16610-80-3Relevant academic research and scientific papers
Nickel(0) Catalysed Additions of Hydrogen Cyanide to Alkynes: Stereochemistry, Mechanism, and Preparative Application
Jackson, W. Roy,Lovel, Craig G.
, p. 1231 - 1232 (1982)
The addition of hydrogen cyanide to both terminal and disubstituted acetylenes occurs with cis-stereospecificity in moderate to excellent yields when catalysed by a nickel(0) complex.
Accelerated Discovery of α-Cyanodiarylethene Photoswitches
Hecht, Stefan,K?nig, Niklas F.,Mutruc, Dragos
supporting information, p. 9162 - 9168 (2021/07/01)
Cyanodiarylethene chromophores are able to undergo constitutional exchange via dynamic covalent chemistry (DCC). During this process, the central ethylene bridge of the molecular scaffold can be broken and thereby enables the assembly of a new combination of aryl moieties around the reformed ethylene bridge. The reversible CC double bond exchange has exemplarily been investigated using α-cyanostilbenes. Establishing a dynamic equilibrium reaction from α-cyanodiarylethene with arylacetonitriles under mild conditions has been the basis to access constitutional libraries of new photoswitches with potentially improved properties. When subject to irradiation with light of adequate wavelength, α-cyanodiarylethenes undergo Z/E isomerization followed by ring-closure. By screening the thus accessible dynamic chromophore libraries using a desired detection wavelength, we could identify specific dithienyl analogues that exhibit three-state photochromism. The combination of dynamic constitutional libraries of functional chromophores in combination with the light-guided screening and selection should lead to more rapid exploration of structural diversity dye chemistry.
Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
, p. 1397 - 1405 (2020/02/04)
We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
, p. 3360 - 3365 (2019/03/26)
The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
, p. 6779 - 6784 (2019/08/26)
Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
Metal-Free Direct C?H Cyanation of Alkenes
Wang, Xi,Studer, Armido
supporting information, p. 11792 - 11796 (2018/09/10)
A metal-free and direct alkene C?H cyanation is described. Directing groups are not required and the mechanism involves electrophilic activation of the alkene by a cyano iodine(III) species generated in situ from a [bis(trifluoroacetoxy)iodo]arene and tri
A Rapid and Highly Efficient Method for the Synthesis of Benzofulvenes via CsOH-Catalyzed Condensation of Indene and Aldehydes
Yi, Rongnan,Chen, Jinyang,Wang, Xueyan,Liang, Zhiwu,Xu, Xinhua
supporting information, p. 1347 - 1351 (2018/04/02)
A fast condensation of indene with a wide range of aldehydes catalyzed by cesium hydroxide monohydrate (CsOH·H2O) for the synthesis of benzofulvenes with good to excellent yields was demonstrated. The condensation can be completed within a few minutes under room temperature and air atmosphere without the use of special ligands or phase-transfer catalysts. In addition, the ratio of indene to aldehydes played an important role in this reaction. The single condensation products 3 can be obtained as main products with a ratio of 1.2:1, whereas the double condensation products 4 can be obtained by changing the ratio to 1:2.2. This protocol provides an efficient, simple and general method for the synthesis of benzofulvenes 3 and double condensation products 4, which are important intermediates in the synthesis of numerous drugs and natural products.
Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
, p. 14036 - 14048 (2018/11/03)
An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
Nickel-Catalyzed Highly Regioselective Hydrocyanation of Terminal Alkynes with Zn(CN)2 Using Water as the Hydrogen Source
Zhang, Xingjie,Xie, Xin,Liu, Yuanhong
supporting information, p. 7385 - 7389 (2018/06/11)
The first efficient and general nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)2 in the presence of water has been developed. The reaction provides a regioselective protocol for the synthesis of functionalized vinyl nitriles with a range of structural diversity under mild reaction conditions while obviating use of the volatile and hazardous reagent of HCN. Deuterium-labeling experiments confirmed the role of water as the hydrogen source in this hydrocyanation reaction.
Highly-phosphorescent tungsten(0) carbonyl pyridyl-imidazole complexes as photosensitisers
Lee, Jia Jin,Yap, Chew Pheng,Chwee, Tsz Sian,Fan, Wai Yip
, p. 11008 - 11012 (2017/08/30)
Photoluminescence data are reported for two W(CO)4L complexes (L = 2-(1H-imidazol-2-yl)pyridine and 2-(2′-pyridyl)benzimidazole) in room-temperature solutions. The bidentate ligands consist of a pyridine and an imidazole moiety connected by a C-C bond. The complexes have been found to exhibit enhanced phosphorescence from the metal-to-ligand charge transfer (MLCT) excited state with quantum yields in the order of 10-3, almost two orders of magnitude higher than those reported for W(CO)4(diimine) complexes. One of the complexes W(CO)4(2-(2′-pyridyl)benzimidazole) can serve as an efficient visible-light photosensitiser for the isomerisation of aromatic alkenes with efficiency comparable to and even exceeding that of the well-studied ruthenium tris-bipyridine complex, Ru(bpy)Cl2.
