Reduction of DDHQ and TCC esters by NaBH4 - Its specificity in the presence of alkyl/aryl esters

Article abstract of DOI:10.1016/S0040-4020(01)80451-8

DDHQ/TCC esters 3a-f, 7a-g were prepared either by oxidation of spiroketones 1 with DDQ/o-chloranil or by condensation of acid chloride with DDHQ/TCC. NaBH₄ reduction of unsaturated DDHQ 3a-b and TCC 7a-c esters gave the corresponding allylic alcohols in good yield without any observable 1,4-addition products. Reduction of saturated esters 3e,7d, gave the corresponding alcohols. Alkyl esters 5 and 6, methyl benzoate and phenyl benzoate remained unaffected under these reduction conditions. In the reduction of compound 7e containing both alkyl and TCC esters, TCC ester is selectively reduced. Reduction of TCC mono esters 7f-g gave the lactones. The observed facile reduction has been rationalised.