- Base-controlled chemoselectivity: direct coupling of alcohols and acetonitriles to synthesise α-alkylated arylacetonitriles or acetamides
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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
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p. 15200 - 15204
(2021/09/06)
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- Tandem Acceptorless Dehydrogenative Coupling-Decyanation under Nickel Catalysis
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The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.
- Babu, Reshma,Balaraman, Ekambaram,Midya, Siba P.,Subaramanian, Murugan,Yadav, Vinita
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supporting information
p. 7552 - 7562
(2021/06/28)
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- Method for synthesizing aromatic acetamide
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The preparation method comprises the following steps: dissolving a compound 1 and a compound 2 in an organic solvent, adding a catalyst, a ligand and an alkaline substance, reacting for 2-10 hours at the temperature of 80-160 DEG C in a protective atmosphere, and post-treating the obtained reaction liquid to obtain a compound 3. According to the method, aryl acetamide is synthesized by using alcohol and aryl acetonitrile in one step, so that not only is the use of a toxic alkylating reagent avoided, but also the amide synthesis step is reduced, and the cost is saved; and no by-product is generated in the reaction process, so that the atom utilization rate reaches 100%, and the development requirement of green chemistry is met.
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Paragraph 0026-0040
(2021/08/07)
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- Nickel-catalyzed hydrogen-borrowing strategy: Chemo-selective alkylation of nitriles with alcohols
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The first nickel-catalyzed hydrogen-borrowing alkylation of a series of aryl acetonitriles with a variety of aryl, heteroaryl, allylic and alkyl alcohols releasing water as the by-product (>33 examples, up to 90% yield) is reported.
- Banerjee, Debasis,Bera, Atanu,Bera, Sourajit
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supporting information
p. 6850 - 6853
(2020/07/04)
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- Synthesis of β-hydroxyamides through ruthenium-catalyzed hydration/transfer hydrogenation of β-ketonitriles in water: Scope and limitations
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A cascade process for the straightforward one-pot conversion of β-ketonitriles into β-hydroxyamides is presented. The process, that proceeds in water employing the arene-ruthenium(II) complex [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] as catalyst in combination with sodium formate, involves the initial hydration of the β-ketonitrile substrates to generate the corresponding β-ketoamide intermediates, which subsequently undergo the transfer hydrogenation (TH) of the carbonyl group. Employing a family of forty different β-ketonitriles, featuring diverse substitution patterns, the scope and limitations of the process have been established.
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
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- Method for synthesizing alpha-alkylarylacetamide
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The invention discloses a method for synthesizing alpha-alkylarylacetamide. In a reaction vessel, aromatic acetonitrile, compound alcohol, a transition metal catalyst metal rhodium complex, alkali, a phosphine ligand and an organic solvent are added; the reaction mixture is subjected to a reaction under a temperature of 130 DEG C in a microwave reactor or under magnetic stirring; the mixture is cooled to room temperature, and is processed through column separation, such that a target compound is obtained. According to the invention, nitrile and alcohol are adopted as initial raw materials; under the participation of the transition metal catalyst, the phosphine ligand and alkali, alpha-alkylarylacetamide is directly synthesized. The reaction has three significant advantages: (1) commercialized or easy-to-prepare nitrile and almost nontoxic alcohol are adopted as initial raw materials; and (2) the reaction has high atomic economy. Therefore, the reaction meets the requirements of green chemistry, and has a good development prospect.
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Paragraph 0021; 0022; 0023; 0024; 0025; 0141; 0142
(2017/06/02)
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- Direct coupling of arylacetonitriles and primary alcohols to α-alkylated arylacetamides with complete atom economy catalyzed by a rhodium complex-triphenylphosphine- potassium hydroxide system
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A direct synthesis of α-alkylated arylacetamides from arylacetonitriles and primary alcohols has been accomplished for the first time. In the presence of the rhodium complex [Rh(cod)Cl]2/triphenylphosphine/potassium hydroxide system, the desired α-alkylated arylacetamides were obtained in 74-92% yield under microwave conditions. The experimental results in this paper are in sharp contrast with previous reports, where the coupling of arylacetonitriles and primary alcohols produced the α-alkylated arylacetonitriles. Mechanistic investigations show that arylacetonitriles are first α-alkylated with primary alcohols to produce α-alkylated arylacetonitriles, which are further hydrated with the water resulting from the α-alkylation step to produce α-alkylated arylacetamides. More importantly, this research shows the potential of developing completely atom-economical reactions that involve the hydrogen autotransfer (or hydrogen borrowing) process.
- Li, Feng,Zou, Xiaoyuan,Wang, Nana
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p. 1405 - 1415
(2015/05/19)
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- Selective hydrolysis of nitriles to amides using NaOH-PEG under microwave irradiation
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We describe here an efficient, rapid and selective method for the conversion of nitriles in to their corresponding amides in the presence of PEG-400, aqueous sodium hydroxide system under microwave irradiation.
- Bendale, Pravin M.,Khadilkar, Bhushan M.
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p. 1713 - 1718
(2007/10/03)
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- Alkylation and hydrolysis of phenylacetonitriles under microwave irradiation
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Alkylation of phenylacetonitriles is performed by solid-liquid phase transfer catalysis in 1-3 minutes under microwave irradiation (one hour with a two-phase system). These nitriles can be quickly hydrolysed in a microwave oven to yield the corresponding amides or acids according to the reaction time.
- Barbry,Pasquier,Faven
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p. 3007 - 3013
(2007/10/03)
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- OXIDATIVE COUPLING. III. THE DUCO REACTION
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Acylsulfonamide dianions function as efficient synthetic intermediates and are especially suitable for Doubly Unsymmetrical Carbanion Oxidation
- Belletire, J. L.,Spletzer, E. G.
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p. 131 - 134
(2007/10/02)
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