Amines => sulfonamides

Instead of amines, sulfonamides have also been used as starting materials, producing the highly reactive sulfonyl isocyanates, which have found apphcations in the manufacture of dmgs for diabetics and as drying agents (qv) (4,9,16). 

Additions of oxygen and nitrogen nucleophiles to vinyloxiranes can be achieved with Pd(0) catalysis [103, 104]. Acetate, silanols, amines, sulfonamides, and azide have been used as nucleophiles, and the stereochemical outcome of these additions, where applicable, is normally the result of two consecutive SN2 reactions. This is demonstrated by the additions of NaNHTs to vinylepoxides 29 and 30, affording syn- and anti-amino alcohols 31 and 32, respectively, in good yields and with high diastereoselectivities (Scheme 9.22) [105]. 

High bulk-densiry NGu and recrystn of NGu from aq soln contg a little HAc and a little of a deriv of NGu such as hyarazone, hyarazide, amide, amine, sulfonamide, sulfate) 20a) Cond-ChemDicr (1961), 805-R (NGu) 21) L.D. Sadwin, Science 143(3611), 1164, 1169(1964) CA 60, 14188(1964) (Explosive welding with NGu)... 

Acetylation Acetyl-CoA /V-Acetyltransferase (cytosol) Amines Sulfonamides, isoniazid, clonazepam, dapsone, mescaline... 

I. Allylic Amines, Sulfonamides and Carbamates via 2-Aza-l-Thia- 2,3] Sigmatropic... 

Acetylation of xenobiotic primary amine groups is a common metabolic pathway, whereas acetylation of xenobiotic hydroxyl and sulfhydryl groups is not. Primary aliphatic and aromatic amines, sulfonamides, hydrazines, and hydrazides are readily N-acetylated in vivo, and the reaction is catalyzed by various acetyl CoA N-acetyltransferases, commonly called N-acetyltransferases, as shown in Figure 16. 

Organocopper reagents are the most reliable species for conjugate additions and a number of approaches towards chiral cuprates has been developed. The approaches are classified into two categories one is the chiral heterocuprate obtained by treatment with chiral alcohols, amines, sulfonamides, and thiols. The other involves organocopper compounds coordinated by chiral external ligands such as phosphines, sulfides, and oxazolines. 

A multitude of iV-sulfinyl compounds and sulfur diimides bearing a variety of substituents on the nitrogen atom(s) have been prepared. The iV-sulfinyl compounds are commonly generated by treatment of the parent aniline, amine, sulfonamide, etc., with thionyl chloride and pyridine [Eq. 

R Organic acids, alcohols, phenols, ketones, esters, ethers, amides, imines, imides, nitriles, aromatic amines, sulfonamides, barbiturates, aromatic hydrocarbons, other miscellaneous groups. Regression equations for calculation of from Kw in any of 20 different solvent/water systems are given. Equations primarily for mono-functional chemical classes. 

Other catalysts such as those depicted in Scheme 2.10 have also been developed following the same concept. In particular, primary amine-sulfonamides 27a and 27b, in which the sulfonamide N-H group plays the role of the hydrogen-donor group, have been successfully applied to the reaction of... 

Scheme 2.10 Enantioselective Michael addition of ketones to nitroalkenes catalyzed by primary amine-sulfonamide catalysts 27a-b and by 9-epi amino cinchona alkaloid 28a.

It has recently been demonstrated that bromo-tns-pyrrolidino-phosphonium hexafluorophosphate (PyBroP) can be functiOTiing as a mild activator of azine N-oxide providing regioselective addition of Ai-nucleophiles (amines, sulfonamides, and NH-heterocycUc compounds) to pyridine, quinoline, and isoquinoline N-oxides (Scheme 53) [112,113]. A strong regiochemical preference for the orf/io-substitution pattern in aU these cases is likely caused by specific electrostatic attraction of nucleophilic species and the intermediate phosphonium salt 76. This synthetic procedure was successfully extended for other types of nucleophilic reagents (phenols, thiols, malonates). 

Glucuronidation occurs at oxygen and nitrogen atoms and is one of the most common phase II reactions. It can occur with alcohols, phenols, hydro-xylamines, carboxylic acids, amines, sulfonamides, and thiols and utilizes the energy-rich co-factor uridine diphosphoglucuronic acid (UDPGA). 

By employing o-(trimethylsilyl)phenyl triflate derivatives (11) as the aryne precursors, Larock and coworkers have developed a facile transition metal-free N-arylation method for amines, sulfonamides and carbamates under very mild reaction conditions (Scheme 12.4) [11]. Aromatic and aliphatic, as well as primary and secondary amines, react well, afTording good to excellent yields of the desired products. Secondary amines generally react faster than primary amines in... 

Recently, by using a primary amine sulfonamide/benzoic acid salt, Liang and Ye [57] developed an unprecedented example in the asymmetric Michael addition of ketones to maleimides (Scheme 5.30). The reaction is quite general, and it provides the corresponding Michael adducts in good to excellent yields with excellent enantioselectivities. 

Asymmetric addition of diorganozincs to aldehydes and ketones has been reviewed, focusing on bifunctional catalysts such as those prepared from salens or BINOLs. Regioisomeric chiral amine-sulfonamide organocatalysts give >99% yield and up to 98% ee in addition of diethylzinc to aldehydes. Switching between regioisomers effectively switches the direction of selectivity. Amino-acid-derived (15,l 5)-4,4 -biquinazoline primary amines catalyse ethylation of aryl aldehydes in up to 95%... 

By using the fluoride-induced generation of arynes from o-(silyl)aryl triflates, Larock and Liu have developed the aryne-mediated A-arylation of amines, sulfonamides, and carbamates as well as the O-arylation of phenols and carboxylic acids. Remarkably, a wide variety of functional... 

Continuing their work on the previously reported magnetite-catalyzed N-alkylation of aryl amines [138], in 2011 Ramon and co-workers reported Ru(0H)3/Fe304-catalyzed A -alkylation reactions of poor nucleophilic amines/ amides, such as aromatic and heteroaromatic amines, sulfonamides, sulfinamides, and nitroarenes (Scheme 26) [139]. The catalyst could be easily removed from the reaction mixture by magnet and reused up to ten times, showing the high activity of the catalyst (1st, 99 % 10th, 93 %). 

Ramon D, Martinez-Asencio A, Yus M (2011) Palladium(ll) acetate as catalyst for the A-alkylation of aromatic amines, sulfonamides, and related nitrogenated compounds with alcohols by a hydrogen... 

Cano R, Ramon DJ, Yus M (2011) Impregnated ruthenium on magnetite as a recyclable catalyst for the N-alkylation of amines, sulfonamides, sulfinamides, and nitroarenes using alcohols as electrophiles by a hydrogen autotransfer process. J Org Chem 76(14) 5547-5557... 

Nitrophenyl amine sulfonamide Foron Yellow SE/GLN Cl Dispersed Yellow 33... 

Publications continue to appear that deal with new applications of known linkers as well as novel linkers to expand the scope of functionality which can serve as a handle for solid-phase synthesis. Prominent among recent manuscripts are linkers for a variety of nitrogen-based functional groups such as amines, sulfonamides, amidines, and hydroxamic acids (Figure 1). 

Uses Foam stabilizer, vise, modifier for detergents, shampoos, bubble baths, and cosmetic toiletries Features High active low amine Sulfonamide" OD [Huntsman]... 

Cationic fluorinated surfactants can be prepared by reacting the pentamer with phenol and, subsequently, with chlorosulfonic acid. The sulfonyl chloride reacts with A,A-dimethylpropanediamine to form a tertiary amine sulfonamide, which can be quaternized to form a cationic surfactant ... 

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