2510-95-4Relevant articles and documents
Base-controlled chemoselectivity: direct coupling of alcohols and acetonitriles to synthesise α-alkylated arylacetonitriles or acetamides
Bai, Liang,Ge, Min-Tong,Li, Chen,Qiu, Yuan-Rui,Wang, Ying,Xia, Ai-Bao,Xu, Dan-Qian
, p. 15200 - 15204 (2021/09/06)
We achieved chemoselective synthesis of α-alkylated arylacetonitriles and acetamides by combining Ir complex-catalysed direct coupling of alcohols and nitriles by a simple adjustment of the base. Methanol and ethanol performed well as the alkylating reagents. This method of acetonitrile alkylation provided a novel approach for carbon chain extension.
Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
Zhang, Jin,Luo, Cui-Ping,Yang, Luo
, p. 283 - 288 (2020/12/01)
A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
Switchable Cobalt-Catalyzed α-Olefination and α-Alkylation of Nitriles with Primary Alcohols
Paudel, Keshav,Xu, Shi,Ding, Keying
supporting information, p. 5028 - 5032 (2021/07/19)
The first switchable α-olefination and α-alkylation of nitriles with primary alcohols catalyzed by a well-defined base transition-metal Co complex was presented. A broad variety of nitriles and primary alcohols are selectively and efficiently converted to the corresponding products by this method. It is noteworthy that the transformation is environmentally benign and atom efficient with H2and H2O being the sole byproducts.
Tandem Acceptorless Dehydrogenative Coupling-Decyanation under Nickel Catalysis
Babu, Reshma,Balaraman, Ekambaram,Midya, Siba P.,Subaramanian, Murugan,Yadav, Vinita
supporting information, p. 7552 - 7562 (2021/06/28)
The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.
α-Alkylation of arylacetonitriles with primary alcohols catalyzed by backbone modified N-heterocyclic carbene iridium(i) complexes
Arslan, Burcu,Gülcemal, Süleyman
, p. 1788 - 1796 (2021/02/16)
A series of backbone-modified N-heterocyclic carbene (NHC) complexes of iridium(i) (1d-f) have been synthesized and characterized. The electronic properties of the NHC ligands have been assessed by comparison of the IR carbonyl stretching frequencies of thein situprepared [IrCl(CO)2(NHC)] complexes in CH2Cl2. These new complexes (1d-f), together with previously prepared1a-c, were applied as catalysts for the α-alkylation of arylacetonitriles with an equimolar amount of primary alcohols or 2-aminobenzyl alcohol. The catalytic activities of these complexes could be controlled by modifying the N-substituents and backbone of the NHC ligands. The NHC-IrIcomplex1fbearing 4-methoxybenzyl substituents on the N-atoms and 4-methoxyphenyl groups at the 4,5-positions of imidazole exhibited the highest catalytic activity in the α-alkylation of arylacetonitriles with primary alcohols. Various α-alkylated nitriles and aminoquinolines were obtained in high yields through a borrowing hydrogen pathway by using 0.1 mol%1fand a catalytic amount of KOH (5 mol%) under an air atmosphere within significantly short reaction times.
α-Alkylation of Nitriles with Primary Alcohols by a Well-Defined Molecular Cobalt Catalyst
Paudel, Keshav,Xu, Shi,Ding, Keying
, p. 14980 - 14988 (2020/12/02)
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.
COMPOUNDS THAT INTERACT WITH THE RAS SUPERFAMILY FOR THE TREATMENT OF CANCERS, INFLAMMATORY DISEASES, RASOPATHIES, AND F1BROTIC DISEASE
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Paragraph 0687, (2020/07/14)
Provided herein are methods and compositions for treating cancers, inflammatory diseases, rasopathies, and fibrotic disease involving aberrant Ras superfamily signaling through the binding of compounds to the GTP binding domain of Ras superfamily proteins including, in certain cases, K-Ras and mutants thereof, and a method for assaying such compositions.
Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols
Huang, Shuang,Hong, Xi,Sun, Yong,Cui, He-Zhen,Zhou, Quan,Lin, Yue-Jian,Hou, Xiu-Feng
, (2020/02/13)
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.
Polysubstituted ethylene compound as well as preparation method and application thereof
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Paragraph 0125-0129; 0225-0229, (2020/12/30)
The invention discloses a polysubstituted ethylene compound as well as a preparation method and application thereof. The invention particularly discloses a preparation method of a polysubstituted ethylene compound as shown in a formula III, which comprises the following step: in an organic solvent, carrying out reaction as shown in the specification on a compound as shown in a formula I and a compound as shown in a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain the polysubstituted ethylene compound as shown in the formula III. The preparation methodcan be suitable for various types of substrates, and the configuration of double bonds is controllable.
A [...] ligand, synthetic method and the application of the asymmetric reaction in
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Paragraph 0178-0181, (2019/04/14)
The invention relates to a novel chiral sulfur-alkene ligand and its synthesis method and use in an asymmetric reaction. The novel chiral sulfur-alkene ligand has a structural formula (I) or (II). In the structural formula (I) or (II), R1, R2, R3, R4, m and n are shown in the following description. The novel chiral sulfur-alkene ligand is simply prepared from aldehyde as a raw material. The novel chiral sulfur-alkene ligand can be used as a chiral ligand for an asymmetric addition reaction of boric acid and carbonyl compound (such as aromatic formaldehyde, isatin (Isatin) and trifluoroacetophenone) in the presence of a rhodium catalyst, and has a good yield and enantioselectivity.
