cas 769-68-6, 2-PHENYLBUTYRONITRILE | Articles data

Articles about 769-68-6Total 67 be found

Article title
Article abstract
Author
Journal number and time
Download

Direct C(sp3)-H Cyanation Enabled by a Highly Active Decatungstate Photocatalyst
A highly efficient, direct C(sp3)-H cyanation was developed under mild photocatalytic conditions. The method enabled the direct cyanation of various C(sp3)-H substrates with excellent functional group tolerance. Notably, complex natural products and bioactive compounds were efficiently cyanated.
Kim, Kunsoon,Lee, Seulchan,Hong, Soon Hyeok
supporting information
p. 5501 - 5505
(2021/07/26)

Base-controlled chemoselectivity: direct coupling of alcohols and acetonitriles to synthesise α-alkylated arylacetonitriles or acetamides
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.
Bai, Liang,Ge, Min-Tong,Li, Chen,Qiu, Yuan-Rui,Wang, Ying,Xia, Ai-Bao,Xu, Dan-Qian
supporting information
p. 15200 - 15204
(2021/09/06)

Photocatalytic Hydromethylation and Hydroalkylation of Olefins Enabled by Titanium Dioxide Mediated Decarboxylation
A versatile method for the hydromethylation and hydroalkylation of alkenes at room temperature is achieved by using the photooxidative redox capacity of the valence band of anatase titanium dioxide (TiO2). Mechanistic studies support a radical-based mechanism involving the photoexcitation of TiO2 with 390 nm light in the presence of acetic acid and other carboxylic acids to generate methyl and alkyl radicals, respectively, without the need for stoichiometric base. This protocol is accepting of a broad scope of alkene and carboxylic acids, including challenging ones that produce highly reactive primary alkyl radicals and those containing functional groups that are susceptible to nucleophilic substitution such as alkyl halides. This methodology highlights the utility of using heterogeneous semiconductor photocatalysts such as TiO2 for promoting challenging organic syntheses that rely on highly reactive intermediates.
Zhu, Qilei,Nocera, Daniel G.
supporting information
p. 17913 - 17918
(2020/12/04)

Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions
The realization of photocatalysis for practical synthetic application hinges on the development of inexpensive photocatalysts which can be prepared on a large scale. Herein an air-stable, visible-light-absorbing photoluminescent tungsten(vi) complex which can be conveniently prepared at the gram-scale is described. This complex could catalyse photochemical organic transformation reactions including borylation of aryl halides, such as aryl chloride, reductive coupling of benzyl bromides for C-C bond formation, reductive coupling of phenacyl bromides, and decarboxylative coupling of redox-active esters of alkyl carboxylic acid with high product yields and broad functional group tolerance.
Chan, Kaai-Tung,Che, Chi-Ming,Du, Lili,Liu, Yungen,Phillips, David Lee,To, Wai-Pong,Tong, Glenna So Ming,Wu, Liang-Liang,Yu, Daohong
p. 6370 - 6382
(2020/07/15)

Ni-Catalyzed hydrocyanation of alkenes with formamide as the cyano source
CN generation from formamide dehydration! A novel Ni-catalyzed hydrocyanation of various alkenes to provide aliphatic nitriles is developed by generating hydrocyanic acid in situ from safe and readily available formamide. Excellent linear or branched regio-selectivity, wide substrate scope, cheap and stable nickel salt as a pre-catalyst, a safe cyano source, slow generation of CN to obviate catalyst deactivation and convenient experimental operation would render this hydrocyanation attactive for laboratory synthesis of aliphatic nitriles.
Shu, Xiao,Jiang, Yuan-Yuan,Kang, Lei,Yang, Luo
supporting information
p. 2734 - 2738
(2020/06/17)

Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols
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.
Huang, Shuang,Hong, Xi,Sun, Yong,Cui, He-Zhen,Zhou, Quan,Lin, Yue-Jian,Hou, Xiu-Feng
(2020/02/13)

Double metal cyanides as heterogeneous Lewis acid catalysts for nitrile synthesis: Via acid-nitrile exchange reactions
A series of transition metal-based double metal cyanides (DMCs) were studied as catalysts for the synthesis of nitriles via acid-nitrile exchange reaction. The best nitrile yields were obtained with Co3[Co(CN6)]2 DMC, which proved to be a versatile, stable, reusable and highly active catalyst, exhibiting an activity comparable to that of homogeneous Lewis acid catalysts.
Marquez, Carlos,Corbet, Matthieu,Smolders, Simon,Marion, Philippe,De Vos, Dirk
supporting information
p. 12984 - 12987
(2019/11/05)

Sustainable Alkylation of Nitriles with Alcohols by Manganese Catalysis
A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This alkylation reaction uses naturally abundant alcohols and readily available nitriles as coupling partners. The reaction tolerates a wide range of functional groups and heterocyclic moieties, efficiently providing useful cyanoalkylated products with water as the only side product. Importantly, methanol can be used as a C1 source and the chemoselective C-methylation of nitriles is achieved. The mechanistic investigations support the multiple role of the metal-ligand manganese catalyst, the dehydrogenative activation of the alcohol, α-C-H activation of the nitrile, and hydrogenation of the in-situ-formed unsaturated intermediate.
Borghs, Jannik C.,Tran, Mai Anh,Sklyaruk, Jan,Rueping, Magnus,El-Sepelgy, Osama
p. 7927 - 7935
(2019/06/24)

Surprising and Highly Efficient Use of Methylmagnesium Chloride as a Non-Nucleophilic Base in the Deprotonation and Alkylation of sp3 Centres Adjacent to Nitriles
Methylmagnesium chloride (MeMgCl) is a key reagent in research and industry typically as a nucleophile. In this article we develop the use of MeMgCl as a non-nucleophilic base in conjunction with catalytic amounts of an amine mediator. Specifically, we use the base to deprotonate α to a variety of nitriles in alkylation reactions, applying it to the synthesis of a wide variety of tertiary and quaternary nitriles, including examples where we successively and successfully added three different substituents on the carbon α to the nitrile. This method is generally applicable, high yielding and much greener than existing methods, and it has considerable advantages for industrial application.
Gbadebo, Omolola,Smith, Dennis,Harnett, Ger,Donegan, Gregory,O'Leary, Patrick
p. 7037 - 7045
(2019/01/04)

Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation
The preparation of nitriles from primary amides or aldoximes was achieved by using oxalyl chloride with a catalytic amount of dimethyl sulfoxide in the presence of Et3N. The reactions were complete within 1 h after addition at room temperature. A diverse range of cyano compounds were obtained in good to excellent yields, including aromatic, heteroaromatic, cyclic, and acyclic aliphatic species.
Ding, Rui,Liu, Yongguo,Han, Mengru,Jiao, Wenyi,Li, Jiaqi,Tian, Hongyu,Sun, Baoguo
p. 12939 - 12944
(2018/10/20)

Dehydration of Amides to Nitriles under Conditions of a Catalytic Appel Reaction
A highly expedient protocol for a catalytic Appel-type dehydration of amides to nitriles has been developed that employs oxalyl chloride and triethylamine along with triphenylphosphine oxide as a catalyst. The reactions are usually complete in less than 10 min with only a 1 mol % catalyst loading. The reaction scope includes aromatic, heteroaromatic, and aliphatic amides, including derivatives of α-hydroxy and α-amino acids.
Shipilovskikh, Sergei A.,Vaganov, Vladimir Yu.,Denisova, Elena I.,Rubtsov, Aleksandr E.,Malkov, Andrei V.
supporting information
p. 728 - 731
(2018/02/09)

Manganese Catalyzed α-Alkylation of Nitriles with Primary Alcohols
The manganese(I) complex bearing a bidentate hydrazone ligand efficiently catalyzes the α-alkylations of nitrile using primary alcohols as alkylating agents. α-Functionalized nitriles were selectively obtained in good to excellent yields. The reaction is environmentally benign, producing water as the sole byproduct. Both benzylic and aliphatic alcohols could be used and functional groups were tolerated.
Jana, Akash,Reddy, C. Bal,Maji, Biplab
p. 9226 - 9231
(2018/09/21)

Enantioseparation of Sulfoxides and Nitriles by Inclusion Crystallization with Chiral Organic Salts Based on l-Phenylalanine
Enantioselective inclusion of aromatic sulfoxides and nitriles was achieved in a host framework created by organic salts comprising achiral benzoic acids and a chiral primary amine (1a) derived from l-phenylalanine. Tuning of the combined achiral acid component successfully changed the chiral recognition ability of the organic salts. The guest molecules were hydrogen-bonded to form three-component inclusion crystals, and the enantiomers of nitriles and sulfoxides were separated with high selectivity up to 92 and 98 % ee. As far as we know, this is the first example of the enantioseparation of non-functionalized aromatic nitriles.
Kodama, Koichi,Kanai, Hayato,Shimomura, Yuki,Hirose, Takuji
supporting information
p. 1726 - 1729
(2018/04/24)

Process for the Catalytic Reversible Alkene-Nitrile Interconversion
The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.
-
Page/Page column 21; 22

(2017/09/02)

Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
p. 7621 - 7627
(2017/07/26)

Facile Ruthenium(II)-Catalyzed α-Alkylation of Arylmethyl Nitriles Using Alcohols Enabled by Metal-Ligand Cooperation
A facile ruthenium(II)-catalyzed α-alkylation of arylmethyl nitriles using alcohols is reported. The ruthenium pincer catalyst serves as an efficient catalyst for this atom-economical transformation that undergoes alkylation via borrowing hydrogen pathways, producing water as the only byproduct. Arylmethyl nitriles containing different substituents can be effectively alkylated using diverse primary alcohols. Notably, using ethanol and methanol as alkylating reagents, challenging ethylation and methylation of arylmethyl nitriles were performed. Secondary alcohols do not undergo alkylation reactions. Thus, phenylacetonitrile was chemoselectively alkylated using primary alcohols in the presence of secondary alcohols. Diols provided a mixture of products. When deuterium-labeled alcohol was used, the expected deuterium transposition occurred, providing both α-alkylation and α-deuteration of arylmethyl nitriles. Consumption of nitrile was monitored by GC, which indicated the involvement of first-order kinetics. Plausible mechanistic pathways are suggested on the basis of experimental evidence. The ruthenium catalyst reacts with base and generates an unsaturated intermediate, which further reacts with both nitriles and alcohols. While nitrile is transformed to enamine via [2 + 2] cycloaddition, alcohol is oxidized to aldehyde. The metal bound enamine adduct reacts with aldehyde via Michael addition, resulting in an ene-imine adduct, which perhaps undergoes direct hydrogenation by a Ru dihydride intermediate, produced from alcohol oxidation. However, in situ monitoring of the reaction mixture confirmed the presence of unsaturated vinyl nitrile in the reaction mixture in minor amounts (10%), indicating the possible dissociation of ene-imine adduct during the catalysis, which may further be hydrogenated to provide the α-alkylated nitriles. Overall, the efficient α-alkylation of nitriles using alcohols can be attributed to the amine-amide metal-ligand cooperation that is operative in the ruthenium pincer catalyst, which enables all of the catalytic intermediates to remain in the +2 oxidation state throughout the catalytic cycle.
Thiyagarajan, Subramanian,Gunanathan, Chidambaram
p. 5483 - 5490
(2017/08/17)

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols
The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.
Li, Junjun,Liu, Yuxuan,Tang, Weijun,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
supporting information
p. 14445 - 14449
(2017/10/07)

Tert-Butoxide-Mediated Arylation of 2-Substituted Cyanoacetates with Diaryliodonium Salts
A transition metal-free direct arylation of 2-substituted cyanoacetates with diaryliodonium salts was developed. With this approach, a wide range of α-tolunitrile derivatives has been synthesized in good to excellent yields of 45-92%. Furthermore, the practicability of this approach is further manifested in the synthesis of a related bioactive agent of glutarimide.
Qian, Xiaofei,Han, Jianwei,Wang, Limin
p. 940 - 946
(2016/04/05)

Nano-K2CO3: Preparation, characterization and evaluation of reactive activities
A novel base, nano-K2CO3, was easily prepared by ultrafine wet milling. The surface properties and the reactive activities of nano-K2CO3 were characterized. It was found that such a base showed higher basicity than normal K2CO3 and could replace sodium (or potassium) alkoxide to carry out monoalkylation and oximation of active methylene compounds. The nano-K2CO3 could be regenarated and reused 10 times without loss of its reactive activity.
Li, Jun-Zhang,Fan, Shi-Ming,Sun, Xuan-Fei,Liu, Shouxin
p. 1865 - 1869
(2016/01/20)

Nitrile synthesis through catalyzed cascades involving acid-nitrile exchange
Irreversible acid-nitrile exchange reactions using both glutaronitrile and (phenylsulfonyl)acetonitrile may be catalyzed by Lewis acids. Whereas a cyclization towards imides displaces the equilibria in the reaction with dinitriles, a decarboxylation step is involved when using the (phenylsulfonyl)acetonitrile. Georg Thieme Verlag Stuttgart New York.
Cartigny, Damien,Dos Santos, Aurelie,El Kaim, Laurent,Grimaud, Laurence,Jacquot, Roland,Marion, Philippe
p. 1802 - 1806
(2014/07/08)

Method for producing compounds comprising nitrile functions
The present invention concerns the production of compounds comprising nitrite functions and cyclic imide compounds. More specifically, the invention relates to the production of compounds comprising nitrile functions from compounds comprising carboxylic functions, advantageously of natural and renewable origin, and from methyl-2 glutaronitrile (MGN) or a mixture N of dinitriles comprising methyl-2 glutaronitrile (MGN), ethyl-2 succinonitrile (ESN) and adiponitrile (AdN).
-
Paragraph 0071-0075; 0077-0078

(2014/12/09)

Synergistic effect of a bis(proazaphosphatrane) in mild palladium-catalyzed direct α-arylations of nitriles with aryl chlorides
The effect of a bis(proazaphosphatrane) ligand on the palladium-catalyzed direct α-arylation of nitriles with various aryl chlorides under mild conditions is reported. Comparisons of the catalytic properties of this ligand with those of three related mono(proazaphosphatrane)s under the same reaction conditions revealed that bis(proazaphosphatrane) displayed a synergistically enhanced activity. In the presence of the bis(proazaphosphatrane) ligand, ethyl cyanoacetate and primary as well as secondary nitriles were efficiently coupled with a wide variety of aryl chlorides that contained electron-rich, electron-poor, and electron-neutral groups.
Han Kim, So,Jang, Wonseok,Kim, Min,Verkade, John G.,Kim, Youngjo
p. 6025 - 6029
(2015/03/30)

A one-pot umpolung method for preparation of α-aryl nitriles from α-chloro aldoximes via organocuprate additions to transient nitrosoalkenes
Conjugate addition of a variety of aryl lithiocyanocuprates to nitrosoalkenes generated from α-chloro aldoximes, followed by in situ dehydration of the crude α-aryl aldoxime product with N,N- dicyclohexylcarbodiimide, affords α-aryl nitriles in good overall yields via a one-pot protocol. Georg Thieme Verlag Stuttgart ? New York.
Sengupta, Ritobroto,Weinreb, Steven M.
p. 2933 - 2937
(2012/10/29)

Novel α-arylnitriles synthesis via Ni-catalyzed cross-coupling of α-bromonitriles with arylboronic acids under mild conditions
An applicable and easy-handling Ni-catalyst can be used to promote direct arylation of α-bromonitriles with various arylboronic acids to construct α-arylnitriles under mild conditions. The methodology tolerates β-hydrogens and functional groups in the substrates.
Yang, Yingying,Tang, Shan,Liu, Chao,Zhang, Huimin,Sun, Zhexun,Lei, Aiwen
supporting information; experimental part
p. 5343 - 5345
(2011/09/13)

Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
supporting information; experimental part
p. 4470 - 4474
(2011/06/24)

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives
Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9′,10′-dihydro-9′,10′-anthraceno-3- pyrrolinium) derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b- dihydrodibenzo[a,f]cyclopropa[cd]pentaleno)}-pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.
Ihmels, Heiko,Luo, Jia
supporting information; experimental part
p. 119 - 126
(2011/05/15)

Synthesis of α-aryl nitriles through B(C6F5)3-catalyzed direct cyanation of α-aryl alcohols and thiols
Various α-aryl nitriles have been prepared in excellent yield from the corresponding α-aryl alcohols employing 3 mol % of B(C6F5)3 (1) as Lewis acid catalyst and (CH3)3SiCN (TMSCN) as cyanide source. Cyano transfer from TMSCN to alcohol proceeds within short reaction time at rt. α-Aryl thiols also produce corresponding nitriles in good to excellent yield at reflux condition.
Rajagopal, Gurusamy,Kim, Sung Soo
experimental part
p. 4351 - 4355
(2009/09/30)

Synthesis of 3,3-and 4,4-alkyl-phenyl-substituted pyrrolidin-2-one derivatives
Syntheses of 3,3-and 4,4-alkyl-phenyl-substituted pyrrolidin-2-one derivatives are described. The final compounds were obtained by the reductive cyclization of relevant cyanoalkanoate esters using NaBH4 and CoCl2.6H2O. The obtained pyrroIidin-2-one derivatives are pharmacophoric fragments for the synthesis of various biologically active compounds.
Kulig,Ignasik,Malawska
scheme or table
p. 1629 - 1636
(2010/07/06)

MUSCARINIC RECEPTOR ANTAGONISTS
The present invention relates to muscarinic receptor antagonists, which are useful, among other uses, for the treatment of various diseases of the respiratory, urinary and gastrointestinal systems mediated through muscarinic receptors. The invention also relates to the process for the preparation of disclosed compounds, pharmaceutical compositions containing the disclosed compounds, and the methods for treating diseases mediated through muscarinic receptors. Also provided herein are pharmaceutical compositions comprising one or more muscarinic receptor antagonists and at least one or more therapeutic agent selected from histamine antagonists, corticosteroids, beta agonists, leukotriene antagonists, EGFR kinase inhibitors, PAF antagonists, 5-lipoxygenase inhibitors, chemokine inhibitors, PDE-4 inhibitors or p38 MAP Kinase inhibitors.
-
Page/Page column 28-29

(2008/12/04)

Binaphthol-based diphosphite ligands in asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene: Influence of steric properties
A series of chiral (R)-binaphthol-based diphosphite ligands with different substituents was prepared and applied in the asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene to investigate the influence of their steric properties. The optimum steric properties for the hydrocyanation reaction lie within a narrow window. With the optimized ligand, hydrocyanation of styrene gave full conversion (Subs/Ni = 100) with 49% ee, the TON was determined to be 600. Hydrocyanation of 1,3-cyclohexadiene gave 50% conversion (Subs/Ni = 500) with an excellent ee of 86 %. This demonstrates that high ees are not only accessible for vinylarenes but also for conjugated dienes in the asymmetric nickelcatalyzed hydrocyanation.
Wilting, Jos,Janssen, Michele,Mueller, Christian,Lutz, Martin,Spek, Anthony L.,Vogt, Dieter
p. 350 - 356
(2008/02/07)

Mild cobalt-catalyzed hydrocyanation of olefins with tosyl cyanide
Mild-mannered and well-behaved: A conceptually new hydrocyanation reaction for non-activated olefins provides secondary and tertiary nitriles in good yields under mild conditions. Salient features of this process include broad functional-group tolerance, readily available starting materials, and ease of execution.
Gaspar, Boris,Carreira, Erick M.
p. 4519 - 4522
(2008/09/17)

Facile one-pot synthesis of 2-aryl-substituted nitriles and 2-aryl-3-keto nitriles via benzyne reaction
2-Aryl-substituted nitriles were prepared in good to excellent yields in a one-pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o-(trimethylsilyl)-phenyl]iodonium triflate, and 2-lithionitriles. 3-Keto nitriles substituted at the 2-position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N-lithiobenzocyclobutanimine intermediate is discussed. Copyright Taylor & Francis Group, LLC.
Kamila, Sukanta,Koh, Benjamin,Biehl, Edward R.
p. 3493 - 3507
(2007/10/03)

Environmentally friendly one-pot synthesis of α-alkylated nitriles using hydrotalcite-supported metal species as multifunctional solid catalysts
A ruthenium-grafted hydrotalcite (Ru/HT) and hydrotalcite-supported palladium nanoparticles (Pdnano/ HT) are easily prepared by treating basic layered double hydroxide, hydrotalcite (HT, Mg6Al 2(OH)16CO3) with aqueous RuCl 3·n H2O and K2[PdCl4] solutions, respectively, using surface impregnation methods. Analysis by means of X-ray diffraction, and energydispersive X-ray, electron paramagnetic resonance, and X-ray absorption fine structure spectroscopies proves that a monomeric RuIV species is grafted onto the surface of the HT. Meanwhile, after reduction of a surface-isolated PdII species, highly dispersed Pd nanoclusters with a mean diameter of about 70 A is observed on the Pdnano/HT surface by transmission electron microscopy analysis. These hydrotalcite-supported metal catalysts can effectively promote α-alkylation reactions of various nitriles with primary alcohols or carbonyl compounds through tandem reactions consisting of metal-catalyzed oxidation and reduction, and an aldol reaction promoted by the base sites of the HT. In these catalytic α-alkylations, homogeneous bases are unnecessary and the only by-product is water. Additionally, these catalyst systems are applicable to one-pot syntheses of glutaronitrile derivatives.
Motokura, Ken,Fujita, Noriaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Jitsukawa, Koichiro,Kaneda, Kiyotomi
p. 8228 - 8239
(2007/10/03)

Nucleophile-catalyzed asymmetric acylations of silyl ketene imines: Application to the enantioselective synthesis of verapamil
All-carbon quaternary stereocenters are generated with good enantioselectivity through a nucleophile-catalyzed acylation reaction of silyl ketene imines (see scheme, TBS = tert-butyldimethylsilyl). The method is applied to the first catalytic asymmetric synthesis of the drug verapamil.
Mermerian, Ara H.,Fu, Gregory C.
p. 949 - 952
(2007/10/03)

A Ruthenium-Grafted Hydrotalcite as a Multifunctional Catalyst for Direct α-Alkylation of Nitriles with Primary Alcohols
Treatment of a hydrotacite, Mg6Al2(OH)16CO3, with an aqueous solution of RuCl3·nH2O afforded a monomeric Ru(IV) species on the surface of the hydrotalcite. This novel Ru-grafted hydrotalcite (Ru/HT) efficiently catalyzed α-alkylation of nitriles with primary alcohols through the cooperative catalysis between the Ru species and the surface base sites. The catalyst system could be further extended for the one-pot synthesis of α,α-dialkylated phenylacetonitriles via the base-catalyzed Michael reaction of α-alkylated phenylacetonitrile with activate olefins. Copyright
Motokura, Ken,Nishimura, Daisuke,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
p. 5662 - 5663
(2007/10/03)

P(i-BuNCH2CH2)3N: An efficient ligand for the direct α-arylation of nitriles with aryl bromides
A new catalyst system for the synthesis of α-aryl-substituted nitriles is reported. The bicyclic triaminophosphine P(i-BuNCH 2CH2)3N (1b) serves as an efficient and versatile ligand for the palladium-catalyzed direct α-arylation of nitriles with aryl bromides. Using ligand 1b, ethyl cyanoacetate and primary as well as secondary nitriles are efficiently coupled with a wide variety of aryl bromides possessing electron-rich, electron-poor, electron-neutral, and sterically hindered groups.
You, Jingsong,Verkade, John G.
p. 8003 - 8007
(2007/10/03)

A General Method for the Direct α-Arylation of Nitriles with Aryl Chlorides
The long-standing challenge of developing a general method for the title methodology is met for a broad range of aryl chlorides through the use of bicyclic P(iBuNCH2CH2)3N (1) as a bulky electron-rich ligand for palladium (see scheme, dba = dibenzylideneacetone).
You, Jingsong,Verkade, John G.
p. 5051 - 5053
(2007/10/03)

Case studies in process screening and optimization utilizing a new automated reactor - Analysis system
The application of a new automated workstation for conducting solution-phase reactions in parallel during chemical process development is described. The fully automated reactor - analysis system is capable of reagent/reactant addition, temperature and agitation control, and sample extraction/quench/injection for online HPLC analysis. Both precision and accuracy of the fluidic delivery and sampling systems were measured through the use of standard ultraviolet chromophore solutions in conjunction with HPLC analysis. Agitation efficiency was evaluated using a phase-transfer catalysis reaction known to be rate-dependent on stirring frequency. Chemistry cases examined included several single and multistep reactions studied to identify the best reagent/solvent combinations (screening) and optimal levels of continuous variables such as temperature, concentration, and stoichiometry (optimization). A multistep route to a chiral substituted imidazolidin-2-one was developed from initial route scouting through reaction condition screening, optimization, and scale-up. Reactions performed included alkylation, reduction, oxidation, reductive amination, displacement, and cyclization.
Gooding, Owen W.,Lindberg, Thomas,Miller, Wendy,Munyak, Edward,Vo, Lanchi
p. 283 - 293
(2013/09/07)

Biosynthesis of porphyrins and related macrocycles. Part 52.1'2 Synthesis of 1-SH11-4Hjporphobilinogen and the (11R)enantiomer for stereochemical studies on hydroxymethylbilane synthase (porphobilinogen deaminase)
A synthetic route is devised for the synthesis of (115)-[11-2H,]porphobilinogen la and of the (1 lβ)-enantiomer Ib. Their absolute configurations and enantiomeric purity are established by degradation to a derivative of [2-2H,]glycine of known stereochemistry. Methods are then developed, based on the synthesis of chiral imidate esters, for determination of the configuration of [2H1]-labelled aminomethylpyrroles by converting them into [2H,]-labelled amidines followed by analysis using 'H-NMR. The labelled samples of PEG la and Ib serve as substrates for hydroxymethylbilane synthase and the products are trapped as [2H1]-labelIed aminomethylbilanes 7c and 7d. Their configurations are determined by the NMR assay to demonstrate that as PBG 1 is enzymically converted into the aminomethylbilane 7, there is overall retention of configuration at the aminomethyl carbon. The Royal Society of Chemistry 1999.
Neidhart, Werner L.,Anderson, Paul C.,Hart, Graham J.,Battersby, Alan R.
p. 2677 - 2689
(2007/10/03)

Synthesis of alkylaryl-and diarylnitriles from ketones via N-(1- arylalkylidene)-cyanomethyl amines
Alkylaryl- and diarylketones (Arcor; R= alkyl, aryl, 1) can be converted into nitriles [ArCH(CN)R, 2] containing an additional carbon atom through a base-promoted reaction of N-(1-arylalkylidene)-cyanomethyl amines [ArC(=NCH2CN)R, 3].
Selva, Maurizio,Bomben, Andrea,Tundo, Pietro
p. 1561 - 1569
(2007/10/03)

Decarboethoxylation of aryl-substituted a-cyanoesters by the method of phase transfer catalysis
-
Glushkov,L'vov,Davydova,Kudinova,Polyakova,Sanzharova,Anisimova
p. 155 - 157
(2007/10/03)

The use of dialkyl carbonates for safe and highly selective alkylations of methylene-active compounds. A process without waste production
The non-toxic compound dimethyl carbonate (DMC) can be used as a methylating and a methoxycarbonylating agent in place of methyl chloride and phosgene, respectively. We report here that DMC and other dialkyl carbonates (DAlkCs: dimethyl, diethyl and dibenzyl carbonates) allow very selective alkylations of a variety of CH2-acidic compounds. Both arylacetonitriles and alkyl arylacetates react with DAIkCs to yield the mono-C-alkylated derivatives (α-alkyl-α-arylacetonitriles and alkyl α-alkyl-α-arylacetates) with a selectivity of up to 99%, at complete conversion. Likewise, the mono-C-methylation by DMC proceeds selectively also on (aryloxy)acetonitriles and methyl (aryloxy)acetates. The reactions are carried out at temperature of 180-220°C in the presence of weak bases (usually K2CO3); under such conditions, DAlkCs efficiently replace the common and very toxic alkylating agents (dialkyl sulfates and alkyl halides). In addition to the high selectivity obtained and the intrinsic safety of the dialkyl carbonates, the reported reactions give rise to neither organic nor inorganic waste products.
Bomben, Andrea,Selva, Maurizio,Tundo, Pietro
p. 256 - 260
(2007/10/03)

Synthesis and utility of α,α'-bis (triethyl ammonium methylene chloride) β-phenyl ethene in hydroxide ion initiated reactions - A new multi-site phase transfer catalyst
A three step synthesis of novel 'multi-site' water soluble phase transfer catalyst viz, α,α'-bis(triethyl ammonium methylene chloride) β-phenyl ethene and its utility in various organic biphase reactions are described.
Balakrishnan,Jayachandran
p. 3821 - 3830
(2007/10/03)

Selective Mono-methylation of Arylacetonitriles and Methyl Arylacetates by Dimethyl Carbonate
Both arylacetonitriles and methyl arylacetates react with dimethyl carbonate (DMC) (20 molar excess) at 180 - 200 deg C in the presence of K2CO3 to produce monomethylated 2-arylpropionitriles and methyl 2-arylpropionates, respectively, with a selectivity >99.5percent.The reaction, with wide application, proceeds by DMC acting as a methoxycarbonylating agent towards the ArCH-X anion (X = CN, CO2Me) and as a methylating agent to ArC-(CO2Me)X.DMC also proved to be the best solvent for such reactions.
Selva, Maurizio,Marques, Carlos Alberto,Tundo, Pietro
p. 1323 - 1328
(2007/10/02)

Trialkyl acyl ammonium halides - A new series of phase transfer catalysts
Trialkyl acyl ammonium halides have found to be superior phase transfer catalysts. They were easy to prepare and afford the reactions to be carried out at elevated temperature, owing to their stability.
Bhalerao,Mathur,Nagabhushan Rao
p. 1645 - 1649
(2007/10/02)

ALKYLATION OF PHENYLACETONITRILE USING POTASSIUM CARBONATE AS A BASE
-
Xu, ChengZhi,Mao, XiangJun,Shen, HongBo,Chen, WenQuiang
p. 153 - 156
(2007/10/03)

Die Isocyanid-Cyanid-Umlagerung - Mechanismus und praeparative Anwendung
Bis vor kurzem war die Isocyanid-Cyanid-Umlagerung hauptsaechlich als Beispiel fuer eine unimolekular verlaufende Gasphasenreaktion bekannt und nur fuer einfache Systeme kinetisch untersucht.Kinetikstudien in Loesung wurden erst moeglich, als man eine ueberlagerte, zum gleichen Produkt fuehrende Radikalkette erkannte und diese inhibieren konnte.Die Geschwindigkeit der Isomerisierung erwies sich als kaum von der Struktur und von Substituenten abhaengig.Allenfalls starke sterische Hinderung in drei Dimensionen wie in tris-α-substituierten Triptylcylisocyaniden fuehrt zu einer deutlichen Erhoehung der Aktivierungsenthalpie.Die Ergebnisse lassen sich mit einem rein sigmatropen Mechanismus deuten und sind damit in Einklang mit Voraussagen aus ab-initio-Rechnungen.Auch praeparativ laesst sich diese Umlagerung inzwischen nutzen.Bei der Blitzpyrolyse sind die Ausbeuten an Cyanid nahezu quantitativ.Allylisocyanide reagieren ohne Allylisomerisierung und optisch aktive Isocyanide unter vollstaendiger Retention.Die Umlagerung kann sowohl Bestandteil wirtschaftlich interessanter Synthesen, z.B. der Entzuendungshemmer Ibuprofen und (S)-Naproxen, sein als auch beim Aufbau optisch aktiver β-Acyloxycyanide, die nuetzliche Synthesebausteine sind, aus optisch aktiven α-Aminosaeuren helfen.
Ruechardt, Christoph,Meier, Michael,Haaf, Klaus,Pakusch, Joachim,Wolber, Erwin K. A.,Mueller, Barbara
p. 907 - 915
(2007/10/02)

ARYNIC CONDENSATION OF NITRILE ANIONS IN THE PRESENCE OF THE COMPLEX BASE NaNH2-CH3CH2(OCH2CH2)2ONa
Nitrile anions are easily condensed with aryl halides in the presence of Complex Base NaNH2-CH3CH2(OCH2CH2)2ONa via the intermediate arynes.
Carre, M. C.,Ezzinadi, A. S.,Zouaoui, M. A.,Geoffroy, P.,Caubere, P.
p. 3323 - 3330
(2007/10/02)

Selective and Continuous-flow Mono-methylation of Arylacetonitriles with Dimethyl Carbonate under Gas-Liquid Phase-Transfer Catalysis Conditions
Very high selectivity in monomethylation of arylacetonitriles is observed when dimethyl carbonate is used as an alkylating agent under g.l.-p.t.c. conditions: thus phenylacetonitrile, reacting on a catalytic bed of corundum spheres coated with K2CO3 and polyethyleneglycol, yields 2-phenylpropionitrile with only 1percent of bismethylated by-product.The method is a new, one-step, general route to the synthesis of 2-arylpropionitriles.
Tundo, Pietro,Trotta, Francesco,Moraglio, Giovanni
p. 1070 - 1071
(2007/10/02)

SYNTHESIS OF FLUORINATED DERIVATIVES OF GLUTETHIMIDE AND AMINOGLUTETHIMIDE
Aminoglutethimide (1), used in the treatment of hormone dependent breast cancer, interacts with enzyme complexes desmolase and aromatase.Its action is not specific and its metabolism gives rise to toxic and non-inhibitory metabolites.The work described here explores the impact of fluorine substitution within the glutethimide (2) framework, on the enzyme inhibitory properties of aminoglutethimide.Four new fluorinated derivatives (5), (6), (8) and (9) have been prepared, in which fluorine substituents have been introduced into the phenyl ring and the ethyl side chain. 4-Fluoroglutethimide (5) and 3-trifluoroglutethimide (6) were synthesised from the corresponding fluorophenylacetonitriles (10) and (14) via sequential monoethylation, Michael addition to methyl propenoate and cyclisation.An alternative strategy, devised for the synthesis of (8), involved the monoarylation of ethyl cyanoacetate, and gave rise to the intermediate (29).Incorporation of fluorine was carried out by SF4 fluorination of the cyanoketoester (33), which was subsequently converted to the difluoroaminoglutethimide (8).For the synthesis of trifluoromethyl glutethimide (9), the trifluoromethyl group was introduced by alkylation of phenylcyanoacetate (16) with 2-iodo-1,1,1-trifluoroethane.Preliminary in vitro enzyme inhibition results have been obtained for compounds (5), (6) and (8).
Hammond, Gerald B.,Plevey, Raymond G.,Sampson, Paul,Tatlow, John Colin
p. 81 - 98
(2007/10/02)