Synthesis of aryl phosphines via phosphination with triphenylphosphine by supported palladium catalysts

The palladium catalyzed phosphination of functionalized aryl bromides, triflates, and chlorides with triphenylphosphine to yield aryldiphenylphosphines was catalyzed by thermally stable palladium catalysts supported on charcoal and aluminia. The addition of NaI promoted both the rates and yields in the phosphination with Pd/C.     

An efficient copper-catalyzed N-arylation of amides: synthesis of N-arylacrylamides and 4-amido-N-phenylbenzamides

Copper-catalyzed intermolecular C–N bond-forming reactions between aryl iodides and amides are described using sodium ascorbate, which is both cheap and nontoxic, as the additive. A variety of functionalized amides including some practical, unique secondary amides, such as N-arylacrylamides and 4-amido-N-phenylbenzamides, which are difficult to obtain by the classical methods, are prepared. Furthermore, some tertiary amides are prepared by using copper thiophenecarboxylate.     

Domino reactions in water for the stereoselective synthesis of novel spiro dihydro-2′H-[indene-2,3′-thiophen]-1(3H)-ones with three contiguous stereocenters

The domino reactions of (E)-2-(aryl)-2,3-dihydro-1H-inden-1-ones and 1,4-dithiane-2,5-diol in the presence of triethylamine in water stereoselectively afforded a library of 2′-(aryl)-4′-hydroxy-4′,5′-dihydro-2′H-spiro[indene-2,3′-thiophen]-1(3H)-ones. This transformation presumably proceeds via the generation of 2-mercaptoacetaldehyde from 1,4-dithiane-2,5-diol followed by Michael addition–intramolecular aldol sequence with C–C and C–S bond formations and creation of three contiguous stereocenters in a one-pot operation.     

3 d Transition Metal‐Catalyzed Hydrogenation of Nitriles and Alkynes

Selective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E‐ and Z‐alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal‐catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.     

Functionalization of silica gel by ultrasound-assisted surface Suzuki coupling

Mesoporous silica gel was functionalized by various organic functional groups using thiol-ene coupling of surface thiol groups with 4-vinylphenylboronic acid followed by Suzuki coupling with aromatic halides. For better performance, the synthesis was conducted under sonication. The presence of surface functional groups was confirmed by thermoanalysis, FT-IR spectroscopy and characteristic reactions of these groups. Solid-phase conditions of the synthesis eliminate the risk of side reactions of boronic acids.     

Synthesis of 2-imidazolines by co-grinding of N-tosylaziridines and nitriles

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Efficient synthesis of fluorinated α- and β-amino nitriles from fluoroalkylated α,β-unsaturated imines

A simple and efficient synthesis of fluoroalkylated α-amino nitrile (4) derivatives by regioselective 1,2-addition of trimethylsilyl cyanide to fluoroalkylated α,β-unsaturated imines (1) is described. Fluoroalkylated β-amino nitriles (7) are also prepared by regioselective 1,2-addition of α-carbanions derived from acetonitrile to fluoroalkylated α,β-unsaturated imines (1). Fluoroalkylated α-(4) and β-amino nitriles (7) are also prepared through an ‘one pot’ procedure by reaction of enaminophosphonate 2 with BuLi, addition of aldehydes and subsequent addition of either trimethylsilyl cyanide or α-carbanion derived from acetonitrile. Basic hydrolysis of α-(4) and β-amino nitriles (7) gives fluoroalkylated α-(5) and β-amino acids (8).     

Synthesis of 2-arylacrylic esters from aryl methyl ketones via Wittig reaction/singlet oxygen ene reaction

An efficient synthetic method has been developed for the synthesis of 2-arylacrylic esters from the corresponding aryl methyl ketones via Wittig reaction and singlet oxygen ene reaction. Wittig reaction to aryl methyl ketones with (methoxymethyl)triphenylphosphonium chloride in basic condition afforded the methyl enol ethers, and then 2-arylacrylic esters were obtained by singlet oxygen ene reaction, followed by tosylation and elimination in one-pot to the methyl enol ethers in good yields.     

Nickel-catalyzed, cascade cycloadditions of 1-ethynyl-8-halonaphthalenes with nitriles: synthesis, structure, and physical properties of new pyrroloarenes

The reaction of 1-ethynyl-8-halonaphthalenes 1 with nitriles in the presence of the catalytic system [NiBr(2)(dppe)]/Zn (dppe=1,2-bis(diphenylphosphino)ethane) is found to produce unusual pyrroloarenes 2. The carbon-nitrogen triple bond in nitrile is activated twice, and five new bonds are formed in a one-pot transformation, which causes a pyrrole and two six-membered rings to be generated simultaneously. The scope and limitations of this reaction are examined. Similarly, alkyl-bridged diynes also furnish the corresponding polycycles. Diaryl-substituted cycloadducts 2 (R(1)=Ar) are fluxional, because of the restriction in rotation of the aryl groups. The rotational barrier is studied by performing (1)H NMR experiments at various temperatures. The structures of several compounds are determined by X-ray crystallographic analysis. The photophysical and electrochemical properties of the pyrroloarenes are also investigated.     

Copper-mediated cyanation reactions

Aryl nitriles can be efficiently synthesized through transition-metal-mediated cyanation of aryl halides, arenes, aryl boronic acids, and so on. Among those most commonly used transition-metals, copper catalysts are surely much more inexpensive and easier to handle, compared to any other metal catalysts. Considering the high-efficiency of copper catalysts in the activation of C–X, C–H, and C–B bond as well as in the formation of C–CN bond, this Letter summarizes various copper-mediated cyanations based on the different kinds of cyanide reagents, such as metal cyanides, potassium hexacyanoferrate(II), acetone cyanohydrins, DDQ, AIBN, benzyl cyanide, malononitrile, nitromethane, and DMF. Our group’s recent contributions to this area are also demonstrated.