Arylsulfonyl Isocyanates Research Articles

Recent advances in reactions of aryl sulfonyl isocyanates.

Aryl sulfonyl isocyanates are important intermediates in organic synthesis. They are used as electrophilic reagents and easily react with nucleophiles to form amides, sulfonyl ureas, pyrrolidine derivatives, lactams, oxazolidinones, and so on. Although there are some reviews on the applications of isocyanates in chemistry, few are concerned about aryl sulfonyl isocyanates. This review focuses on recent advances related to aryl sulfonyl isocyanates in organic synthesis, mainly including three special characteristics. The mechanisms of the typical reactions are also discussed.

ChemInform Abstract: Synthesis of N‐Sulfonylamidated and Amidated Azobenzenes under Rhodium Catalysis.

AbstractA rhodium(III)‐catalyzed direct C—H N‐sulfonyl amidation of azobenzenes with arylsulfonyl isocyanates is developed.

Synthesis of N-Sulfonylamidated and Amidated Azobenzenes under Rhodium Catalysis.

The rhodium(III)-catalyzed ortho-C-H amidation of azobenzenes with arylsulfonyl and aryl and alkyl isocyanates is described. The N-sulfonyl amidation reaction using arylsulfonyl isocyanates is first reported in the C-H activation strategy. These transformations provide the facile and efficient construction of a range of amide moieties into azobenzenes.

Pyridine-Mediated Synthesis of 1,3-Diazetidin-2-ones (Aza-β-lactams): Novel Investigations on Isocyanate-Carbodiimde Reaction

The reported cycloaddition reaction of isocyanates and symmetric carbodiimides is reinvestigated in the presence of pyridine. The Huisgen zwitterion generated by the 1:1 addition of pyridine to arylsulfonyl isocyanate is trapped by dialkyl carbodiimide to obtain symmetrical 1,3-diazetidin-2-ones via a novel intramolecular rearrangement.

ChemInform Abstract: A Facile and Efficient Synthesis of Arylsulfonamido‐Substituted 1,5‐Benzodiazepines and N‐[2‐(3‐Benzoylthioureido)aryl]‐3‐oxobutanamide Derivatives.

AbstractThe reaction of 1,2‐diamine (I), diketene (II) and arylsulfonyl isocyanate (III) or benzoylisothiocyanate (V) leads to the formation of the corresponding title compounds.

A new strategy for the chemoselective sulfonamide N-alkylation of sulfonyl ureas under neutral and mild conditions

An efficient and chemoselective sulfonamide N-alkylation of sulfonyl ureas is described. The sulfonyl urea derivatives, prepared in situ by the addition of an amine to an arylsulfonyl isocyanate, are selectively alkylated in excellent yields under neutral and mild conditions by treatment with trialkylphosphite–dimethyl acetylenedicarboxylate at ambient temperature.

ChemInform Abstract: Direct Conversion of 4-Amino-2-oxazolines into 2-Imidazolidinones.

Abstract A convenient new method for the synthesis of polysubstituted 2-imidazolidinones has been established involving the reaction of 4-alkylamino-2-aryl-2-oxazolines with arylsulfonyl isocyanates. It has been applied successfully in preparing previously unknown 3-alkyl-4-aroylamino-1-arylsulfonyl-2-imidazolidinones in high yields.

ChemInform Abstract: Protease Inhibitors. Part 5. Alkyl/Arylsulfonyl- and Arylsulfonylureido-/Arylureido- Glycine Hydroxamate Inhibitors of Clostridium histolyticum Collagenase.

Reaction of alkyl/arylsulfonyl halides with glycine afforded a series of derivatives which were first N-benzylated by treatment with benzyl chloride, and then converted to the corresponding hydroxamic acids with hydroxylamine in the presence of carbodiimide derivatives. Other derivatives were obtained by reaction of N-benzyl-glycine with aryl isocyanates, arylsulfonyl isocyanates or benzoyl isothiocyanate, followed by conversion of their COOH group into the CONHOH moiety, as mentioned above. The 90 new compounds reported here were assayed as inhibitors of the Clostridium histolyticum collagenase (EC 3.4.24.3), a zinc enzyme which degrades triple helical regions of native collagen. The prepared hydroxamate derivatives were generally 100-500 times more active than the corresponding carboxylates. In the series of synthesized hydroxamates, substitution patterns leading to the best inhibitors were those involving perfluoroalkylsulfonyl- and substituted-arylsulfonyl moieties, such as pentafluorophenylsulfonyl, 3- and 4-carboxyphenylsulfonyl-, 3-trifluoromethyl-phenylsulfonyl or 1- and 2-naphthyl among others. Thus, it seems that similarly to the matrix metalloproteinase (MMP) hydroxamate inhibitors, Clostridium histolyticum collagenase inhibitors should incorporate hydrophobic moieties at the P(1') and P(2') sites, whereas the alpha-carbon substituent may be a small and compact moiety (such as H, for the Gly derivatives reported here). Such compounds might lead to the design of collagenase inhibitor-based drugs useful as anti-cancer, anti-arthritis or anti-bacterial agents for the treatment of corneal keratitis.

ChemInform Abstract: Protease Inhibitors: Synthesis of Clostridium histolyticum Collagenase Inhibitors Incorporating Sulfonyl-L-alanine Hydroxamate Moieties.

A series of hydroxamates was obtained by the reaction of N-(4-nitrobenzyl)-L-alanine with alkyl/arylsulfonyl halides, followed by conversion of the COOH group into CONHOH. Structurally-related compounds were prepared similarly by using arylsulfonyl isocyanates, aryl isocyanates or arylsulfenyl halides instead of the sulfonyl halides. Many of the new compounds showed nanomolar affinity for the bacterial collagenase isolated from the pathogen Clostridium histolyticum.

A Facile and Efficient Synthesis of Arylsulfonamido‐Substituted 1,5‐Benzodiazepines and N‐[2‐(3‐Benzoylthioureido)aryl]‐3‐oxobutanamide Derivatives

AbstractA facile and efficient synthesis of 1,5‐benzodiazepines with an arylsulfonamido substituent at C(3) is described. 1,5‐Benzodiazepine, derived from the condensation of benzene‐1,2‐diamine and diketene, reacts with an arylsulfonyl isocyanate via an enamine intermediate to produce the title compounds of potential synthetic and pharmacological interest in good yields (Scheme 1). In addition, reaction of benzene‐1,2‐diamine and diketene in the presence of benzoyl isothiocyanate leads to N‐[2‐(3‐benzoylthioureido)aryl]‐3‐oxobutanamide derivatives (Scheme 2). This reaction proceeds via an imine intermediate and ring opening of diazepine. The structures were corroborated spectroscopically (IR, 1H‐ and 13C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this type of cyclization is proposed (Scheme 3).

Synthesis of Novel Aryl(heteroaryl)sulfonyl Ureas of Possible Biological Interest

The course of reaction of aryl and heteroaryl sulfonamides with diphenylcarbonate (DPC) and 4-dimethylaminopyridine (DMAP) was found to depend on the pKa of the sulfonamide used. Aryl sulfonamides with pKa ~ 10 gave 4-dimethylamino-pyridinium arylsulfonyl-carbamoylides, while the more acidic heteroaryl sulfonamides (pKa ~ 8) furnished 4-dimethylaminopyridinium heteroarylsulfonyl carbamates. Both the carbamoylides and carbamate salts reacted with aliphatic and aromatic amines with the formation of appropriate aryl(heteroaryl)sulfonyl ureas, and therefore, can be regarded as safe and stable substitutes of the hazardous and difficult to handle aryl(heteroaryl)sulfonyl isocyanates.

ChemInform Abstract: Synthesis of Sulfonamides (III) and 1,3‐Oxazine‐2,4‐diones (IV) from Arylsulfonyl Isocyanates and Diketene.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Sulfonamides and 1,3-Oxazine-2,4-diones from Arylsulfonyl Isocyanates and Diketene

An effective route to functionalized N 1 -[(2,6-dimethyl-4-oxo-4 H-pyran-3-yl)carbonyl]-1-arylsulfonamide and 3-(arylsulfonyl)-6-methyl-2 H-1,3-oxazine-2,4(3 H)-dione derivatives is described. This involves the reaction of arylsulfonyl isocyanates and diketene in the presence of N-heteroaromatic compounds such as 1,3,5-triazine, 1-methyl-1 H-imidazole, or pyridine as catalyst. The reactive 1:1 zwitterions obtained from the addition of N-heteroaromatic compound to arylsulfonyl isocyanates were trapped by diketene to produce functionalized sulfonamide and 1,3-oxazine-2,4(3 H)-dione derivatives.

One-Pot Synthesis of Arylsulfonamides and Azetidine-2,4-diones via Multicomponent Reaction of an Amine, an Acetylenic Compound, and an Arylsulfonyl Isocyanate

An effective route to novel arylsulfonamides is described. It involves the reaction of an enamine derived from the addition of primary or secondary amines to acetylenecarboxylates (dialkyl acetylenedicarboxylates or alkyl propiolates) with an arylsulfonyl isocyanate. These arylsulfonamides show dynamic NMR behavior in solution. A different reactivity pattern was observed with the methyl 3-(diethylamino)acrylate. The latter, generated in situ from Et 2 NH and methyl propiolate, on reaction with an arylsulfonyl isocyanate afforded exclusively the azetidine-2,4-dione (malonimide-) derivatives in good yield. These malonimides also show dynamic NMR behavior in solution because of restricted rotation around the C-N bond resulting from conjugation of the side-chain N-atom with the adjacent α,β-unsaturated carbonyl group.

Stereospecific Synthesis of Functionalized C5-Unsaturated Hydantoin Derivatives via a Three-Component Reaction

An effective route to functionalized C5-unsaturated hydantoin derivatives is described. This involves the reaction of a urea derivative, derived from the addition of a primary amine to an arylsulfonyl isocyanate, and a dialkyl acetylenedicarboxylate in the presence of isoquinoline.

One‐Pot Synthesis of Functionalized Hydantoin Derivatives via a Four‐Component Reaction Between an Amine, an Arylsulfonyl Isocyanate and an Alkyl Propiolate or Dialkyl Acetylenedicarboxylate in the Presence of Triphenylphosphine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

One-pot synthesis of functionalized hydantoin derivatives via a four-component reaction between an amine, an arylsulfonyl isocyanate and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine

An effective route to functionalized hydantoin derivatives is described, involving the reaction of a urea derivative resulting from the addition of a primary amine to an arylsulfonyl isocyanate, and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine. The reactive 1:1 intermediate obtained from the addition of triphenylphosphine to the alkyl propiolate or dialkyl acetylenedicarboxylate was trapped by NH-acids such as the urea derivative to produce functionalized hydantoin derivatives.

A New Method for the Synthesis of Functionalized 5‐Hydroxy‐1,5‐dihydro‐2H‐pyrrol‐2‐one: Reaction of an Enamine, Derived from Addition of a Secondary Amine to Dibenzoylacetylene, with an Arylsulfonyl Isocyanate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Facile preparation of N-acylsulfonamides by using sulfonyl isocyanate

N-Acylsulfonamide is widely used as a carboxylic acid bioisostere. A rapid and mild acyl sulfonamide preparation methodology from carboxylic acid and arylsulfonyl isocyanate in the presence of amine is described. The preparation of biologically active acylsulfonamide by our methodology is also presented.

4‐Dimethylaminopyridinium Carbamoylides as Stable and Non‐Hazardous Substitutes of Arylsulfonyl and Heteroaryl Isocyanates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.