- Enantioselective borohydride 1,4-reduction of α,β-unsaturated carboxamides using optically active cobalt(II) complex catalysts
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The enantioselective borohydride reduction catalyzed by cobalt(II) complex was successfully applied to 1,4-reduction of β,β-disubstituted α,β-unsaturated carboxamides. In the presence of less than 1 mol% of optically active aldiminato cobalt(II) complex c
- Yamada, Tohru,Ohtsuka, Yuhki,Ikeno, Taketo
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- Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water
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Herein, unprecedented manganese-catalyzed direct α-alkenylation of amides using alcohols is reported. Aryl amides are reacted with diverse primary alcohols, which provided the α,β-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies indicate that Mn(I) catalyst oxidizes the alcohols to their corresponding aldehydes and also plays an important role in efficient C═C bond formation through aldol condensation. This selective olefination is facilitated by metal-ligand cooperation by the aromatization-dearomatization process operating in the catalytic system. Biorenewable alcohols are used as alkenylation reagents for the challenging α-alkenylation of amides with the highly abundant base metal manganese as a catalyst, which results in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.
- Pandia, Biplab Keshari,Gunanathan, Chidambaram
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p. 9994 - 10005
(2021/07/31)
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- Cross-Dehydrogenative Cyclization-Dimerization Cascade Sequence for the Synthesis of Symmetrical 3,3′-Bisoxindoles
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The synthesis of symmetrical 3,3′-bisoxindoles from simple acyclic β-oxoanilides is reported. The described method forges three new C-C bonds in a single step via a sequential Mn(OAc)3·2H2O mediated oxidative radical cyclization-fragmentation-dimerization process. The scope of this reaction is demonstrated in the preparation of a variety of 3,3′-bisoxindoles, as well as its application toward the formal synthesis of the Calycanthaceae alkaloid, (±)-folicanthine.
- Dobah, Farhaan,Mazodze, C. Munashe,Petersen, Wade F.
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supporting information
p. 5466 - 5470
(2021/07/31)
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- Efficiency Enhancement of a Photocatalytic Decarbonylation of an Aminocyclopropenone by Benzothiophene Substitution
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To improve the efficiency of the photocatalytic decarbonylation of cyclopropenones, the effects of substituents on cyclopropenone were explored. A benzothiophene-substituted aminocyclopropenone exhibited significantly improved decarbonylation efficiency t
- Mishiro, Kenji,Nomura, Mitsuki,Furuyama, Taniyuki,Kunishima, Munetaka
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p. 3625 - 3636
(2021/03/03)
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- method for alpha-alkylation of acetamides and thioacetamides under catalysis of nickel
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The invention discloses a method for alpha-alkylation of acetamide and thioacetamide under the catalysis of nickel. The method comprises the following steps: by taking a complex generated in situ by adivalent nickel salt and a phosphine ligand as a catalyst and primary alcohol as an alkylation reagent, performing alpha-alkylation reaction on acetamide or thioacetamide in an alkaline environment to prepare amide or thioamide. According to the alpha-alkylation reaction of acetamide and thioacetamide, the active catalyst can be generated in situ from a bivalent nickel salt and a phosphine ligand, so that the catalyst is prevented from being prepared in advance, the operation is simple and convenient, and experimental steps and cost are saved.
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Paragraph 0067-0072
(2020/12/05)
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- Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy
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A simple catalyst of Ni(OAc)2 and P(t-Bu)3 enables selective C-alkylation of thioacetamides and primary acetamides with alcohols for the first time. Monoalkylation of thioamides, amides and t-butyl esters occurs in excellent yields (>95%). Mechanistic studies reveal that the reaction proceeds via a hydrogen autotransfer pathway. This journal is
- Yang, Peng,Wang, Xiuhua,Ma, Yu,Sun, Yaxin,Zhang, Li,Yue, Jieyu,Fu, Kaiyue,Zhou, Jianrong Steve,Tang, Bo
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supporting information
p. 14083 - 14086
(2020/11/20)
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- Rh(i)-Catalyzed regioselective arylcarboxylation of acrylamides with arylboronic acids and CO2
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The first Rh(i)-catalyzed regioselective arylcarboxylation of electron-deficient acrylamides with arylboronic acids under atmospheric pressure of CO2 has been developed. A range of acrylamides and arylboronic acids were compatible with this reaction under redox-neutral conditions, leading to a series of malonate derivatives that are versatile building blocks in organic syntheses.
- Cai, Lei,Fu, Lei,Gao, Yuzhen,Li, Gang,Li, Shangda,Zhou, Chunlin
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supporting information
p. 7328 - 7332
(2020/11/19)
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- One-Pot Controlled Reduction of Conjugated Amides by Sequential Double Hydrosilylation Catalyzed by an Iridium(III) Metallacycle
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A single and accessible cationic iridiumIII metallacycle effectively catalyzes the one-pot sequential double hydrosilylation of challenging α,β-unsaturated secondary and tertiary amides to afford, in a controlled and straightforward way, the co
- Agbossou-Niedercorn, Francine,Corre, Yann,Djukic, Jean-Pierre,Kalocsai, Dorottya,Michon, Christophe,Nagyházi, Márton,Rysak, Vincent,Trivelli, Xavier
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supporting information
p. 6212 - 6220
(2020/10/02)
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- Chemoselective amide reductions by heteroleptic fluoroaryl boron Lewis acids
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The heteroleptic borane catalyst (C6F5)2B(CH2CH2CH2)BPin is found to hydrosilylatively reduce amides under mild conditions. Simple tertiary amides can be reduced using Me2EtSiH, whereas tertiary benzamides required a more reactive secondary silane, Et2SiH2, for efficient reduction. The catalytic system described exhibits exceptional chemoselectivity in the reduction of oligoamides and tolerates functionalities which are prone to reduction under similar conditions.
- Peruzzi, Michael T.,Mei, Qiong Qiong,Lee, Stephen J.,Gagné, Michel R.
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supporting information
p. 5855 - 5858
(2018/06/13)
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- Method for preparing N-aryl tertiary amide with substituted Meldrum's acid as acylating agent in water phase
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The invention discloses a method for preparing N-aryl tertiary in a water phase. According to the method, water is used as the solvent, and substituted Meldrum's acid and N-aryl secondary amine react at 80-100 DEG C for 1-10 h to obtain the N-aryl tertiary. The molar ratio of substituted Meldrum's acid to N-aryl secondary amine is 1:10-10:1. The reaction concentration of substituted Meldrum's acid or N-aryl secondary amine is 0.5-4 mol/L. The method overcomes the defect that in the prior art, acyl chloride, anhydride, dehydration coupling reagent, organic solvent, phase transfer catalyst or metal catalyst needs to be adopted, and has the advantages that by using substituted Meldrum's acid as an acylating agent, pre-activating of carboxylic acid or using of a dehydration coupling reagent is avoided; due to the fact that substituted Meldrum's acid is easy to prepare, using of certain carboxylic acid and activated derivatives which are hard to get or expensive is avoided; water is used as the solvent, so that using of toxic organic solvent is avoided; no acid, alkali or metal catalyst is adopted, so that influences of acid and alkali on sensitive groups and equipment and metal ion residues in products are avoided. The synthesis method can play an important role in industrial production of N-aryl tertiary, especially N-aryl tertiary of complex carboxylic acid.
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Paragraph 0010; 0011
(2017/04/22)
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- Rh-Catalyzed Domino Addition-Enolate Arylation: Generation of 3-Substituted Oxindoles via a Rh(lll) Intermediate
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A Rh-catalyzed domino conjugate addition-arylation sequence via a Rh(III) intermediate is reported. This process involving a proposed intramolecular oxidative addition of a rhodium enolate was utilized to achieve the synthesis of 3-substituted oxindole derivatives in moderate to excellent yields.
- Jang, Young Jin,Yoon, Hyung,Lautens, Mark
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supporting information
p. 3895 - 3897
(2015/08/18)
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- A Baker-Venkataraman retro-Claisen cascade delivers a novel alkyl migration process for the synthesis of amides
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A simple extension of the carbamoyl Baker-Venkataraman rearrangement has been developed. If residual water in the reaction is not strictly excluded a Baker-Venkataraman retro-Claisen cascade takes place, giving amide products, in which an alkyl group apparently migrates between two functionalities of the substrate.
- Ameen, Dana,Snape, Timothy J.
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p. 1816 - 1819
(2015/03/30)
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- Rhodium(I)-catalyzed arylation of β-chloro ketones and related derivatives through domino dehydrochlorination/conjugate addition
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Highly efficient arylations of β-chloro ketones and their ester and amide derivatives were achieved by means of domino dehydrochlorination/Rh(I)- catalyzed conjugate addition. In situ generated vinyl ketones and their analogues were identified as the reaction intermediates. The present synthetic protocol provides a concise route to (chiral) β-aryl ketones, esters, and amides. Copyright
- Jiang, Quanbin,Guo, Tenglong,Wang, Qingfu,Wu, Ping,Yu, Zhengkun
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supporting information
p. 1874 - 1880
(2013/07/19)
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- Water solvent method for esterification and amide formation between acid chlorides and alcohols promoted by combined catalytic amines: Synergy between N-methylimidazole and N,N,N′,N′-tetramethylethylenediamine (TMEDA)
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An efficient method for esterification between acid chlorides and alcohols in water as solvent has been developed by combining the catalytic amines, N-methylimidazole and N,N,N′,N′-tetramethylethylenediamine (TMEDA). The present Schotten-Baumann-type reaction was performed by maintaining the pH at around 11.5 using a pH controller to prevent the decomposition of acid chlorides and/or esters and to facilitate the condensation. The choice of catalysts (0.1 equiv.) was crucial: the combined use of N-methylimidazole and TMEDA exhibited a dramatic synergistic effect. The catalytic amines have two different roles: (i) N-methylimidazole forms highly reactive ammonium intermediates with acid chlorides and (ii) TMEDA acts as an effective HCl binder. The production of these intermediates was rationally supported by a careful 1H NMR monitoring study. Related amide formation was also achieved between acid chlorides and primary or secondary amines, including less nucleophilic or water-soluble amines such as 2-(or 4-)chloroaniline, the Weinreb N-methoxyamine, and 2,2-dimethoxyethanamine.
- Nakatsuji, Hidefumi,Morita, Jun-Ichi,Misaki, Tomonori,Tanabe, Yoo
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p. 2057 - 2062
(2007/10/03)
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- Conversion of α-Anilino Alkenenitriles to Amides by Chemoselective Palladium-Catalyzed Arylations
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The reactions of α-anilino alkenenitriles with iodobenzene catalyzed by palladium gave amides and benzonitrile. A general mechanism is proposed to explain the chemoselective arylation at the cyano group.
- Yang, Chau-Chen,Tai, Huo-Mu,Sun, Pei-Jiun
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p. 812 - 814
(2007/10/03)
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