Reactivities of novel [hydroxy(tosyloxy)iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes for alpha-tosyloxylation and alpha-phosphoryloxylation of ketones.

Novel [hydroxy(tosyloxy)iodo]arenes bearing 2-thienyl, 3-thienyl, N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifluoromethy)phenyl as an aromatic group, and [hydroxy(phosphoryloxy)iodo]arenes bearing N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifluoromethy)phenyl as an aromatic group, were prepared. alpha-Tosyloxylation and alpha-phosphoryloxylation of ketones with these compounds were carried out, respectively. Their reactivities were compared with that of the parent [hydroxy(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)iodo]benzene, respectively, and consequently [hydroxy(tosyloxy)iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes bearing 3-trifluoromethylphenyl and 3,5-bis(trifluoromethy)phenyl as an aromatic group showed the best reactivity. These new compounds can be used as powerful alpha-tosyloxylation and alpha-phosphoryloxylation reagents, instead of the parent [hydroxy(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)iodo]benzene.