Versatile syntheses of secondary and tertiary amines by highly efficient direct N-alkylation primary with alcohols or deaminative self-coupling have been successfully realized means a heterogeneous bimetallic Pt-Sn/γ-Al(2)O(3) catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through borrowing-hydrogen strategy. In the presence oxygen, imines were also efficiently prepared from tandem reactions between two amines. The proposed mechanism reveals that an alcohol amine substrate is initially...

Manganese(I) complexes bearing a pyridyl-supported pyrazolyl-imidazolyl ligand efficiently catalyzed the direct β-alkylation of secondary alcohols with primary under phosphine-free conditions. The β-alkylated were obtained in moderate to good yields water formed as byproduct through borrowing hydrogen pathway. β-Alkylation cholesterols was also effectively achieved. present protocol provides concise atom-economical method for C–C bond formation from and alcohols.

A ruthenium(II)–NNC pincer complex containing an unsymmetrical tridentate pyrazolyl–pyridyl–tolyl ligand was synthesized and structually characterized. This exhibited excellent catalytic activity for the transfer hydrogenation of ketones in 2-propanol at reflux, Oppenauer-type dehydrogenative oxidation alcohols acetone reflux (see scheme).

Ru(III) and Ru(II) complexes bearing a tridentate 2-(3′,5′-dimethylpyrazol-1′-yl)-6-(3″,5″-bis(trifluoromethyl)pyrazol-1″-yl)pyridine or 2-(benzimidazol-2′-yl)-6-(3″,5″-bis(trifluoromethyl)pyrazol-1″-yl)pyridine ligand were synthesized applied to the transfer hydrogenation of ketones. The complex was structurally confirmed by X-ray crystallographic analysis achieved up 2150 turnover numbers final TOFs 29700 h–1 in benzimidazolyl moiety with an unprotected NH functionality exhibited...

Ruthenium(II) complexes bearing a pyrazolyl–pyridyl–pyrazole ligand were synthesized and exhibited exceptionally high catalytic activity in the transfer hydrogenation of ketones refluxing isopropyl alcohol, reaching final TOFs up to 720 000 h–1. The β-NH functionality pyrazole arm demonstrated remarkable acceleration effect on reaction rate. unsymmetrical nature (hemilability) presence convertible NH group is attributed complex catalyst.

FeCl(3)·6H(2)O-catalyzed efficient C3-alkenylation of indoles was realized through the condensation aldehydes and indole derivatives in presence 2 equiv ethanol at ambient temperature, forming 3-vinylindoles up to 93% yields. Ethanol promoted formation desired products. An obvious solvent effect observed, bisindoles were identified as reaction intermediates.

CuCl2-mediated intramolecular C–H/C–H cross-dehydrogenative coupling (CDC) of thioalkyl-substituted α-acetyl or α-aroyl ketene N,S-acetals afforded 2-thioalkyl indoles. Tunable C–S bond transformations the resultant indoles led to highly functionalized N-heterocyclic compounds. A β-thioalkyl is necessary activate N,S-acetal substrate and enable CDC reaction occur, relevant mechanism studies revealed that follows a radical pathway.

Abstract Potassium tert ‐butoxide‐promoted acceptorless dehydrogenation of N‐heterocycles was efficiently realized for the generation N‐heteroarenes and hydrogen gas under transition‐metal‐free conditions. In presence KO t Bu base, a variety six‐ five‐membered N‐heterocyclic compounds underwent to afford corresponding H 2 in o ‐xylene at 140 °C. The present protocol provides convenient route aromatic nitrogen‐containing gas. magnified image

FeCl3- and FeBr3-promoted cyclization/halogenation of alkynyl diethyl acetals has been efficiently realized, selectively affording (E)-2-(1-halobenzylidene or alkylidene)-substituted five-membered carbo- heterocycles which were then transformed to vinylarenes by Suzuki coupling. The present protocol provided a new alternative route vinylic C−Cl C−Br bond formation.

Gestational diabetes mellitus (GDM) is a metabolic and low-grade inflammatory disease most commonly found in pregnant women with high body mass index non-Caucasian ethnicities; however, not all of high-risk groups develop GDM. We hypothesized that regulatory T cells (Tregs) might present role suppressing GDM development. To this end, 55 at early pregnancy (first trimester) were recruited, 21 them developed while the other 34 did not. Compared to those subjects who (non-GDM), patients...

Iron-promoted difunctionalization of α,α-diaryl and α-aryl-α-alkyl allylic alcohols has been efficiently achieved by means N-(phenylseleno)phthalimide (N-PSP) under mild conditions. An in situ generated phenylselenium cation (PhSe+) was added to the olefinic C═C bond initiate regioselective phenylselenylation with concomitant 1,2-aryl migration, following a migration preference contrary well-known radical pathway. Hydrazonation resultant alkene products, that is, α-aryl-β-phenylselenyl...

Dinuclear ruthenium(II)-NNN complexes were efficiently assembled by means of coordinatively unsaturated 16-electron mononuclear ruthenium(II)-pyrazolyl-imidazolyl-pyridine complex and 4,4′-linked bipyridine ligands. The diruthenium(II)-NNN through 4,4′-(CH2)3-bipyridine exhibited exceptionally high catalytic activity for the transfer hydrogenation (TH) ketones in refluxing 2-propanol reached TOF values up to 1.4 × 107 h–1, demonstrating a remarkable cooperative effect from functionalities.

A pincer-type Ru(II)-NNP complex bearing a pyrazolyl-(NH-PtBu2)-pyridine ligand was synthesized and structurally characterized by NMR, IR, elemental analysis, X-ray single-crystal crystallographic determinations, which efficiently catalyzed the synthesis of multisubstituted pyrroles pyridines means reactions secondary alcohols β- or γ-amino through deoxygenation selective C–N C–C bond formation. The coupling took place with 0.3 mol % catalyst loading tolerated diverse functional groups....

CuCl2 and CuBr2-mediated intramolecular oxidative C-H/N-H cross-coupling/halogenation of β-thioalkyl-substituted α-alkenoyl ketene N,S-acetals occurred efficiently, affording 4-halo-5-thioalkyl-3-pyrrolones. Tunable C-S C-halo bond transformations the resultant pyrrolone derivatives led to highly functionalized N-heterocyclic compounds.

Abstract Formal olefinic C−P cross‐coupling between alkenyl sulfonium salts and secondary phosphine oxides H‐phosphinates has been developed. A base enables construction of bonds as well aliphatic at ambient temperature under an air atmosphere. This protocol provides alternative access to multisubstituted phosphinates in 40–99% yield from functionalized alkenes through interrupted Pummerer activation/base‐promoted C−S bond phosphinylation sequence. Gram‐scale preparation feasible...

Abstract Palladium‐catalyzed stereoselective olefinic C−H alkynylation of gem ‐diarylsubstituted ethylenes with propargylic alcohols was achieved to access diverse unsymmetrical 1,3‐enynes. The regio‐ and stereoselectivities were established through a 1,4‐palladium migration from aryl vinyl in the presence 2‐FC 6 H 4 OH as additive. Mechanistic investigations suggest that cleavage bond might not be involved rate‐determining step catalytic process.

Brønsted acid p-TsOH·H2O-catalyzed hydrovinylation of styrenes with internal olefins α-oxo ketene dithioacetals was efficiently achieved in the presence N-phenylselenophthalimide (N-PSP), regioselectively affording Markovnikov phenylselenative products through PhSe transfer phenylseleno dithioacetal intermediates. Radical reduction resultant PhSe-alkyl-substituted AIBN/n-Bu3SnH gave corresponding anti-Markovnikov formally from linear codimerization and olefins.

A concise synthetic route to spiroindoline-fused S-heterocycles was developed through copper-catalyzed [4 + 1] annulation using enaminothiones as donor-acceptor synthons. Both 3-diazoindolin-2-imines and 3-diazooxindoles were amenable work effective C1 building blocks. The reaction proceeds via a cascade process involving the in situ generation of copper(I) carbene C-S/C-C bond formation. This protocol features use readily available substrates, diverse substituent tolerance, good excellent yields.

Efficient palladium-catalyzed regioselective vinylic C–H polyfluoroarylation of gem -disubstituted ethylenes with polyfluoroarenes was realized via an aryl to vinyl 1,4-palladium migration process access various polyfluorinated triarylethenes.

The direct synthesis of triazole 2-oxides has posed a challenge in the field N-heterocyclic chemistry. A novel copper(I)-catalyzed nitrosylation/annulation cascade enaminones provides straightforward route to 1H-1,2,3-triazole by forming new C-N, N=N, and N-N bonds using noncorrosive tert-butyl nitrite (TBN) as both N NO sources. synthetic protocol features easily accessible starting materials, wide substrate scopes, good tolerance toward various functional groups while avoiding use explosive azides.

Abstract The Brønsted acid‐mediated alkylation and alkenylation of indoles were efficiently achieved by means 3‐(dimethylamino)acrylonitrile. Regulating the acidity reaction medium with para ‐toluenesulfonic acid monohydrate ( p ‐TsOH⋅H 2 O) and/or acetic (HOAc) led to versatile formation 3‐alkylated 3‐alkenylated indole derivatives under mild conditions. products could be nearly quantitatively transformed corresponding separable E )‐ Z )‐3‐alkenylated indoles. magnified image