ISSN:
0899-0042
Keywords:
atropisomerism
;
gossypol stereochemistry
;
molecular mechanics
;
circular dichroism
;
anhydrogossypol
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The optical stability of gossypol [1,1',6,6',7,7'-hexahydroxy-3,3'-dimetyl-5,5'-bis(1-methylethyl)-2,2'-binaphthalene-8,8'-dicarboxaldehyde], a natural product exhibiting profoundly enantiospecific antitumor and male antifertility action, was investigated by means of computational methods and thermal racemization experiments. The calculations on gossypol and several derivatives and model compounds were carried out using the MM2 force field; energies and geometries of minimum energy conformations, as well as structures along various inversion pathways, were calculated. According to the calculations, gossypol (the dialdehyde form) and its simple analogues are not thermally racemizable (energy barriers for rotational inversion above 50 kcal/mol). By contrast, the calculations suggest that the acetal tautomer of gossypol and its dehydration product (anhydrogossypol) are thermally racemizable, although the energy barriers are still relatively high (35-40 kcal/mol). Optically pure (+)-anhydrogossypol was prepared and characterized; its racemization became rapid only at high temperatures (180-200°C). When dehydration of gossypol was hindered (in aqueous solution), no racemization of gossypol was observed after prolonged heating at 90°C. © 1992 Wiley-Liss, Inc.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chir.530040403
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