.
Rodríguez R
Gastón H.
GH
Laboratoire de Chimie Organique Biologique Associé au CNRS 31, Institut de Chimie, Faculté de Chimie, Université Louis Pasteur, 1, rue Blaise Pascal, F67008 Strasbourg, France.
Biellmann
Jean-François
JF