Synthetic applications of N-carboalkoxysulfamate esters

Oxidation of diethyl N‐sulfinylphos‐phoramidates

“…of iodosobenzene (2). The formation of two products, namely the N,Nbis(diethyl phosphor)sulfamide (3a) and diethyl phosphoramidate (4a), was registered by 31 P NMR in this reaction (Scheme 1).…”

“…The performed oxidations of N-sulfinylphosphoramidate 1a by iodosobenzene (2), and/or iodoxybenzene (5) in the presence of benzyl alcohol, ethanol, or phenol, in dichloromethane in the wide range of temperature, gave no evidence of formation of the N-phosphoryl sulfamates in these reactions. However, in the reaction of 1a with cumene peroxide (8) in the presence of 2,2-dimethyl-propan-1-ol (9) at low temperature in dichloromethane the formation of two products was observed in the 31 P NMR spectra.…”

“…By Iodosobenzene (2). The suspension of 0.092 g (0.42 mmol) of 2 in the solution of 0.085 g (0.42 mmol) 1a in 10 mL dry acetonitrile was stirred for 1 h at room temperature.…”

“…N-sulfonylamines, the structural analogs of sulfur trioxide, have been prepared previously [1][2][3] and are used as highly reactive electrophiles [4][5][6][7][8][9][10][11]. They are mostly available by the dehydrohalogenation of sulfamic acid chlorides as a compound stable only at low temperature in the solution (Eq.…”

Burgess Reagent ([Methoxycarbonylsulfamoyl]triethylammonium Hydroxide, Inner Salt): Dehydrations and More

“…In 1970, E. Burgess et al [1] discovered, that treatment of secondary and tertiary alcohols 1 with the inner salt of (methoxycarbonylsulfamoyl)triethylammonium hydroxide (2) causes their smooth dehydration to the corresponding olefines 4 [2]. A mechanism has been proposed for the reaction, which involves a stereospecific syn-elimination via ion-pair formation from an intermediate sulfamate 3, comparable to the Chugaev elimination of dithiocarbonate (xanthate) esters and following Saytzeff's rule [1].…”