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Relevant academic research and scientific papers

α-Alkylation of Nitriles with Primary Alcohols by a Well-Defined Molecular Cobalt Catalyst

The α-alkylation of nitriles with primary alcohols to selectively synthesize nitriles by a well-defined molecular homogeneous cobalt catalyst is presented. Thirty-two examples with up to 95% yield are reported. Remarkably, this transformation is environmentally friendly and atom economical with water as the only byproduct.

Copper(i)-catalyzed intermolecular cyanoarylation of alkenes: Convenient access to α-alkylated arylacetonitriles

A novel Cu(i)-catalyzed intermolecular cyanoarylation of alkenes with diaryliodonium salts as a radical arylating reagent and tetra-butylammonium cyanide as an electrophilic cyanating reagent was established. A broad range of α-alkylated arylacetonitriles were efficiently constructed in good to excellent yields under base- and oxidant-free and mild conditions. This journal is

Copper-catalyzed radical oxidative C(sp3)–H/C(sp3)–H cross-coupling between arylacetonitriles and benzylic compounds

For the first time, a novel copper-catalyzed direct C(sp3)–H/C(sp3)–H cross-coupling of arylacetonitriles with unactivated benzylic compounds was described, allowing various a-benzylated arylacetonitriles to be readily accessible under base-free conditions. Mechanistic investigations suggested that the reaction proceeds through radical process and the C(sp3)–H cleavage of arylacetonitriles probably is the rate-determining step.

Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols

Six tridentate NNN ligand precursors derived from 2-(pyridin-2-yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron-donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high-resolution mass spectroscopy, and Fourier transform infrared (FT-IR). The molecular structures of 1f, 2a, and 2f have been determined by X-ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five-membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α-alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru-H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.

Nickel-catalyzed hydrogen-borrowing strategy: Chemo-selective alkylation of nitriles with alcohols

The first nickel-catalyzed hydrogen-borrowing alkylation of a series of aryl acetonitriles with a variety of aryl, heteroaryl, allylic and alkyl alcohols releasing water as the by-product (>33 examples, up to 90% yield) is reported.

α-Alkylation of Nitriles with Alcohols Catalyzed by NNN′ Pincer Ru(II) Complexes Bearing Bipyridyl Imidazoline Ligands

A series of unsymmetrical NNN′ ruthenium(II) complexes supported by a tridentate bipyridyl imidazoline ligand with variable steric hindrance (2a-c; R1 = tBu, iPr, or Bn) and electronic effect (2d-h; R2 = H, CH3, OCH3, Br, or NO2) were prepared. The molecular structures of ligands 1f and 1g, and Ru complex 2a were further determined by X-ray single-crystal diffraction. The catalytic activity of these eight complexes for α-alkylation of nitriles with alcohols was evaluated, which could be controlled by the substituents on the imidazoline moiety. Ru complex 2h bearing a strong electron-withdrawing group (R2 = NO2) demonstrated the highest catalytic activity, with alkylated nitriles achieved in up to 97% yield.

Base-Promoted α-Alkylation of Arylacetonitriles with Alcohols

A practical method to synthesize α-alkylated arylacetonitriles from arylacetonitriles and alcohols without using any expensive transition metal complexes is demonstrated here. Following this base-catalysed sustainable procedure, various arylacetonitriles were successfully alkylated with different alcohols. The practical applicability of this protocol was extended by one-pot synthesis of important carboxylic acid derivatives.

Nickel-Catalyzed α-Benzylation of Arylacetonitriles via C-O Activation

Efficient Ni-catalyzed direct cross-couplings of benzylic alcohol derivatives with arylacetonitriles via C-O activation are described. Various α-benzylated arylacetonitriles including those with functional groups can be prepared under mild reaction conditions.

Dual gold catalysis: Synthesis of polycyclic compounds via C-H insertion of gold vinylidenes

New and interesting polycyclic compounds have been synthesized from non-conjugated diyne systems by dual gold catalysis. A quaternary carbon center in the backbone and the accompanying Thorpe-Ingold effect enabled the unprecedented insertion of sp3 and sp2 C-H bonds that for the first time were incorporated within the backbone of the diyne system and allowed the construction of complex polycyclic carbon scaffolds inaccessible by previous approaches in which the C-H bonds for the insertion were situated at the other end of the alkyne.

Dialkylamino cyclopentadienyl ruthenium(II) complex-catalyzed α-alkylation of arylacetonitriles with primary alcohols

Aminocyclopentadienyl ruthenium complexes, [(η5-C 5H4NMe2)Ru(PPh3)2(CH 3CN)]+BF4- and [(η5- C5H4NEt2)Ru(PPh3) 2(CH3CN)]+BF4-, are moderately active catalysts for α-alkylation of arylacetonitriles with primary alcohols; on the other hand, the analogous unsubstituted cyclopentadienyl ruthenium complex [(η5-C5H 5)Ru(PPh3)2(CH3CN)] +BF4- shows very low catalytic activity. On the basis of experimental results and theoretical calculations, rationalization for the much higher catalytic activity of the aminocyclopentadienyl complexes over that of the unsubstituted Cp complex is provided. In the catalytic systems with the former, it is possible to regenerate the active solvento complexes via protonation of the metal hydride intermediates and subsequent ligand substitution; this process is, however, very nonfacile in the catalytic system with the latter. The Royal Society of Chemistry 2010.