Cyclodehydration Diethoxytriphenylphosphorane

Trimethylamine N-oxide, 325 Vinyltrimethylsilane, 343 Other reactions (Phenylsulfonyl)allene, 247 Cyclodehydration Diethoxytriphenylphosphorane, 109 Hexamethylphosphoric triamide, 142 Cycloprop anation Simmons-Smith reaction Diiodomethane-Diethylzinc, 276 Simmons-Smith reagent, 275 by other reagents which add CH2 to a carbon-carbon multiple bond Dibromomethane-Zinc-Copper(I) chloride, 93... 

Diethoxytriphenylphosphorane (the product of insertion of triphenylphosphine into diethyl peroxide) finds use as a mild, neutral reagent which initiates cyclodehydration of N- and C-substituted g-aminoalcohols to form aziridines in excellent yield,... 

The pioneering work of Denney et ai19 on the synthetic utility of oxyphosphoranes has been thoroughly exploited by Evans et al. in demonstrating that diethoxytriphenylphosphorane promotes mild and efficient cyclodehydration of diols (e.g. 11) to cyclic ethers (e.g. 13) via the cyclic phosphorane (12)20>21. Simple 1,2-, 1,4-, and 1,5- diols afford good yields of the cyclic ethers but 1,3-propanediol and 1,6-hexandiol give mainly 3-ethoxy-l-pro-panol and 6-ethoxy-l-hexanol respectively whereas tri- and tetra-substituted 1,2-diols afford the relatively stable 1,3,2- diox-phospholanes. In some instances (e.g. 14), ketones (e.g. 16) are formed by a synchronous 1,2-hydride shift within (15). The synthetic utility has been extended to diethoxyphosphoranes supported on a polystyrene backbone22. 

Diethoxytriphenylphosphorane, (C6H5),P(OC2H5)2 (1). The phosphorane is obtained by reaction of diethyl peroxide (caution) with triphenylphosphine at 0-70°. Cyclodehydration of dioIs to ethers. 1,3-, 1,4-, and 1,5-Diols react with 1 to... 

Murray, W.T., Kelly, J.W., and Evans, S.A., Jr., Synthesis of substituted 1,4-oxathianes, mechanistic details of diethoxytriphenylphosphorane — and triphenylphosphine/tetra-chloromethane — promoted cyclodehydrations and 13C NMR spectroscopy, J. Org. Chem., 52, 525, 1987. 

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