29127-83-1Relevant articles and documents
Z-Selective α-Arylation of α,β-Unsaturated Nitriles via [3,3]-Sigmatropic Rearrangement
Chen, Mengyuan,Liang, Yuchen,Dong, Taotao,Liang, Weijian,Liu, Yanping,Zhang, Yage,Huang, Xin,Kong, Lichun,Wang, Zhi-Xiang,Peng, Bo
, p. 2339 - 2345 (2021)
The Morita-Baylis–Hillman (MBH) reaction and [3, 3]-sigmatropic rearrangement are two paradigms in organic synthesis. We have merged the two types of reactions to achieve [3,3]-rearrangement of aryl sulfoxides with α,β-unsaturated nitriles. The reaction was achieved by sequentially treating both coupling partners with electrophilic activator (Tf2O) and base, offering an effective approach to prepare synthetically versatile α-aryl α,β-unsaturated nitriles with Z-selectivity through direct α-C-H arylation of unmodified α,β-unsaturated nitriles. The control experiments and DFT calculations support a four-stage reaction sequence, including the assembly of Tf2O activated aryl sulfoxide with α,β-unsaturated nitrile, MBH-like Lewis base addition, [3,3]-rearrangement, and E1cB-elimination. Among these stages, the Lewis base addition is diastereoselective and E1cB-elimination is cis-selective, which could account for the remarkable Z-selectivity of the reaction.
Method for preparing alpha-aryl nitrile and compound
-
Paragraph 0120; 0123-0124, (2021/01/12)
The invention discloses a method for preparing alpha-aryl nitrile, which comprises the following steps: assembling aryl sulfoxide and alpha, beta unsaturated nitrile under the action of an activator to form a rearrangement precursor, rearranging the rearrangement precursor under the action of alkali to obtain a rearrangement intermediate, adding inorganic alkali, and reacting at room temperature to obtain alpha-aryl nitrile. The invention also discloses a product obtained by the preparation method. Compared with the prior art, the method synthesizes alpha-aryl nitrile from aryl sulfoxide and alpha, beta unsaturated nitrile under mild conditions, and has the advantages that 1) the method is mild in reaction condition, good in selectivity, high in yield, easy in product separation, simple tooperate and good in functional group compatibility; 2) the raw materials used in the method are cheap and easily available, so that the defects that the alkalinity is too strong, the reaction condition requirement is strict and the reaction substrate is limited in the traditional method are avoided; and 3) the reaction mechanism is novel, and a new synthetic route is opened up for benzene ring ortho-position functionalization.
PROCESS FOR HYDROCYANATION OF TERMINAL ALKYNES
-
Page/Page column 13; 37, (2018/12/13)
The present invention refers to a process for a Rh-catalyzed Anti-Markovnikov hydrocyanation of terminal alkynes which process discloses, for the first time, the highly stereo- and regio-selective hydrocyanation of terminal alkynes to furnish E- configured alkenyl nitriles and the catalyst used in the present process.
Rh-Catalyzed Anti-Markovnikov Hydrocyanation of Terminal Alkynes
Ye, Fei,Chen, Junting,Ritter, Tobias
supporting information, p. 7184 - 7187 (2017/06/05)
We report the first highly stereo- and regioselective hydrocyanation of terminal alkynes to furnish E-configured alkenyl nitriles. Acrylonitriles can be accessed on gram scale with broad substrate scope and functional group tolerance. The hydrocyanation reaction employs acetone cyanohydrin as a practical alternative to HCN gas.
Synthesis of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs' catalysts
Rountree, Sandra M.,Taylor, Sarah F.R.,Hardacre, Christopher,Lagunas, M. Cristina,Davey, Paul N.
, p. 94 - 104 (2015/09/28)
A series of α,β-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (≥90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.
Solid-phase synthesis of (E)-3-substituted acrylonitriles from polystyrene-supported α-selenoacetonitrile
Wang, Chao-Li,Huang, Yi-Xiang,Sheng, Shou-Ri,Yang, Wei,Cai, Ming-Zhong
experimental part, p. 1282 - 1289 (2009/09/25)
A facile method for solid-phase organic synthesis of (E)-3-substituted acrylonitriles in good yields using polystyrene-supported α- selenoacetonitrile has been developed. The advantages of this method include straightforward operation, lack of odor, good
Highly active ruthenium-based catalyst for metathesis of cyano-contained olefins
Zhang, Wenzhen,Zhang, Rong,He, Ren
, p. 4203 - 4205 (2008/02/05)
Ruthenium benzylidene complex (H2IMes)(2-CH3-C5H4N)(Cl)2Ru{double bond, long}CHPh [H2IMes = 1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] (4), which introduced ortho substituted pyridine as dissociating ligand to weaken Ru-N bond and accelerate initiation through steric hindrance, was prepared by the reaction of (H2IMes)(PPh3)(Cl)2Ru{double bond, long}CHPh (1) with 2-methylpyridine and proved to exhibit enhanced catalytic activity for cyano-contained olefin metathesis.
Benzylideneruthenium complexes bearing pyridine-based ligands and their influence on the formation of mono- or bis(pyridine) complexes
Zhang, Wen-Zhen,He, Ren,Zhang, Rong
, p. 5345 - 5352 (2008/09/17)
Benzylideneruthenium complexes bearing the N-heterocyclic carbene (NHC) ligand 1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (H 2IMe) and one or two pyridine-based ligands have been prepared by treating [RuCl2-(=CHPh) (H
Indium(I) bromide-mediated coupling of dibromoacetonitrile with aldehydes followed by Boord elimination of bromine and oxygen of β-bromo alkoxides for preparation of 3-organyl-2-alkenenitriles
Peppe, Clovis,de Azevedo Mello, Paola,das Chagas, Rafael Pav?o
, p. 2335 - 2339 (2007/10/03)
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles.
