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Carbolithiation of S-alkenyl-N-aryl thiocarbamates: Carbanion arylation in a connective route to tertiary thiols

S-Alkenyl-N-arylthiocarbamates are formed from allylic alcohols by sigmatropic rearrangement and isomerization or C=C bond cleavage. They undergo carbolithiation with a range of organolithium reagents, generating benzyllithium intermediates in a stereospecific manner which may undergo N to C aryl migration to yield thiocarbamates with tertiary substituents. A simple base-promoted alcoholysis reveals a series of hindered tertiary thiols with branched carbon skeletons.

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An unusual substitution reaction directed by an intramolecular re-arrangement

Secondary amines and thiols undertake a substitution reaction on the side chain of 2-bromoethyl-pyridinium derivatives ‘directed’ by an intramolecular re-arrangement. Experimental investigations strongly indicate that the reaction is initiated by an alpha addition of the nucleophile onto the iminium moiety of the N-heteroaromatic cation, followed by a cyclisation and an oxidative ring opening. This novel substitution process is able to occur with less reactive nucleophiles that would not undergo conventional substitution with ‘isolated’ bromoethyl moieties.

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Palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines with amines

A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.

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REACTIONS OF N-POLYFLUOROPHENYLCARBONIMIDOYL DICHLORIDES WITH SECONDARY AMINES. KINETICS AND MECHANISM OF THE FORMATION OF N-POLYFLUOROPHENYLCHLOROFORMAMIDINES

The reactions of N-polyfluorophenylcarbonimidoyl dichlorides with secondary aliphatic and aliphatic-aromatic amines in aprotic solvents were studied.In acetonitrile at 25 deg C N-polyfluorophenylchloroformamidines are formed with high yields.Increase in the temperature and reaction time leads to the formation of N-polyfluorophenylguanidines.The kinetics of the formation of N-polyfluorophenylchloroformamidines were studied.The reaction rate is described by a second-order equation.It is found that the reaction series is highly sensitive to the electronic effects in the substrate and in the nucleophile.It is suggested that the reaction takes place by an addition-elimination mechanism.

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Tungstate catalysis: Pressure-switched 2- and 6-electron reductive functionalization of CO2 with amines and phenylsilane

An efficient and environmentally benign tungstate catalyst for reductive functionalization of CO2 with amines and phenylsilane was developed. By simply varying the pressure, 2-electron or 6-electron reduction of CO2 was successfully achieved with simultaneous C-N bond formation, thus leading to the formation of formamides and methylamines, respectively. That is, secondary and primary amines furnished the corresponding methylamines or dimethylamines in excellent yields under atmospheric pressure of CO2, while various formamides were formed in yields ranging from 52% to 98% when increasing the CO2 pressure to 2 MPa. 1H NMR studies and control experiments demonstrate that N-formylation proceeds through the formation of silyl formate, while N-methylation proceeds through an aminal intermediate generated by 4-electron reduction of CO2.

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Copper(II)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere

The combination of a catalytic amount of Cu(OTf)2 and less than a stoichiometric amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under an O2 atmosphere effectively promoted the N-nitrosation of both secondary aromatic/aliphatic amines and tertiary aromatic amines with nitromethane (CH3NO2) leading to the preparation of N-nitrosamine derivatives.

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Transition metal and base-free synthesis of 3,3-diaryl-2-oxindoles from 2,2,N-triarylacetamides

A transition metal and base-free synthesis of 3,3-diaryl-2-oxindoles has been developed from 2,2,N-triarylacetamides in the presence of montmorillonite K-10 in 1,2-dichlorobenzene under O2 balloon atmosphere.

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Reductive N-methylation of amines with calcium hydride and Pd/C catalyst

The methylation of amines by paraformaldehyde in the presence of calcium hydride as a source of hydrogen and palladium on charcoal as catalyst was studied. Depending on the quantity of paraformaldehyde, monomethylated and dimethylated amines were selectively and efficiently prepared in one pot with good yields.

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INHIBITORS OF HUMAN IMMUNODEFICIENCY VIRUS REPLICATION

Compounds of Formula I with activity against HIV, including pharmaceutical compositions and methods for using these compounds in treating human immunodeficiency virus (HIV) infection, are set forth: Formula :(I)

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Direct Synthesis of 4-Quinolones via Copper-Catalyzed Anilines and Alkynes

A unique and direct approach for constructing 4-quinolones from simple and readily available anilines and alkynes is described. Under the optimal conditions, both N-alkyl- and N-aryl-substituted anilines can be successfully transformed into the corresponding 4-quinolones. This reaction is characterized by mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis.

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