Reactions Of Fluoroalkanesulfonyl Azides Research Articles

Facile Synthesis of Phosphorus N‐Fluoroalkanesulfonyl Amidines by Cu‐catalyzed One‐pot Three‐component Reaction

AbstractIn the presence of Cu(I) and triethyl amine, one‐pot three‐component reaction of fluoroalkanesulfonyl azides, alkynes and iminophosphoranes in CH2Cl2 at room temperature gave a novel class of fluorinated phosphorus amidines in good yields.

ChemInform Abstract: Reactions of Fluoroalkanesulfonyl Azides with Pyrrole and Its Derivatives.

AbstractThe reactions between the title compounds proceed smoothly under mild conditions affording the 3‐(fluoroalkanesulfonylamido) pyrroles (III) and (V) as exclusive products in good to very good yields.

ChemInform Abstract: Reactions of Fluoroalkanesulfonyl Azides with Pyridine and Its Derivatives.

ChemInform Abstract: Reactions of Fluoroalkanesulfonyl Azides with Pyridine and Its Derivatives.

Reactions of fluoroalkanesulfonyl azides with pyrrole and its derivatives

The reactions of fluoroalkanesulfonyl azides with pyrrole and its derivatives were studied. The reaction proceeded smoothly under mild conditions to give the 3-(fluoroalkanesulfonamido) pyrroles in good yield. The electron donating groups on the pyrrole core accelerated the reaction, while the electron withdrawing groups decelerated it. All the products were fully characterized by spectrum methods, and one of the products was further confirmed by X-ray diffraction analysis. A possible reaction mechanism for these reactions was proposed.

Study on the Reactions of Fluoroalkanesulfonyl Azides with Cycloalkenyl Ether and Aryl Ynamines.

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Unexpected sulfonylamino migration in the reactions of carbazole derivatives with fluoroalkanesulfonyl azides

The reactions of fluoroalkanesulfonyl azides 1 with carbazole derivatives have been studied in detail. At room temperature 1 reacted with 1,2,3,4-tetrahydrocarbazole 2 readily to afford ring-contraction spiroindole derivatives 3 together with an unexpected 4a-fluoroalkanesulfonylamino-1,2,3,4-tetra-hydrocarbazoles 4 . However, in the case of 9-methyl-1,2,3,4-tetrahydrocarbazole 5 , unexpected sulfonylamino migration occurred and a similar product 9-methyl-1-fluoroalkanesulfonylamino-2,3,4,9-tetrahydro-1 H-carbazoles 6 were obtained as major products in moderate yields. These new products were fully characterized by spectral methods and single X-ray diffraction analyses. Possible mechanisms for these reactions were proposed.

Study on the reactions of fluoroalkanesulfonyl azides with cycloalkenyl ether and aryl ynamines

The reactions of fluoroalkanesulfonyl azides 1 with some electron-rich compounds have been studied in detail. Cycloalkenyl vinyl ethers reacted with 1 readily at 0 °C to give the corresponding ring-contraction N-fluoroalkanesulfonyl amidine analogues 3 . In contrast, aryl ynamine generated in situ reacted with 1 affording fluorinated α-diazoamidines 9 , which were decomposed slowly at room temperature to form [1-diethylamino-2-(4-nitro-phenyl)-2-oxo-eth-( Z)-ylidene]-fluoroalkanesulfinyl imine 10 with elimination of nitrogen gas. Possible mechanisms for these reactions were proposed.

Study on the Reactions of Fluoroalkanesulfonyl Azides with Indole Derivatives.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Study on the reactions of fluoroalkanesulfonyl azides with indole derivatives

The reactions of fluoroalkanesulfonyl azides 1 with different indole derivatives have been studied in detail. Treatment of 1 with equimolar amount of 1,3-dimethylindole 3 in 1,4-dioxane at room temperature afforded 2-(1,3-dimethyl-1,3-dihydro-indolinylidene) fluoroalkanesulfonylimines 5 in moderate to good yields. However, under the same reaction conditions, in the case of 1 with 1,2-dimethylindole 4, the corresponding 2-fluoroalkanesulfonyl (1,2-dimethyl-1 H-indol-3-yl)-amide 6 was obtained in moderate yields. In addition, the reactions of 1 and indole 7 gave different products under different conditions. Possible mechanisms of these reactions were proposed.

Study on the Reactions of Fluoroalkanesulfonyl Azides with N‐Alkylindoles.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Study on the reactions of fluoroalkanesulfonyl azides with N-alkylindoles

The reactions of fluoroalkanesulfonyl azides R fSO 2N 3 1 with N-alkylindoles 2 have been studied in detail. It was found that both solvent and the amount of the azides seriously affected the product distribution. 1 reacted with an equimolar amount of 2 in ether or 1,4-dioxane affording 2-( N-substituted-indolinylidene)fluoroalkane sulfonylimines 3 as major product; While, the treatment of 2 with two equivalent of 1 in ethanol afforded N-substituted-2-fluoroalkanesulfonimino-3-diazo-indolines 4 as an unexpected product in good yields. The reaction mechanism was discussed.

Reactions of Fluoroalkanesulfonyl Azides with Vinyl Ether and Tetrakis(dimethylamino)ethylene.

Abstract The reactions of fluoroalkanesulfonyl azides 1 with some electron-rich olefins have been studied. Alkyl vinyl ethers reacted with 1 readily at 0 °C or room temperature (RT) and did not give the corresponding N-fluoroalkanesulfonyl azilidines but 1-fluoroalkanesulfonyl-1,2,3-triazolines 3, which decomposed slowly at room temperature to form 1,4-fluoroalkanesulfonyl-2,5-alkoxyl-piperazines 4 with elimination of nitrogen gas. In contrast, more electron-rich alkene, tetrakis(dimethylamino)ethylene (TDAE) reacted with 1 affording N-fluoroalkanesulfonyl bis(dimethylamino)amidines 6 accompanying the release of N2. Reaction mechanisms are discussed.

Reactions of fluoroalkanesulfonyl azides with vinyl ether and tetrakis(dimethylamino)ethylene

The reactions of fluoroalkanesulfonyl azides 1 with some electron-rich olefins have been studied. Alkyl vinyl ethers reacted with 1 readily at 0 °C or room temperature (RT) and did not give the corresponding N-fluoroalkanesulfonyl azilidines but 1-fluoroalkanesulfonyl-1,2,3-triazolines 3, which decomposed slowly at room temperature to form 1,4-fluoroalkanesulfonyl-2,5-alkoxyl-piperazines 4 with elimination of nitrogen gas. In contrast, more electron-rich alkene, tetrakis(dimethylamino)ethylene (TDAE) reacted with 1 affording N-fluoroalkanesulfonyl bis(dimethylamino)amidines 6 accompanying the release of N 2. Reaction mechanisms are discussed.

A New Method for the Synthesis of N‐Protected β‐Amino‐α‐keto Esters from Fluoroalkanesulfonylazides and α‐Keto Esters.

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A new method for the synthesis of N-protected β-amino-α-keto esters from fluoroalkanesulfonylazides and α-keto esters

In the presence of a secondary amine, treatment of α-keto esters with fluoroalkanesulfonyl azides at room temperature afforded N-sulfonyl protected β-amino-α-keto esters in good to excellent yields. This reaction provided a novel, direct and convenient access to N-sulfonyl protected β-amino-α-keto esters from α-keto esters and fluoroalkanesulfonyl azides under mild conditions. However, the reaction of fluoroalkanesulfonyl azides with β-ketoester enamines afforded two products: N-fluoroalkanesulfonyl amidines and diazoacetate. The reaction mechanism is discussed.

A new route to fluorine-containing aziridines and α-amino esters

The reaction of fluoroalkanesulfonyl azides with several silyl ketene acetals has been investigated. 1-Ethoxyl-1-trimethylsilyloxy-ethylene reacted readily with azides to afford N-fluoroalkanesulfonyl substituted glycinates in good yields. However, reaction of mono- or dialkyl-substituted silyl ketene acetals with azides gave rise to N-substituted α-amino esters and substituted N-perfluoroalkanesulfonyl aziridines. Acidic hydrolysis of the aziridines was also investigated. Mechanisms for the formation of the aziridines and α-amino esters are discussed.

ChemInform Abstract: Reactions of Fluoroalkanesulfonyl Azides with Carbocyclic β-Keto Esters: Structural Influence of Dicarbonyl Substrate on Distribution of Diazo and Ring-Contraction Products.

Abstract The diazo transfer reactions of fluoroalkanesulfonyl azides 1 with ethyl 2-oxocyclopentanecarboxylate 2, in the presence of triethylamine, give ring-opened diazo amido esters 3a–3d in high yields. Rhodium-catalyzed decompositions of these novel diazocarbonyl compounds 3 have been examined. The results show that β-hydride elimination by an intermediate carbene or rhodium-carbenoid is exclusively preferred, and the intramolecular cyclization onto the N-sulfonylcarbamoyl substituent does not take place. However, when fluoroalkanesulfonyl azides 1 react with ethyl 2-oxocyclohexanecarboxylate 5, the ring-contraction product cyclopentanecarboxylate 6 is formed as the only product.

Study on the reactions of fluoroalkanesulfonyl azides with pyridine and its derivatives

The thermal reactions of fluoroalkanesutfonyl azides R fSO 2N 3 1 with pyridine and its derivatives have been investigated in detail. In many cases , N-fluoroalkanesulfonyl pyridinium imides Y +-N −SO 2R f(Y: pyridine, 3-picoline 3,5-lutidine and quinoline) and the hydrogen abstraction products R fSO 2NH 2 were obtained. 2-Picoline and 4-picoline reacted with 1 to give R fSO 2NH 2 exclusively. Interestingly in the reaction of azides 1c IC 2F 4OC 2F 4SO 2N 3 with 4-picolinc or quinoline, the ω-iodine of the azide was substituted to formn ArC 2F 4OC 2F 4SO 2NH 2.

Reactions of fluoroalkanesulfonyl azides with trimethylsilyl enol ethers

Reactions of per(poly)-fluoroalkanesulfonyl azides R fSO 2N 3 with trimethylsilyl enol ethers RCHC(H)OSiMe 3 (R 1= t-Bu, Ph) afforded α-[ N-(fluoroalkanesulfonyl)]amino ketones RC(O)CH 2NHSO 2R f in good yields. The cycloanalog 1-cyclohexenyl trimethylsilyl ether reacted with the azides to give one-carbon ring-contracted product N-fluoroalkanesulfonyl cyclopentanecarboxamides, c-C 5H 11CONHSO 2R f. In the case of 1-cyclooctenyl trimethylsilyl ether, however, two products α-[ N-(fluoroalkane sulfonyl)amine cyclooctanones and c-C 7H 13CONHSO 2R f were obtained.

Synthesis and reactions of fluoroalkanesulfonyl azides and N,N-dichlorofluoroalkanesulfonamides

Thermolysis or photolysis of fluoroalkanesulfonyl azides RFSO2N3 afforded the corresponding nitrene intermediates RFSO2N which reacted readily with alkanes, alkenes, benzene, dimethyl sulfide, dimethyl sulfoxide, pyridine and triphenylphosphine to give insertion or addition products. Similar results were obtained by the reactions of N, N-dichlorofluoroalkanesulfonamides, RFSO2NCl2, with the same reagents in the presence of zinc powder. Treatment of RFSO2NCl2 with alkene in the absence of zinc powder gave only a 1 : 1 adduct via a free-radical intermediate RFSO2NCl.