アラインを用いた複素環化合物の合成

Abstract

Synthesis of nitrogen, oxygen, sulfur, and selenium containing heterocycles from aryne intermediates was reviewed. Reaction of (2-trimethylsilylphenyl)phenyliodonium triflate with thiobenzophenones in the presence of CsF gave the corresponding [4+2] cycloadducts, whereas reaction with thiopivalophenones afforded the [2+2] cycloadducts. Reaction of selones with benzyne produced from (2-trimethylsilyl)phenyl triflate also produced benzoselenetes. In the case of selenofenchone, initial cycloadduct further reacted with another molar of benzyne to give the corresponding selenoxanthene. Benzyne also reacted with ortho-substituted hydroxybenzoyl derivatives to afford the xanthene derivatives. Three component reaction involving benzyne, THF, and chloroform afforded phenyl ω-trichloroalkyl ethers via 1,3-oxonium zwitterion intermediates. Carbon-carbon single bond insertion of benzyne into β-diketones followed by intramolecular aldol reaction gave 4-substituted 2-naphthols regioselectively, which further oxidized by vanadium oxide to afford 4,4’,2,2’-binaphthols in good yields. This methodology would be applicable for the synthesis of biologically or pharmaceutically active products such as isocoumarins and benzodiazepines in one-pot operation.