Organoiodinane Reagents for Phosphate Cleavage: Experimental and Computational Studies

摘要

Several analogues of 1-oxido-1,2-benziodoxol-3(1H)-one, 1 (the valence tautomer of o-iodosobenzoate), were examined for their ability to cleave p-nitrophenyl diphenyl phosphate in aqueous micellar cetyltrimethylammonium chloride at pH 8. These included the 5,5-dimethyl (7) and 5,5-bis(trifluoromethyl) (8) analogues, as well as the parent 1-oxidoiodoxol-(3H)-ones 9 and 10. The results are discussed in terms of the relative acidities shown by the I-OH forms of the catalysts and the nucleophilicities of their I-O conjugate bases. Ab initio molecular orbital calculations were performed on 10, its conjugate acid (10-OH), the desoxo analogues (11, 11-OH), and their dimethyl (12, 12-OH) and bis(trifluoromethyl) (13, 13-OH) derivatives to aid this analysis. The electronic structures of these species are discussed in detail. Keywords: Reprints, Organic chemistry. (JES)