The solid phase synthesis of tertiary hydroxyesters from symmetrical diacid chlorides using organomanganese reagents

Abstract

A 1% crosslinked divinylbenzene–styrene copolymer, incorporating benzyl alcohol groups, was used to monoblock the symmetrical diacid chlorides, ClOC(CH2)nCOCl (where n = 4 and 8). Further reaction of the polymer-bound monoester monoacid chloride with phenylmanganese iodide or butylmanganese iodide gave their respective polymer-bound tertiary hydroxyesters. Subsequent base cleavage and esterification yielded methyl 6-hydroxy-6, 6-diphenylhexanoate, methyl 10-hydroxy-10,10-diphenyldecanoate, methyl 6-butyl-6-hydroxydecanoate, and methyl 10-butyl-10-hydroxytetradecanoate and some recovered dimethyl alkanoates. The reactions of some polymer-bound monoester monoacid chlorides with phenylcadmium chloride were also studied.

Chemistry of Organomanganese(II) Compounds

“…Finally, organomanganese iodides were used in solid-phase synthesis for the chemoselective conversion of carboxylic acid chlorides to tertiary alcohols (one-pot acylation/1,2-addition procedure) …”

Solid-Phase Synthesis of Isoxazoles Using Vinyl Ethers as Chameleon Catches

“…Several authors have studied the synthesis of isoxazoles using solid-phase chemistry . These include the condensation of 1,3-dicarbonyl compounds with hydroxylamine, the addition of nitrile oxides to supported alkynes, or the anchoring of a nitrile oxide precursor onto the solid phase . However, all methods suffer from a lack of regioselectivity, and the linker remains unchanged in the released product.…”