Philip L. Robinson

THE CHEMISTRY OF α, ω-MERCAPTOALCOHOLS IN THE PRESENCE OF DIETHOXYTRIPHENYLPHOSPHORANE. TEMPERATURE DEPENDENCE OF CYCLODEHYDRATIONS AND S-ETHYLATIONS

Abstract Diethoxytriphenylphosphorane (DTPP) is easily prepared by oxidative addition of triphenylphosphine with diethyl peroxide. DTPP converts a variety of mercaptoalcohols to cyclic sulfides as well as hydroxythioethers. The temperature dependence (+25 → −25°C) of the product distribution has synthetic potential.

The Synthetic Utility Of Dioxyphosphoranes In Organic Synthesis

Abstract Diethoxytriphenylphosphorane. DTPP. prepared by reaction of triphenylphosphine and diethyl peroxide. is a “hydrolytically active” dioxyphosphorane which promotes mild and efficient cyclodehydration of diols to cyclic ethers in neutral media. Simple 1,2-, 1,4-, and 1,5-diols afford good yields of the cyclic ethers but 1,3-propanediol and 1,6-hexanediol give mainly 3-ethoxy-1-propanol and 6-ethoxy-1-hexanol. respectively. with DTPP. Tri- and tetra-substituted 1,2-diols afford the relatively stable 1,3,2-dinxaphospholanes in the presence of DTPP and the reaction conditions dictate whether epoxides, ketones, or allylic alcohols are obtained.

Dioxyphosphoranes, an Emerging Class of Versatile Reagents for Organic Synthesis

Abstract Several [sgrave]-dioxyphosphoranes have been prepared and their structural characterizations using NMR techniques support the trigonal bipyramidal conformer as the most stable for the acyclic phosphoranes. Their utility in smooth conversions of hydroxylated substrates [HO(CHR)n XH, n=2–6; X=O,S,NH] to the corresponding X-heterocycles is documented.