Dimethylphosphinothioate

Peptide synthesis in methanol or ethanol.1 The dimethylphosphinothioic anhydrides prepared from N-protected amino acids with 1 are stable to water or alcohols in the absence of a base, probably because of the P=S bond. As a consequence these active esters can be used for peptide syntheses in methanol or... 

Inazu, T, Hosokawa, H, Satoh, Y, Glucosylation using glucopyranosyl dimethylphosphinothioate,... 

Yamanoi, T, Nakamura, K, Takeyama, H, Yanagihara, K, Inazu, T, New synthetic methods and reagents for complex carbohydrates. 8. Stereoselective a- and 3-mannopyranoside formation from glycosyl dimethylphosphinothioates with the C-2 axial benzyloxyl group. Bull. Chem. Soc. Jpn., 67, 1359-1366, 1994. 

Inazu, T, Yamanoi, T, A novel glycosylation reaction of 2-amino-2-deoxy-D-glucopyranose using dimethylphosphinothioate, Chem. Lett., 69-72, 1989. 

An intriguing system using mannosyl dimethylphosphinothioate 41 was developed by Inazu and coworkers [62] (O Scheme 20). When reacted with glucose-derived acceptor 42 in the... 

Studies on the alkaline hydrolysis of various phosphonic and phosphinic esters have provided information on the electronic or steric effects of substituents and the effects of changes in reaction conditions amongst the substrates so extensively examined are the O-aryl esters of dimethylphosphinothioic acid (552) esters of diphenylphosphinic acid and O-aryfand S -aryf esters of diphenylphosphinothioic acid (553 Z, Y = O or S). Other studies have concentrated on aryl esters of diaryIphosphinic acids (554) , and the effects of the stepwise replacement of P-Me by P-Ph in esters of dimethyl-, methylphenyl- and diphenyl-phosphinic acids The esters 555 (R = EtO, R = Me or Ph, R = R = Ph X = SEt or hydrolyse under alkaline conditions faster than do the comparable 5 -(4-substituted-butyl) esters. Comparable steric and electronic influences on the hydrolyses of phosphonic and phosphinic fluorides phosphinic chlo-rides the phosphonothioic chlorides 556 and other phosphonic and phosphinic esters have been noted. Phosphonic and phosphinic halides are prone to undergo halo-gen-exchange reactions, a process which, in general, is faster for derivatives of phosphonic than for those of phosphonothioic and phosphonoselenoic acids, and to be particularly important for acid fluorides . ... 

Startg. methyl glycoside in benzene added to a mixture of 3,4,6-tri-0-benzyl-2-benzyloxycarbonylamino-2-deoxy-a-D-glucopyranosyl dimethylphosphinothioate. 

Branched Homotrisaccharides.— By use of glycosyl dimethylphosphinothioate derivatives the branched mannotriose a-D-Maiip-(l- 6)-[a-D-Manp-(l->3)]-D-Man has been prepared. ... 

A soln. of bromine in GGI4 added dropwise below 0° to a well-stirred mixture of tetramethyl bi (phosphine sulfide) and GGI4, stirring continued a few hrs. at room temp., then distilled in vacuo dimethylphosphinothioic bromide. Y 94%. H.J. Harwood and K. A. Pollart, J. Org. Ghem. 28, 3430 (1963). 

---