Toluenesulfonylmethyl isocyanide

The use of a vinylphosphonium salt as the source of the QQ fragment instead of the more commonly employed 1,2-dicarbonyl substrate is illustrated by the pyrrole synthesis in Scheme 79b (8UOC2570). A particularly interesting feature is the intramolecular Wittig reaction with an amide carbonyl group. A very useful synthesis of pyrroles depends upon the addition of the anion of p-toluenesulfonylmethyl isocyanide (TOSMIC) to a,/3-unsatur-... 

A useful pyrrole synthesis depends upon the addition of the anion of p-toluenesulfonylmethyl isocyanide (TOSMIC) to a,(3-unsaturated ketones or other Michael acceptors (72TL5337) (Scheme 56). 

T10425>. Through a proper use of the Suzuki-Miyamura and van Leusen oxazole synthesis it was possible to synthesize a wide variety of aromatic derivatives substituted with oxazole rings. The strategy was based on the initial synthesis of the aromatic scaffold and the subsequent reaction of the carbonyl functions with toluenesulfonylmethyl isocyanide (TosMIC) as depicted in the following scheme<07S3653>. 

Samanta et al. [23] conveniently synthesized the 1,5-disubstituted imidazoles (xxv) on a polymeric support using base-promoted 1,3-dipolar cycloaddition reaction of p-toluenesulfonylmethyl isocyanide (TOSMIC) with immobilized imines under microwave irradiation. 

Samanta SK, Kylanlahti 1, Yli-Kauhaluoma J (2005) Microwave-assisted synthesis of imidazoles reaction of p-toluenesulfonylmethyl isocyanide and polymer-bound imines. Bioorg Med Chem Lett 15 3717-3719... 

PS-p-toluenesulfonylmethyl isocyanide (TosMIC) reagent, developed by Barrett et al. was found to be effective for the conversion of a range of aryl aldehydes into highly pure 4-aryl oxazoles in the presence of BTMG (2) [79] (Scheme 4.29b). A typical procedure involved the reaction of aldehyde with the gel (4 equiv.) in acetonitrile (0.2M sol) and BTMG (2) (4 equiv.) for 12 h at 65 °C. ... 

Diethoxyphosphoryl-4-methyl-3-phenyl B. From p-toluenesulfonylmethyl isocyanide (TsMIC) 2-Nitropropen-1 -ylbenzene 58 93S473... 

A new silver-catalyzed heteroaromatization of propargyhc alcohols with p-toluenesulfonylmethyl isocyanide (TosMIC) was developed that provided an efficient and modular approach to sulfonyl benzo[l ]furans.The TosMIC played a dual role sulfonyl source and ligand (14OL6204). 

Carbon disulfide and isothiocyanates have also proven suitable electrophiles for the preparation of thiazoles via the Schollkopf reaction. Isocyanides bearing electron-withdrawing a-substituents are insufficiently nucleophilic to react with nitriles to afford the eorresponding imidazoles, however iV-alkyl 4-tosylimidazoles are accessible through the sodium hydride-mediated condensation of toluenesulfonylmethyl isocyanide and imidoyl chlorides. Furthermore, the more electron-rich -tolylthiomethyl isocyanide reacts smoothly with carbodiimides and nitriles to afford the corresponding imidazoles. ... 

The reaction of solid-supported imines and p-toluenesulfonylmethyl isocyanide (TOSMIC) gave resin-bound imidazoles. In this case, the cleavage of the products occurred with the 2-methoxy-substituted linker because the imidazole core was attached directly to the aryl ring with a carbon-carbon bond. 

Ethyl 3-trifluoromethylacetylenecarboxylate (180) and toluenesulfonylmethyl isocyanide (TOSMIC) 363 provided the B-CFs-pyrrole 364 containing a tosyl group in 2-position [118]. 

Diverse sugar-derived aldehydes 15 (Scheme 11.6) were used as chiral auxiliaries to perform the diastereoselective three-component Passerini reaction by reaction with p-toluenesulfonylmethyl isocyanide (17a, TosMIC) and carboxylic acids 16, giving... 

Krishna, P. R., Dayaker, G., Reddy, P. V. N. (2006). Diastereoselective Passerini reaction using p-toluenesulfonylmethyl isocyanide (TosMIC) as the isonitrile component. Tetrahedron Letters, 47, 5977-5980. 

Scheme 4.22 Synthesis of imidazo[l,5-a]quinoxaline from quinoxaline and dilithium derivative of /r-toluenesulfonylmethyl isocyanide...

Other liquid isocyanides, such as the positional isomeric picolyl isocyanides, on the contrary, do not smell at all. The isocyanide derived from L-phenylglycine methyl ester smells of rhubarb. Toluenesulfonylmethyl isocyanide (TosMIC) and adamantyl isocyanide are not as offensive as others. To avoid the distressing smell of isocyanides, there is a continuous effort among the scientific community to develop fragrant smelling isocyanides. 

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