Reaction Of Tosylmethyl Isocyanide Research Articles

ChemInform Abstract: Reaction of Tosylmethyl Isocyanide with N‐Heteroaryl Formamidines: An Alternative Approach to the Synthesis of N‐Heteroaryl Tosylimidazoles.

To our knowledge there is no report on the use of hetero-aryl formamidines for the synthesis of imidazoles usingtosylmethyl isocyanide. Hence, we decided to explore thereaction of TosMIC with N-heteroaryl formamidines in theconstruction of 2-(4-tosyl imidazo-1-yl)pyridines and 2-(4-tosyl imidazo-1-yl)pyrimidines based on the followingreasoning. Cunningham

Reaction of Tosylmethyl Isocyanide with N-Heteroaryl Formamidines: an Alternative Approach to the Synthesis of N-Heteroaryl Tosylimidazoles

To our knowledge there is no report on the use of hetero-aryl formamidines for the synthesis of imidazoles usingtosylmethyl isocyanide. Hence, we decided to explore thereaction of TosMIC with N-heteroaryl formamidines in theconstruction of 2-(4-tosyl imidazo-1-yl)pyridines and 2-(4-tosyl imidazo-1-yl)pyrimidines based on the followingreasoning. Cunningham

Reaction of Bromomethylazoles and Tosylmethyl Isocyanide. A Novel Heterocyclization Method for the Synthesis of the Core of Marine Alkaloids Variolins and Related Azolopyrimidines.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reaction of bromomethylazoles and tosylmethyl isocyanide. A novel heterocyclization method for the synthesis of the core of marine alkaloids variolins and related azolopyrimidines.

A novel and efficient synthesis of the pyrido[3',2':4,5]pyrrolo[1,2-c]pyrimidine system, the heterocyclic core of the variolin family of marine alkaloids, is described. The route involves the reaction of 3-bromo-2-(bromomethyl)pyrrolo[2,3-b]pyridine and tosylmethyl isocyanide (TosMIC) under phase-transfer conditions. This unprecedented reaction was also used to synthesize a series of new methoxycarbonyl azolopyrimidines by reaction of TosMIC with bromomethylindoles, bromomethylbenzimidazole, and bromomethylpyrazole. Hydrolysis and decarboxylation of 5-bromo-7-methoxycarbonylpyrido[3',2':4,5]pyrrolo[1,2-c]pyrimidine obtained by this heterocyclization process and installation of the pyrimidine moiety in the C5 position open an alternative approach to complete a total synthesis of variolin B.

Synthesis and X-ray Crystal Structures of Bis(oxazolinyl)phenyl-Derived Chiral Palladium(II) and Platinum(II) and -(IV) Complexes and Their Use in the Catalytic Asymmetric Aldol-Type Condensation of Isocyanides and Aldehydes

The transmetalation of (Phebox)SnMe3 (3; Phebox = 2,6-bis(oxazolinyl)phenyl) with PdCl2(PhCN)2 or K[PtCl3(C2H4)](H2O) gave (Phebox)MIICl complexes (4, M = Pd; 5, M = Pt) in modest to good yields. The (Phebox)PtIVCl3 complexes 8 were also synthesized by the reaction of 5 with CuCl2(H2O)2 as an oxidant. These chloride complexes, 4, 5, and 8, were in turn converted to the cationic complexes by treatment with the corresponding silver salts (AgX: X = BF4, OTf, OCOCF3). X-ray structure studies revealed that the octahedral structure of (Phebox)PtIVCl2 fragment G is isosteric with the (Phebox)RhIIICl2 fragment D, and the (Phebox)MII fragment H (M = Pd, Pt) is almost the same configuration with a square-planar structure. In these complexes, the cationic BF4 aqua complexes (9, M = PdII; 10, M = PtII; 11, M = PtIV) were found to act as chiral catalysts for the aldol-type condensation of isocyanides and aldehydes in the presence of i-Pr2NEt. Excellent trans diastereoselectivities and modest to good enantioselectivities were obtained in the reaction of tosylmethyl isocyanide (TosMIC, 1) by the use of [(i-Pr-Phebox)PtII(H2O)](BF4) (i-Pr-10).

Arylsulfonylpyrroles from Reaction of Tosylmethyl Isocyanide (TOSMIC) with 3-Arylsulfonyl Acrylates as Michael Acceptors

Ethyl 3-(arylthio)acrylates did not react with α-alkali metalated tosylmethyl isocyanide (TosMIC) to afford 4-(arylthio)pyrrole-3-carboxylic acid ethyl esters. Oxidation of thioethers to sulfones generated reactive 3-(arylsulfonyl) acrylates, which promptly underwent cycloaddition with TosMIC in the presence of base giving ethyl 4-(arylsulfonyl)pyrrole-3-carboxylates. Contrary to expectation, the use of ethyl 3-(5-chloro-2-nitrophenylsulfonyl)acrylate led to ethyl ester of 5-tosylpyrrole-3-carboxylic acid instead of the expected ethyl 4-(5-chloro-2-nitrophenylsulfonyl)pyrrole-3-carboxylate.

Synthesis of some indolylpyrroles and indolylpyrrolylketones

The 2-(7-indolyl)pyrrole 12 has been synthesised from 4,6-dimethoxy-2,3-diphenylindole 4 via the 1,4-diketone 11, generated from the 4-nitroketone 7. Reaction of tosylmethylisocyanide with some α,β-unsaturated ketones also yielded the indolylpyrrole 15 and the indolylpyrrolylketones 13 and 17.

A Convenient Synthesis of Tryptamines

Abstract Reaction of tosylmethyl isocyanide with substituted formyl indoles gave the nitrile with one more carbon atom. Hydrogenation of this nitrile afforded the corresponding tryptamine.

ChemInform Abstract: SYNTHESIS OF (3N)CYCLOPHANES AND RELATED COMPOUNDS BY ALKYLATION OF TOSYLMETHYL ISOCYANIDE WITH BIS(BROMOMETHYL)BENZENES

AbstractDurch Alkylierung von Tosylmethylisocyanid (II) mit Bis‐brommethyl‐benzolen (I) unter den Bedingungen der Phasentransfer‐Katalyse werden die Verbindungen (III) und weiter die Cyclophane (IV)‐(IX) erhalten.

Synthesis of (3n)cyclophanes and related compounds by alkylation of tosylmethyl isocyanide with bis(bromomethyl)benzenes.

Bis (2-isocyano-2-tosylethyl) benzenes (12a, 12b, and 12c), synthesized by the reaction of tosylmethyl isocyanide (7) with bis (bromomethyl) benzenes (11a, 11b, and 11c) in 2 : 1 molar ratio, reacted again with 11a, 11b, and 11c under phase-transfer conditions to form 2, 11-diisocyano-2, 11-ditosyl[32]cyclophanes of ortho, meta, and para types (14, 15, and 17), 2, 11, 20-triisocyano-2, 11, 20-tritosyl[33]paracyclophane (19), and 2, 11, 20, 29-tetratosyl[34]cyclophanes of meta and para types (16 and 18). [32]Metacyclophane (1), [33]paracyclophane (31), and [34]meta- and paracyclophanes (32 and 33) could be obtained by hydrolysis and Wolff-Kishner reduction of the above intermediates (15, 16, 18, and 19). Hydrolysis of 2, 11-diisocyano-2, 11-ditosyl[32]orthocyclophane (14) yielded 5, 6, 11, 12-tetrahydro-dibenz[b, g]-azulen-5-one (30) instead of the corresponding ketone (26). Structural properties of the prepared cyclophanes (15, 17, 21, 23, 24, 31, and 33) are described on the basis of the proton magnetic resonance (PMR) spectra.

ChemInform Abstract: SYNTHESIS OF FURAN DERIVATIVES. LXXXV. CONDENSATION OF HETEROAROMATIC ALDEHYDES WITH TOSYLMETHYL ISOCYANIDE

AbstractDie heteroaromatischen Aldehyde (I) bilden mit dem Isocyanid (II) die 5‐substituierten Oxazole (III).

Reaction of tosylmethyl isocyanide with methyl 3-substituted propiolates as acetylenic Michael acceptors.

The reaction of tosylmethyl isocyanide (7) with methyl propiolate (14a), dimethyl acetylenedicarboxylate (14b), methyl 3-(2-furoyl) propiolate (14c), and methyl 3-benzoylpropiolate (14d) in the presence of an equimolar amount of base at room temperature gave the corresponding 1 : 2 adducts, i.e., methyl 3-(1-pyrrolyl) acrylate derivatives (16a, 16b, 16c, and 16d, respectively) as final products. The temperature dependence of the reaction made it possible to isolate the pyrroles (15a and 15b), postulated as intermediates of the reaction, at low temperature.

Synthesis of furan derivatives. LXXXV. Condensation of heteroaromatic aldehydes with tosylmethyl isocyanide.

Reaction of tosylmethyl isocyanide (2) with heteroaromatic aldehydes, i.e., 2-furaldehyde (1a), 5-nitro-2-furaldehyde (1b) and 5-methoxycarbonyl-2-furaldehyde (1c) ; thiophene-2-carbaldehyde (1d) and 5-nitrothiophene-2-carbaldehyde (1e) ; 1-methylpyrrole-2-carbaldehyde (1f) ; 2-, 3- and 4-pyridinemonocarbaldehyde (1g, 1h and 1i) in the presence of an equimolar amount of potassium carbonate in refluxing methanol afforded the corresponding 5-substituted oxazoles (3a-i). However, a similar treatment of pyrrole-2-carbaldehyde (4) with 2 gave 3-tosylpyrrolo [1, 2-c] pyrimidine (6) instead ; a mechanism for this reaction is proposed.