- Asymmetric Deoxygenative Cyanation of Benzyl Alcohols Enabled by Synergistic Photoredox and Copper Catalysis?
-
Summary of main observation and conclusion. An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis. This reaction features the use of organic photosensitizer and low-cost 3d metal catalyst, simple and safe operations, and extremely mild conditions. A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantiocontrols from readily available feedstocks (22 examples, up to 93% yield and 92% ee).
- Chen, Hong-Wei,Lu, Fu-Dong,Cheng, Ying,Jia, Yue,Lu, Liang-Qiu,Xiao, Wen-Jing
-
supporting information
p. 1671 - 1675
(2020/11/03)
-
- Preparation method of alkyl nitrile compound
-
The invention discloses a preparation method of an alkyl nitrile compound. Specifically, the preparation method comprises the following step: in an organic solvent, in the presence of a protective gasand under the action of a catalyst, carrying out a reduction reaction as shown in the specification on olefin as shown in a formula I, a cyanation reagent and water, wherein the alkyl nitrile compound 1 is a compound II and/or a compound III. The preparation method provided by the invention is mild in condition, can realize hydrocyanation of olefin more safely and efficiently, and has good substrate universality and functional group compatibility.
- -
-
Paragraph 0137-0139
(2020/08/18)
-
- α-Methylation of 2-Arylacetonitrile by a Trimethylamine-Borane/CO2 System
-
A highly selective monomethylation of 2-arylacetonitrile using CO2 is described. The utilization of trimethylamine-borane facilitates the six-electron reduction of CO2. This reaction is the first selective six-electron reductive functionalization of CO2 faciliated by C(sp3)-H bonds. A variety of 2-arylpropionitrile was obtained in good yields. The reaction could also be applied at the gram scale.
- Zhang, Xiaowei,Wang, Sheng,Xi, Chanjuan
-
p. 9744 - 9749
(2019/08/16)
-
- Selective α-Monomethylation by an Amine-Borane/N,N-Dimethylformamide System as the Methyl Source
-
A new and practical α-monomethylation strategy using an amine-borane/N,N-dimethylformamide (R3N-BH3/DMF) system as the methyl source was developed. This protocol has been found to be effective in the α-monomethylation of arylacetonitriles and arylacetamides. Mechanistic studies revealed that the formyl group of DMF delivered the carbon and one hydrogen atoms of the methyl group, and R3N-BH3 donated the remaining two hydrogen atoms. Such a unique reaction pathway enabled controllable assemblies of CDH2-, CD2H-, and CD3- units using Me2NH-BH3/d7-DMF, Me3N-BD3/DMF and Me3N-BD3/d7-DMF systems, respectively. Further application of this method to the facile synthesis of anti-inflammatory flurbiprofen and its varied deuterium-labeled derivatives was demonstrated.
- Xia, Hui-Min,Zhang, Feng-Lian,Ye, Tian,Wang, Yi-Feng
-
supporting information
p. 11770 - 11775
(2018/09/10)
-
- 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)
-
- Methylation of C(sp3)-H/C(sp2)-H bonds with methanol catalyzed by cobalt system
-
A highly efficient Co-based catalytic system, composed of a commercially available Co salt, a tetradentate phosphine ligand P-(CH2CH2PPh2)3(PP3), and a base (denoted as [Co]/PP3/base), is developed for the methylation of C(sp3)-H and C(sp2)-H bonds using methanol as a methylating reagent. The Co(BF4)2.6H2O/PP3/K2CO3 catalytic system showed high catalytic activity for the methylation of C-H bonds in aryl alkyl ketones, aryl acetonitriles, and indoles, with wide substrate scope and good functional group tolerance, and methylsubstituted products were obtained in good to excellent yields at 100 °C. This cheap, readily available, and highly efficient Co-based catalytic system may have promising applications in methylation reaction using methanol.
- Liu, Zhenghui,Yang, Zhenzhen,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
-
supporting information
p. 5228 - 5231
(2017/11/06)
-
- 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 19
(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)
-
- Hiyama reactions of activated and unactivated secondary alkyl halides catalyzed by a nickel/norephedrine complex
-
(Chemical Equation Presented) An active partner: Nickel in combination with an amino alcohol ligand (norephedrine) was found to provide the most versatile and efficient catalyst for Hiyama cross-coupling reactions of alkyl electrophiles that has been described to date. Unprecedented Hiyama reactions of activated secondary alkyl bromides were achieved, as were the first Hiyama couplings of (activated) alkyl chlorides (see scheme, X = Br, Cl; HMDS = 1,1,1,3,3,3-hexamethyldisilazane, DMA = N,N-dimethylacetamide).
- Strotman, Neil A.,Sommer, Stefan,Fu, Gregory C.
-
p. 3556 - 3558
(2008/02/14)
-
- Mild palladium-catalyzed selective monoarylation of nitriles
-
Two new palladium-catalyzed procedures for the arylation of nitriles under less basic conditions than previously reported have been developed. The selective monoarylation of acetonitrile and primary nitriles has been achieved using α-silyl nitriles in the presence of ZnF2. This procedure is compatible with a variety of functional groups, including cyano, keto, nitro, and ester groups, on the aryl bromide. The arylation of secondary nitriles occurred in high yield by conducting reactions with zinc cyanoalkyl reagents. These reaction conditions tolerated base-sensitive functional groups, such as ketones and esters. The combination of these two methods, one with a-silyl nitriles and one with zinc cyanoalkyl reagents, provides a catalytic route to a variety of benzylic nitriles, which have not only biological significance but utility as synthetic intermediates. The utility of these new coupling reactions has been demonstrated by a synthesis of verapamil, a clinically used drug for the treatment of heart disease, by a three-step route from commercial materials that allows convenient variation of the aryl group.
- Wu, Lingyun,Hartwig, John F.
-
p. 15824 - 15832
(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)
-
- 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)
-
- SOME NEW ANALOGUES OF VERAPAMIL AND MEPAMIL. SYNTHESIS AND BASIC PHARMACOLOGICAL PROPERTIES
-
Some new analogues of verapamil (Ia) and mepamil (Ib), calcium antagonists of arylkylamine type, were synthesized and screened for cardiovascular activities.The basic structure was modified a) on the phenyl ring, attached to the quaternary carbon, b) on the alkyl group, attached to the quaternary carbon and c) on the alkylamino group, attached in position 3 to the n-propyl fragment.Except of 2-(2-chlorophenyl)-2-isopropyl-5-(N-methylhomoveratrylamino)valeronitrile (VIa), all the synthesized compounds exhibited lower hypotensive activity, than the mother compound, verapamil.
- Butora, Gabriel,Blaha, Ludvik,Rajsner, Miroslav,Helfert, Ivan
-
p. 1967 - 1981
(2007/10/02)
-
- An Easy Access to α-Aryl Alkyl Nitriles
-
The preparation of α-aryl alkyl nitriles (2), precursors of the nonstereoidal antiinflammatory α-arylaliphatic acids, via the displacement of the corresponding halides with sodium cyanide employing benzyltriethylammonium chloride as catalyst in acetonitrile in 70-85percent yield (>95percent purity), is described.
- Singh, N. P.,Kumar, A.
-
p. 1195 - 1196
(2007/10/02)
-
- Oxidative Decyanation of Secondary Nitriles to Ketones
-
Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.
- Freerksen, Robert W.,Selikson, Sandra J.,Wroble, Randall R.,Kyler, S. Keith,Watt, David S.
-
p. 4087 - 4096
(2007/10/02)
-