Sulfamides synthesis

Scheme 17.31 Enantioselective sulfamidate synthesis using ruthenium catalysis.

Bis(triarylphosphoranylidene)sulfamides and iV ,iV-dialkyl-iV -(triarylphosphoranylidene)-sulfamides, synthesis 30 Chlorine (I) nitrate, synthesis 33 Anhydrous metal chlorides, synthesis 35 Complexes of rhenium(V), synthesis 38... 

Phenyllead(IV) azides, synthesis 15 Tetraphosphorus hexamethylhexaimide, synthesis 16 Diphenyl phosphorochloridite, synthesis 17 Diphenylphosphinic acid, synthesis 18 (2,2-Dimethylhydrazino)diphenylphosphine, synthesis 19 Alkoxy- and aryloxycyclophosphazenes, synthesis 20 Mercapto derivatives of chlorocyclophosphazencs, synthesis 21 Dialkylsulfamoyl chlorides, synthesis 27 N- and J T,A1 -Substituted sulfamides, synthesis 28 Dialkylamides of (trichlorophosphoranylidene)sulfamic acid, synthesis 29... 

Bis(trichlorophosphoranylidene)sulfamide, synthesis 30 Aminomethanesulfonic acid, synthesis 31 Diperoxotriamminechromium(IV), synthesis 33 Tris(4-p-toluidino-3-penten-2-onato)chromium(III), synthesis 38... 

Of the various possible types of -substituted sulfamoyl (sulfamyl) chlorides, the dialkyl compounds are of particular interest because they serve as intermediates in the syntheses of substituted sulfamides (synthesis 28) and of certain of their derivatives (synthesis 29). The dialkyIsul-famoyl chlorides have been prepared by the reaction of sulfuryl chloride with an appropriate amine or its hydrochloride, " by the treatment of secondary 7V-chloroamines with liquid sulfur dioxide, and by the reaction of dialkyl-aminosulfinic acids with chlorine in carbon tetrachloride. Although either of the first two procedures can be recommended in terms of convenience and yield, the availability of starting materials normally dictates that the first be used. It is of interest that treatment of sulfuryl chloride with either ammonia or ammonium chloride in terms of this procedure does not give the parent sulfamoyl chloride, H2NSO2CI. This compound is obtained in an altogether different way. ... 

Bis(trichlorophosphoranylidene)sulfamide, synthesis 30 Tris(l,l,l-trifluoro-2,4-pentanedionato)chromium(lII), synthesis 35... 

Bower JF, Szeto P, Gallagher T. Enantiopure 1,4-henzoxa-zines via 1,2-cyclic sulfamides. Synthesis of levofioxacin. Org. Lett. 2007 9(17) 3283-3286. 

Cyclic sulfamides 326 serve as key intermediates in the synthesis of a series of potent and selective y-secretase inhibitors with potential for the treatment of Alzheimer s disease. 

Reaction of [ F]fluoride anion on cyclic precursors (epoxides [220], cyclic sulfonates [221], cyclic sulfamidates [222, 223]) is an efficient strategy for the stereospecific synthesis of )3- F-fluoroalcohols or )9- F-fluoroaniines. Typical examples are shown in Scheme 54. 

Intermolecular reactions of hydroxylamines with secondary alkyl halides and mesylates proceed slower than with alkyl triflates and may not provide sufficiently good yield and/or stereoselectivity. A nseful alternative for these reactions is application of more reactive anions of 0-alkylhydroxamic acids or 0-alkoxysulfonamides ° like 12 (equation 8) as nucleophiles. The resulting Af,0-disubstituted hydroxamic acids or their sulfamide analogs of type 13 can be readily hydrolyzed to the corresponding hydroxylamines. The same strategy is also helpful for synthesis of hydroxylamines from sterically hindered triflates and from chiral alcohols (e.g. 14) through a Mitsunobu reaction (equation 9). 

An improved method for the synthesis of a-fucosyl (l- 3)-3-thio-glycoside (65 c) involved the nucleophilic displacement of a cyclic sulfamidate derived from allosamine (67). The regioselective opening of (67) with (30b) led to (65c) in good yield (Scheme 21) [51]. 

Many of the most versatile and widely used syntheses of pyrimidines are straightforward examples of [3+3] condensations of amidines, guanidines, ureas and thioureas with 1,3-dielectrophiles, and clearly a considerable measure of control over the degree and nature of the substitution pattern in the final product is possible by appropriate choice of the two three-component units. Representative examples are given in equations (112)—(115), and the use of sulfamide in place of amidines, etc., allows the method to be extended to the synthesis of polyheteroatom systems e.g. equation 116). 

The general method for the synthesis of cyclic sulfamides including the respective l,l-dioxo-3,6-dihydro-thiadia-zepines 46 from 44 has been described <2003T6051> (Scheme 5) in which the yield of the final step was 75%. 

The cyclic sulfamidates of the allosamine derivative 126 (see Scheme 18) are prepared by reaction with 1,1 -sulfuryl diimidazole <1996CC127>, and this method seems to be promising for the synthesis of other sulfamidates. 

This methodology was successfully used for the synthesis of a-disposed sulfamidates of diverse carbohydrate templates (D-glucose, D-galactose, L-rhamnose) <2004JA6234, 2004CEJ5581>. 

The traditional synthesis of cyclic sulfimidates from /3-aminoalcohols and SOCl2 in the presence of amine as a base has been developed further to the preparation of the enantiopure monocyclic as well fused sulfimidates (Schemes 26 and 27). 1,2,3-Oxathiazolidine mono-.Y-oxides are readily oxidized to corresponding sulfamidates by RuCR and NalCb, and the synthesis of sulfamidates can be performed in a one-pot procedure from -aminoalcohols without isolation of intermediate sulfimidates (Equation 37). The reaction of sulfamate esters 145 with PhI(OAc)2 and various catalysts proved to be a reliable method for the enantioselective preparation of cyclic sulfamidates 146 (Equation 35). 

A class of HIV-l protease inhibitors extensively examined in our department are the cyclic sulfamides [73,74]. These compounds are related to our linear 1,2-dihydroxyethylene inhibitors described above in that they are also derived from L-mannitol and employ a 1,2-dihydroxyethylene transition-state isostere. These cyclic inhibitors are comprised of seven-membered rings where the sulfonyl oxygens are designed to displace a structural water in the enzyme when the inhibitors bind to the active site [73]. The synthesis of the... 

All the recorded derivatives of these systems have the sulfur atom in the fully oxidized state, the N—S02—N grouping being introduced by the use of sulfamide or a substituted derivative. The 3-unsubstituted 2,2-dioxopyrazolo[3,4-c][l,2,6]triazines (176) and (177 R = H) are formed by heating with sulfamide. With the substituted sulfamides, cyclization of the intermediate is achieved with either alcoholic sodium hydroxide or trifluoracetic acid in moderate yields (Scheme 17) <85S190>. In a similar synthesis (Equation (25)) the tetrahydro-2,2-dioxopyrazolo[4,3-c][l,2,6]thiadiazine (179) is formed from the aminopyrazole (178) <76IJC(B)766>. 

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