ヌクレオシドの糖部分における炭素-炭素結合の構築 : 不飽和糖ヌクレオシドの有用性

抄録

Unsaturated-sugar nucleosides have been shown to serve as versatile substrates for constructing C-C bond at the sugar portion. Various types of appropriate reactions were adopted to 1', 2'-, 2', 3'-, 3', 4'-, and 4', 5'-unsaturated derivatives. These are electrophilic addition followed by substitution with organosilicon and organoaluminum reagents, radical-mediated 1, 2-acyloxy migration of the adducts, nucleophilic addition of benzenethiolate followed by radical substitution, aldol reaction of an enol ester, Pd-catalyzed cross-coupling and halogen-lithium exchange reactions of nucleosidic vinyl bromides, S_N2' reaction, addition reaction of carbon radicals, and epoxide ring opening with organometallic reagents. Consequently, C-C bond formation at the 1'-, 2'-, 3'-, 4'-, and 5'-positions of nucleoside became possible.