Amino-sulfonation

Ethyleneimine reacts rapidly with sulfurous acid to give taurine [107-35-7] in high yield, a reaction of importance not only for the preparation of this amino sulfonic acid but also for the decontamination of ethyleneimine solutions (130). 

The reaction with methanesulfonyl chloride in the presence of a proton abstracter like triethyl amine gave not the enamine, but a cyclic amino-sulfone (64). 

Polar C=Y double bonds (Y = NR, O, S) with electrophilic carbon have been added to suifinic acids under formation of sulfones. As in the preceding section one must distinguish between carbonyl groups and their derivatives on the one hand, and carboxylic acids (possessing leaving groups at the electrophilic carbon) on the other. Aldehydes " of sufficient reactivity—especially mono-substituted glyoxals - —and their aryl or arylsulfonyl imines have been added to suifinic acids (in a reversible equilibrium) to yield a-hydroxy or a-amino sulfones the latter could also be obtained from the former in the presence of primary amines (equation 26). 

A highly stereoselective synthesis of the (3-substituted P-amino sulfone 271 involves the addition of a sulfonyl anion, derived from A-PMB sultam 268 upon treatment with NaHMDS, to chiral A-sulfinyl imine (5)-269 <06OL789>. Removal of the A-sulfinyl followed by basic workup affords amine 271. The stereochemical outcome of the adduct 270 was established via proton NMR analysis of the Mosher s amide derived from 271. 

Selected Examples of Enantiomer Separation Data of N-Derivatized Amino Acids (See Also Table 1.3), Amino Sulfonic, Phosphonic and Phosphinic Acids on tBuCQN-Based CSP ... 

Table 2 Bi(0Tf)3-4H20-catalyzed allylation of Cbz-amino sulfones 1 with allyltrimethylsilane...

Table 6 Bi(0Tf)3-4H20-catalyzed Mannich-type reactions with various iV-benzyloxycarbonyl-amino sulfones and silyl ketene acetals...

Note Accdg to Kemixon Reporter, Nov 1963, p 1312, Item 10—6189, the following compn was of Wasag-Chemi, GerP 1143425 AN 82, TNT 15, DNT 1 woodflour 2% with added 0.05% of desensitizer, 4-amino-diphenyl amino-sulfonic acid or 4,4 -diamino-dtphenyl amino-sulfonic acid had impact sensitivity value using Koenen app 2.0m/kg, vs 0.75m/kg for the same expl without added desensitizer... 

By ring-opening of the new diastereo- and enantiomerically pure y-sultones R,R) -125 a pathway to pharmacologically interesting sulfonic acid derivatives was opened proceeding via an Sn2 mechanism with inversion of configuration at the attacked y-carbon atom. In this manner, we prepared the y-alkoxy sulfonates (R,S)-126 [98], the y-hydroxy sulfonates R,S)-127 [99], and the y-amino sulfonates (R,S)-128 [100], all in excellent diastereo- and enantiomeric excesses of de, ee> 98% (Scheme 1.1.35). 

Scheme 1.1.36 As)rmmetric synthesis ofy-hydroxy, y-nitro, and y-amino sulfonates.

The presence of an NH group is essential, since the Boc-p-amino sulfone derived from Pro could only be coupled with lower yields (-20%). This method is also suitable for the preparation of pseudodipeptides having functionalized side chains such as those of Ser and AsnJ72l The p-oxo sulfone 51, which was obtained by reacting Boc-pAla-OMe with the dilithium anion of methyl phenyl sulfone, cleanly reacted with ethyl bromoacetate to give the p-oxo sulfone 52 (86%). The latter was reduced using LLAIH4, which on reductive elimination produced the over-reduced Boc-Alai)i(CH2—CH2]Gly-OMe isostere (80%). 

Attempts to convert the Akacyl derivatives of the moderately stable a-amino sulfonic acids by turning them into sulfonyl chlorides and then directly to sulfonamides have failed it appears that the critical requirement for C-S bond rupture is related to a sufficient activation of the sulfonate. 1061 Any synthetic approach to the desired sulfonamide derivatives which utilizes N-protection of aminomethane sulfonic acid as the initial step seems to offer little likelihood of success. In the context of the overactivation of the sulfonyl group of N-protected aminoalkyl sulfonic acid, (l-elimination of the S02C1 is favored over the corresponding sulfonamide, with amines acting merely as bases, not as nucleophiles (Scheme 24). 107 ... 

Amino-sulfonation of alkenes has been performed in a three-component reaction with S03-dimethylformamide complex (SO3 DMF) and acetonitrile followed by hydrolysis.912 Whereas amino-sulfonation occurs without the use of triflic acid, the acid accelerates the reaction considerably and prevents the formation of byproducts. The X-ray structure of intermediate 282 provided evidence that the addition is completely regio- and stereoselective [Eq. (5.338)]. 

As shown in Figure 14.7, taurine is a /3-amino sulfonic acid (2-aminoethane sulfonic acid) and can be synthesized from cysteine by three pathways ... 

The same authors rearranged j6-lactam amino-sulfone 110 (Scheme 39) with DBU in DMF but the yield of the respective methyl sulfone 111 amounted to only 14%. 

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