From sulfonamides

For a general, simple high yield indole synthesis from anilines and methylthioacetaldehyde etc. see JACS 95,588,591,2718,6508 (1973). For indoles from N-( /3 -hydroxy-ethyl aniline esters see BSC 2485(1973). For a 2-acyl-indoles in one step from orthoamino-ketones and alpha-haloketones or 2-carboxyindoles from sulfonamides of ortho-aminocarbonyls see JOC 38,3622-24(1972). Indole and 5-Br-indole in 4 steps from beta-naphthol see Chem. Het. Cpds. (Russ.) 753(1973). Indole-JOC 37,3622(1972). 

A-Sulfinylarylamines react sluggishly with dienes (equation 125)116,117. TV-Sulfmylsulfo-namides (from sulfonamides and thionyl chloride) are much more reactive dienophiles... 

When optically active allylic alcohol 6a and propargylic alcohol 6p were reacted with amides 2c and 2f, only racemic products 7ac, 7af, and 7pf were obtained (Scheme 2). The results suggested a mechanism through the formation of a carbe-nium intermediate. The observed racemization can also be ascribed to the reversibility of the present reaction. The result shown in Scheme 3 indicated that the reaction is reversible under the reaction conditions. When 7af was treated with 5 mol% of Bi(OTf)3 and KPF6 and 1 equiv of carbamate 2c, a mixture of 7af (28%) and 7ac (68%) was recovered after 1 h. The result suggested that Bi(OTf)3/KPF6 cleaved the C-N bond in 7af derived from sulfonamide 2f, and that 7ac is thermodynamically more stable than 7af. We assume that the desiccant (Drierite) had a beneficial effect on the reactions of substrates shown in Tables 10-12 because of the observed reversibility of the present reaction. In this reaction, the possibility... 

The unanticipated loss of S02 from sulfonamides in collision-induced dissociation. Rapid Commun. Mass Spectrom. 17 81-86. 

This class, also described as phenyliodonium ylides, has several members, notably those coming from sulfonamides, of the general formula PhI = NS02R, where R is an aromatic, aliphatic or heterocyclic group. 

Starnes et al. [34] synthesized a disulfonamide porphyrin receptor 37. Anion binding was detected by the perturbations of the porphyrin Soret and Q bands. The Soret band of 37 at 422 nm showed a red shift upon addition of anions in CH2C12 and isosbestic points were observed. Compound 37 was able to bind F via hydrogen bonding from sulfonamide NH protons in a 2 1 anion-to-ligand ratio with lCal=255,000 M"1 and iCa2= 1,700 M"1. 

The simplest 1,3-dipolar cycloadditions of diazomethane were presented in Figure 15.36. Diazomethane is generated from sulfonamides or alkyl carbamates of A-nitrosomethylamine. The preparation shown in Figure 15.40 is based on the commercially available />ara-toluene-sulfonylmethylnitrosamide (Diazald ). In a basic medium, this amide forms a sulfonylated... 

From sulfonamides and amides, varied diols were prepared. 

Amino-4-imidazolecarboxamide was isolated from sulfonamide-inhibited cultures of Escherichia coli. - ° This substance also accumulates when Escherichia coli are inhibited by aminopterin, and is found in the culture medium of a purine-requiring mutant of Escherichia coZf. °... 

The use of CAB as a chiral reagent seems to be more effective for this reaction, which proceeds faster and with higher yields and enantiomeric excess. Kiyooka et al. first described the use of various chiral oxaborolidines, derived from sulfonamides of a-amino acids and borane, in the course of the selective aldol reaction between silyl ketene acetals and aldehydes (Eq. 47) [43a]. Stereoselectivity and yields were relatively high. 

Liberation of amines from sulfonamides, particularly from benzothiazo-2-ylsulfonyl derivatives, can be achieved by treatment with benzenethiol and a base. 

The scission of the chemical bond between two heteroatoms by Smij is the basis for deprotection of amines from sulfonamides. - The nascent samarium species can be employed as nucleophiles sulfide anions from RSCN for opening of epoxides, from... 

Specific T-cell activation Exanthem from sulfonamides Minor, not serious... 

Kiyooka et al. have reported that stoichiometric use of chiral oxazaborolidines (e.g. (S)-47), derived from sulfonamides of a-amino acids and borane, is highly effective in enantioselective aldol reactions of ketene TMS acetals such as 48 and 49 (Scheme 10.39) [117]. The use of TMS enolate 49 achieves highly enantioselective synthesis of dithiolane aldols, which can be readily converted into acetate aldols without epimerization. The chiral borane 47-promoted aldol reaction proceeds with high levels of reagent-control (Scheme 10.40) [118] - the absolute configuration of a newly formed stereogenic center depends on that of the promoter used and not that of the substrate. 

Figure 4. Schematic representation of the therapeutic areas which evolved from sulfonamide research...

The [ArS02] ions, produced by dissociative secondary electron capture from sulfonamides 103c and 103d, dissociated both by simple cleavage (equation 35a-d) and by rearrangement (equation 35e) processes, as shown by their CAD MIKE spectra83. 

A five-step process was planned to provide a focused array of compounds incorporating three points of diversity arising from sulfonamide formation, A -alkylation, and substituent variation (Scheme 18.21). The route makes use of established reliable reactions such that the entire process was readily antomated using a Zinsser Sophas robotic platform. The first reaction uses apolymer-supported sulfonyl transferreagent, derived from the immobilization... 

Pb-tetraacetate added with stirring at room temp, to a soln. of tosyl amide in dimethyl sulfoxide, warmed 0.5 hr. at 50°, triethylamine added, and the product isolated after an additional hr. N-tosyldimethylsulfoximine. Y 61. F. e., also sulfonylsulfilimines from sulfonamides and tbioetbers, s. T. Ohashi et al.. Synthesis 1971, 96. 

The heterocyclic base, 5-amino-4-imidazole carboxamide, was isolated in 1945 from sulfonamide-inhibited cultures of Escherichia coli, but its possible role as a precursor of purines was suggested only somewhat later. This re-... 

Since all of the methods described by George Levitt earlier in this work are available for synthesizing sulfonylureas from sulfonamides, our goal was to find methods to prepare the wide range of sulfonamides represented by the structures shown below. 

The synthesis of ynol ethers from sulfonamides using potassium alkoxides proceeded in moderate yields under mild conditions (Scheme 2.124) [195]. The chemistry entailed initial conversion of alcohols into potassium alkoxides through the addition of potassium to solutions of the alcohol, followed by the sulfonamide. An amine was needed for a successful conversion and dimethyl amine was a convenient choice. There was a level of operational complexity to this approach in that elemental potassium needed to be handled. Provided that the commercially available solutions were active in the chemistry, it would be more practical to obtain solutions of the alkoxides. 

SCHEME 5.68 Synthesis of aUcynyl sulfides from sulfonamides [107]. 

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