ChemInform Abstract: Synthesis and Properties of Covalent Organic Perchlorates

Abstract

ChemInform Abstract (141 refs. from 1841 to 1987).

Organic Polyvalent Iodine Compounds

“…Triflate 9 and perchlorate 166 are prepared from (diacetoxyiodo)benzene and aqueous perchloric or trifluoromethanesulfonic acid (eq 88). 286 In a more convenient procedure triflate 9 can be generated in situ from PhIO and triflic anhydride (eq 3, see Section III.A.1). 69 Both triflate 9 and perchlorate 166 react with alkenes to afford vic-diperchlorates or ditriflates; in the case of cyclohexene this reaction proceeds as a stereospecific syn-addition (eq 89).…”

“…57 Iodoalkanes react with triflate 9 and perchlorate 166 to give the respective products of oxidative substitution of iodine 167 in good yield (eq 90). 286 Sulfur trioxide can form two different adducts with PhIO (11 and 12) depending on the ratio of reactants (eq 5, see Section III.A.1). 73,91 Both sulfates 11 and 12 react with alkenes under mild conditions to give the respective cyclic sulfate esters, such as 168-170 (eqs 91 and 92).…”

“…Even very weak nucleophiles, such as perchlorate and triflate anions, can participate in the oxidatively assisted nucleophilic substitution of iodine. [351][352][353] Oxidation of alkyl iodides 261 in the presence of lithium perchlorate or tetrabutylammonium sulfonates in nonnucleophilic solvents affords the respective alkyl perchlorates or sulfonates 262 as principal products (eq 130). 256 The oxidatively assisted nucleophilic substitution of iodine with perchlorate anion in primary and secondary substrates most likely has an S N 2 mechanism as indicated by the stereochemistry of this reaction in the polycyclic substrates 263 (eq 131).…”

“…151,153,369,370 (Dicyano)iodonium triflate 286 generated in situ reacts with tributyltin derivatives of aromatic compounds 446 affording the corresponding diaryliodonium salts 441 (eq 226). 370 Since (dicyano)iodonium triflate (286) does not possess any pronounced electrophilic or oxidizing properties and is not acidic, it is especially useful for the synthesis of various bis(heteroaryl)iodonium salts from acid-sensitive substrates. 369 For example, reagent 286 reacts with stannylated derivatives of furan, thiophene, indole, and pyrazole under very mild condition to afford the respective iodonium salts 448, 450, and 452 in good yield (eqs 227-229).…”

“…Triflate 9 and perchlorate 166 are prepared from (diacetoxyiodo)benzene and aqueous perchloric or trifluoromethanesulfonic acid (eq 88) . In a more convenient procedure triflate 9 can be generated in situ from PhIO and triflic anhydride (eq 3, see Section III.A.1) .…”