3333-14-0Relevant articles and documents
PHOTOCHEMICAL REACTIONS OF ARENECARBONITRILES WITH ALIPHATIC AMINES. 1. EFFECT OF ARENE STRUCTURE ON AMINYL VS. alpha -AMINOALKYL RADICAL FORMATION.
Lewis,Zebrowski,Correa
, p. 187 - 193 (1984)
The photochemical reactions of several singlet arenecarbonitriles with aliphatic amines have been investigated. The reactions of 9-phenanthrenecarbonitrile with diethylamaine and its N- and alpha -C deuterated derivatives result in exclusive N-H atom transfer to yield the diethylaminyl and 9-cyano-9,10-dihydrophenanthren-9-yl radicals in benzene solution. Increased solvent polarity results in the formation of both diethylaminyl and 1-(ethylamino)ethyl radical. Similar results are obtained with 9-anthracenecarbonitrile. The competition between aminyl vs. alpha -aminoalkyl radical formation in this and other reactions is reviewed. Aminyl radical formation is characteristic of relatively nonpolar heteroexcimers in which hydrogen bonding may favor N-H transfer. Pure charge-transfer exciplexes, like alkoxyl radicals, yield predominantly the thermodynamically more stable alpha -aminoalkyl radical.
Rearrangements in Aryl Substituted α,β-Unsaturated Nitriles. A Collisional Activation Study
Madhusudanan, K. P.,Murthy, V. S.,Fraisse, D.
, p. 812 - 816 (1989)
The rearrangement reactions following electron ionization in a number of aryl substituted conjugated nitriles have been studied using labelled compounds and collisional activation (CA) spectroscopy.The results indicate that α-phenyl cinnamonitriles and 9,10-dihydro-9-cyanophenanthrene rearrange to a common intermediate which loses CH3(.) or Ch2CN(.) to give the ions at m/z 190 and 165.The CA spectrum of the deuterated analogue (compound 2) shows that there is a complete hydrogen scrambling prior to the loss of the CH3(.) radical.The fluoroderivatives (compounds 5 and 6) behave similarly to the parent nitrile.The introduction of chlorine or bromine into the aromatic ring alters the fragmentation pattern and the only favoured decomposition pathway is the loss of a halogen radical.The CA spectra of the doubly charged ions at m/z 102 and 88 are also discussed.The CA spectrum of the M(1+.) ion 1,1-dicyano-2-phenyl ethylene is characterized by the presence of a rearrangement ion at m/z 103 (PhCN(1+.)).
Enantioselective Arylcyanation of Styrenes via Copper-Catalyzed Radical Relay?
Chen, Pinhong,Liu, Guosheng,Zhuang, Weiwen
, p. 50 - 54 (2021)
The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions, which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good
Crystalline C - C and C=C Bond-Linked Chiral Covalent Organic Frameworks
Yuan, Chen,Fu, Shiguo,Yang, Kuiwei,Hou, Bang,Liu, Yan,Jiang, Jianwen,Cui, Yong
, p. 369 - 381 (2021)
While crystalline covalent organic frameworks (COFs) linked by C-C bonds are highly desired in synthetic chemistry, it remains a formidable challenge to synthesize. Efforts to generate C-C single bonds in COFs via de novo synthesis usually afford amorphous structures rather than crystalline phases. We demonstrate here that C-C single bond-based COFs can be prepared by direct reduction of C=C bond-linked frameworks via crystal-to-crystal transformation. By Knoevenagel polycondensation of chiral tetrabenzaldehyde of dibinaphthyl-22-crown-6 with 1,4-phenylenediacetonitrile or 4,4′-biphenyldiacetonitrile, two olefin-linked chiral COFs with 2D layered tetragonal structure are prepared. Reduction of olefin linkages of the as-prepared CCOFs produces two C-C single bond linked frameworks, which retains high crystallinity and porosity as well as high chemical stability in both strong acids and bases. The quantitative reduction is confirmed by Fourier transform infrared and cross-polarization magic angle spinning 13C NMR spectroscopy. Compared to the pristine structures, the reduced CCOFs display blue-shifted emission with enhanced quantum yields and fluorescence lifetimes, while the parent CCOFs exhibit higher enantioselectivity than the reduced analogs when be used as fluorescent sensors to detect chiral amino alcohols via supramolecular interactions with the built-in crown ether moieties. This work provides an attractive strategy for making chemically stable functionalized COFs with new linkages that are otherwise hard to produce.
Rapid and Simple Access to α-(Hetero)arylacetonitriles from Gem-Difluoroalkenes
Hu, Dandan,Liu, Jiayue,Ren, Hongjun,Song, Jinyu,Zhang, Jun-Qi,Zhu, Guorong
supporting information, p. 786 - 790 (2022/01/28)
A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reacti
Catalyst for α alkylation of nitriles and uses thereof
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Paragraph 0060-0063; 0067, (2021/06/22)
The invention discloses a nitrile alpha-alkylation reaction catalyst and application thereof. The nitrile alkylation reaction catalyzed by pyridine-pyridine-imidazoline asymmetric pincerlike rutheniumcompounds has a reaction general formula shown in the specification, and in the general formula, a catalyst is a pyridine-pyridine-imidazoline asymmetric pincerlike ruthenium compound, R1 is aryl, and R2 is aryl or alkyl, wherein aryl is phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl, thiophene and the like, and alkyl is n-butyl, phenylpropyl and the like. The synthesis method comprisesthe following synthesis steps: adding an asymmetric pincerlike ruthenium compound, an alkali, a nitrile compound and an alcohol into a solvent for reaction, and after the reaction is finished, conducting separating and purifying to obtain a corresponding target product. Alcohol is used as an alkylating reagent, generated water is a unique by-product, the method conforms to the ideas of atom economy and environmental friendliness, and meanwhile, the method has the advantages of use of a catalytic amount of alkali, short reaction time, economy and the like.
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.
Manganese-catalyzed homogeneous hydrogenation of ketones and conjugate reduction of α,β-unsaturated carboxylic acid derivatives: A chemoselective, robust, and phosphine-free in situ-protocol
Topf, Christoph,Vielhaber, Thomas
, (2021/07/10)
We communicate a user-friendly and glove-box-free catalytic protocol for the manganese-catalyzed hydrogenation of ketones and conjugated C[dbnd]C[sbnd]bonds of esters and nitriles. The respective catalyst is readily assembled in situ from the privileged [Mn(CO)5Br] precursor and cheap 2-picolylamine. The catalytic transformations were performed in the presence of t-BuOK whereby the corresponding hydrogenation products were obtained in good to excellent yields. The described system offers a brisk and atom-efficient access to both secondary alcohols and saturated esters avoiding the use of oxygen-sensitive and expensive phosphine-based ligands.
