Alkynylation of benzotriazole with silylethynyliodonium triflates. Regioselective synthesis of 2-ethynyl-2H-benzotriazole derivatives.

Phenyl(trimethylsilylethynyl)iodonium and tert-butyldimethylsilylethynyl(phenyl)iodonium triflates were applied to alkynylation of benzotriazole. Treatment of the silylethynyliodonium triflates with the potassium salt of benzotriazole ion in (t)BuOH and CH(2)Cl(2) gave 2-(trimethylsilylethynyl)-2H-1,2,3-benzotriazole and 2-(tert-butyldimethylsilylethynyl)-2H-1,2,3-benzotriazole in 74% and 76% yields, respectively. The regioisomers, 1-silylethynyl-1H-1,2,3-benzotriazole derivatives, were minor. In both cases of the silyl-substitued ethynyliodonium salts, novel regioselective alkynylation of benzotriazole at the 2 position was observed.

Preparation of optically pure α-trifluoromethyl-α-amino acids from N-tosyl-2-trifluoromethyl-2-alkyloxycarbonyl aziridine.

The preparation of optically pure α-trifluoromethyl-α-amino acids from N-tosyl-2-trifluoromethyl-2-alkyloxycarbonylaziridine is described. Optically pure aziridine was prepared with a 60% yield via three steps from optically pure 2,3-epoxy-1,1,1-trifluoropropane (TFPO). Ring-opening reactions of the aziridine with a variety of nucleophiles and subsequent deprotection of the N-tosyl moieties gave the optically pure ß-substituted-α-trifluoromethyl-α-amino acids in moderate to good yields (up to 85%) without racemization at the quaternary stereogenic center of the amino acid.