28769-48-4Relevant articles and documents
Method for preparing alkenyl cyanide compounds
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Paragraph 0175; 0179-0181, (2019/10/23)
The invention discloses a method for preparing alkenyl cyanide compounds represented by formula II. Alkynes represented by formula I and a cyanation reagent are subjected to a reduction reaction represented by a formula shown in the description in an organic solvent under the protection of a gas at 20-100 DEG C under the action of a nickel catalyst, a reducing agent and H2O to prepare the alkenyl cyanide compounds represented by formula II. The preparation method of the invention, which adopts the cheap nickel as the catalytic system, has the advantages of simplicity in operation, mild reaction conditions, good compatibility of functional groups, wide application range of the substrate, high reaction efficiency and high yield, so the method has high application and promotion values.
Direct Access to Versatile Electrophiles via Catalytic Oxidative Cyanation of Alkenes
Gao, De-Wei,Vinogradova, Ekaterina V.,Nimmagadda, Sri Krishna,Medina, Jose M.,Xiao, Yiyang,Suciu, Radu M.,Cravatt, Benjamin F.,Engle, Keary M.
supporting information, p. 8069 - 8073 (2018/06/22)
Nucleophilic attack on carbon-based electrophiles is a central reactivity paradigm in chemistry and biology. The steric and electronic properties of the electrophile dictate its reactivity with different nucleophiles of interest, allowing the opportunity to fine-tune electrophiles for use as coupling partners in multistep organic synthesis or for covalent modification of proteins in drug discovery. Reactions that directly transform inexpensive chemical feedstocks into versatile carbon electrophiles would therefore be highly enabling. Herein, we report the catalytic, regioselective oxidative cyanation of conjugated and nonconjugated alkenes using a homogeneous copper catalyst and a bystanding N-F oxidant to furnish branched alkenyl nitriles that are difficult to prepare using existing methods. We show that the alkenyl nitrile products serve as electrophilic reaction partners for both organic synthesis and the chemical proteomic discovery of covalent protein ligands.
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.
Metallo-β-lactamase inhibitors by bioisosteric replacement: Preparation, activity and binding
Skagseth, Susann,Akhter, Sundus,Paulsen, Marianne H.,Muhammad, Zeeshan,Lauksund, Silje,Samuelsen, ?rjan,Leiros, Hanna-Kirsti S.,Bayer, Annette
, p. 159 - 173 (2017/04/26)
Bacterial resistance is compromising the use of β-lactam antibiotics including carbapenems. The main resistance mechanism against β-lactams is hydrolysis of the β-lactam ring mediated by serine- or metallo-β-lactamases (MBLs). Although several inhibitors of MBLs have been reported, none has been developed into a clinically useful inhibitor. Mercaptocarboxylic acids are among the most prominent scaffolds reported as MBL inhibitors. In this study, the carboxylate group of mercaptocarboxylic acids was replaced with bioisosteric groups like phosphonate esters, phosphonic acids and NH-tetrazoles. The influence of the replacement on the bioactivity and inhibitor binding was evaluated. A series of bioisosteres of previously reported inhibitors was synthesized and evaluated against the MBLs VIM-2, NDM-1 and GIM-1. The most active inhibitors combined a mercapto group and a phosphonate ester or acid, with two/three carbon chains connecting a phenyl group. Surprisingly, also compounds containing thioacetate groups instead of thiols showed low IC50 values. High-resolution crystal structures of three inhibitors in complex with VIM-2 revealed hydrophobic interactions for the diethyl groups in the phosphonate ester (inhibitor 2b), the mercapto bridging the two active site zinc ions, and tight stacking of the benzene ring to the inhibitor between Phe62, Tyr67, Arg228 and His263. The inhibitors show reduced enzyme activity in Escherichia coli cells harboring MBL. The obtained results will be useful for further structural guided design of MBL inhibitors.
Pd-catalyzed threefold arylation of Baylis-Hillman bromides and acetates with triarylbismuth reagents
Rao, Maddali L. N.,Giri, Somnath
, p. 4580 - 4589 (2012/11/07)
Functionalized alkyl 2-benzylacrylates and 2-benzylacrylonitriles were synthesized by means of atom-economic cross-couplings of Baylis-Hillman bromides or acetates with BiAr3 under palladium-catalyzed conditions. These reactions, involving thre
A New Simple Synthesis of α-Substituted Acrylonitriles
Baraldi, P. G.,Pollini, G. P.,Zanirato, V.,Barco, A.,Benetti, S.
, p. 969 - 970 (2007/10/02)
An efficient preparation of α-substituted acrylonitriles 6 based on the utilization of 4-cyano-3-ketothiolane enolate anion (3) as a synthetic equivalent to α-acrylonitrile anion (1) is described.
CONVENIENT SYNTHETIC ROUTES TO α-OLIGOSILOXANYLACRYLONITRILES
Kawakami, Yuhsuke,Hisada, Hirofumi,Yamashita, Yuya
, p. 5835 - 5836 (2007/10/02)
Novel 1,4-elimination reaction of C,N-bis(trimethylsilyl)-C-trimethylsiloxymethylketenimine and retro Diels-Alder reaction of 2-oligosiloxanyl-5-norbornene-2-carbonitrile cleanly gave α-oligosiloxanylacrylonitriles in excellent yield.
STEREOCHEMICAL COURSE OF THE PALLADIUM-CATALYSED ARYLATION OF DISUBSTITUTED ACTIVATED ALKENES WITH BENZOYL CHLORIDE
Spencer, Alwyn
, p. 209 - 216 (2007/10/02)
The palladium-catalysed arylation of ten 1,1- and 1,2-disubstituted activated alkenes with benzoyl chloride was studied.In most cases, more than one product was formed.The stereochemical course of the arylation appears to be controlled by the polarity of
Phenyl- and Tolylthallium(III) Bis(trichloroacetate)s; Preparation and Reactions
Uemura, Sakae,Miyoshi, Haruo,Wakasugi, Mikio,Okano, Masaya,Itoh, Osamu,et. al.
, p. 553 - 554 (2007/10/02)
Phenyl- and tolylthallium(III) bis(trichloroacetate)s were prepared from thallium(III) oxide, trichloroacetic acid, benzene, and toluene.The replacement of the thallium moiety in 1 with iodo, chloro, cyano, selenocyanato, and nitro groups and the aromatic coupling of 1 proceeded smoothly to give the corresponding aromatic derivatives in good yields.In the presence of PdCl2-NaOAc, 1 (Ar=phenyl) reacted with acrylonitrile and methacrylonitrile to afford cinnamonitriles (trans and cis) and a mixture of α-benzylacrylonitrile and β-phenylmethacrylonitriles (Z and E) respectively.
