Sulfonylaminates

There was no evidence of a second-order term in amine, nor did amine self-association account for the non-linear behaviour. Hammett p values (for variation of RNHSO2) determined for formation of the complex [S.amine] (p = 1.64) and for expulsion of the anion ( ONp) (pacyi = -1-78) are consistent with an E cB process and uncomplicated by any steric effects of bound amine in the complex. The value of Pacyi is identical with that reported previously for ElcB reaction of the same esters in 50% acetonitrile-water and much greater than for their 2-type reactions in chloroform. Consequently, an ElcB mechanism involving extensive S-O bond cleavage with the formation of a A(-sulfonylamine, ArN=S02, is supported. 

Pronucleophiles Serving as Ammonia Surrogates N,N-Diacylamines, Trifluoroacetamide and N-Sulfonylamines... 

Primary amines react with 1,3,2-benzodioxathiole 2,2-dioxide affording sulfonylamines (72), which themselves are readily hydrolyzed to sulfamic acid salts (Equation (13)) <80JOC5371> this two-step procedure represents a mild, high yielding method for the sulfamoylation of primary... 

In contrast to the reaction of Af-thionylanilinc, the analogous reaction of IV-sulfonylamines 42 with nitrilimines 41 is not regioselective. A mixture of regioisomeric thiatriazoles 43 and 44 is formed in this reaction along with a substantial amount of by-product 45 <1985M1321>. Because of the very low yield of 1,2,3,5-thiatriazoles, this method is not recommended for the preparation of these compounds (Equation 13) <1985M1321>. 

An extension of the synthetic applicability of lithium halomethanes is achieved by the simultanous presence of another main group heteroatom at the same carbon. Thus, if one of the chlorine atoms of dichloromethyllithium is replaced by a sulfonylamin group, the following products are obtained by reaction with electrophiles (Eq. (23)) 25). The substituted carbenoid can be converted to normal carbonyl adducts as well as to olefins and cyclopropanes. 

Hasegawa, Y, Ohkubo, T., Sogabe, K., et al. (2000) Luminescence of novel neodymium sulfonylaminate complexes in organic media. Angewandte Chemie International Edition, 39, 357. 

A method to synthesize amino sulfoxides 212 and 213 was developed based on the rearrangement of sulfinamides 211300 (equation 81). The adduct of phenyl sulfonylamine and quadricyclane, i.e. 1,2-thiazetidine-A-oxide 214, underwent smooth rearrangement to furnish the fused 1,4-thiazine-A-oxide 215301 (equation 82). 

The reaction of triphenylbismuth carbonate with cyclic 1,3-dicarbonyl compounds, such as dimedone and Meldrum s acid, gives highly stabilized triphenylbismuthonium ylides (Section 3.5.1). Moderately stabilized acyclic bismuthonium ylides can be prepared from triphenylbismuth dichloride and a 1,3-diketone or a 1,3-disulfone in the presence of a suitable base. A similar base-promoted reaction of triphenylbismuth dihalides with Al-sulfonylamines or amides has been used for the preparation of stabilized bismuthine imides bearing the Af-sulfonyl or Af-acyl moiety (Section 3.6.1). 

Imines are generated in situ from A -Boc a-sulfonylamines, therefore the adducts are useful precursors for coupling with ArB(OH)2. Chiral benzhydrylamine derivatives are obtained when the Rh-catalyzed reaction is conducted in the presence of the pyrrolidinodiphosphine 98. ... 

W.G. Grot, Heat-treated fluorocarbon sulfonylamine cation permselectivity, USP 3,969,285 (July 13, 1976). Jpn. Pat. JP 52-13228 (examined application). 

N-Sulfonylamine activation. Iminoiodine(III) compounds (which can serve as nitrene sources) are produced when sulfonamides are combined with PhI(OAc)2." In the presence of sulfides, A-sulfonylsulfilimines (R2S=NS02R ) are formed. ... 

Conjugate additions. The Yb(OTf)3-catalyzed addition of a chiral V-amino-2-methoxymethylpyrrolidine to alkenyl sulfones is crucial to a process for the synthesis of optically active p-sulfonylamines. ... 

Another series of inner anhydrides, namely that of the general formula X = S02, is found in the bottom row of the table the members are sulfenes, iV-sulfonylamines and sulfur trioxide, the inner anhydrides of, respectively, sulfonic, sulfamic and sulfuric acids. The analogy is again helpful one of the most conspicuous features of sulfur trioxide is its high reactivity toward water and other nucleophiles this property is shared by sulfenes and sulfonylamines7. 

Attempts were made to prepare a terminal 5,6-epiminofuranose derivative by treatment of 6-benzamido-6-deoxy-l,2-(9-isopropylidene-5-(9-methanesulfonyl-ot-D-glucofuranose with lithium aluminum hydride or sodium ethoxide. In both cases, only 6-benzamido-6-deoxy-l,2-(9-isopropylidene-ot-D-glucofuranose was obtained, indicating hydrolysis of the methanesulfonate. b. A-Aryl(alkyl)sulfonylamines.—In comparison with the preceeding method, eyelization of vicinal sulfonamido-sulfonates has two advantages formation of oxazolines is excluded, and the reaction proceeds more readily because of enhanced acidity of the N-H group and facile formation of the N anion, which is considered the reactive species. Lower temperatures and weaker bases are therefore sufficient to induce eyelization. 

Sodium hydride can also be used to deprotonate certain sp carbon atoms. Deprotonation of acyldiazomethanes using sodium hydride followed by treatment with Al-sulfonylamines gave N-tosyl diazoketamines in good yields (eq 53). ... 

Sulfonic acid amides (s. a. N-Sulfonyl..., Sulfonylamines) elimination of sulfur dioxide 24,278... 

---