- Sustainable Alkylation of Nitriles with Alcohols by Manganese Catalysis
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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
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p. 7927 - 7935
(2019/06/24)
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- Preparation method of high activity myclobutanil
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The invention relates to a preparation method of high activity myclobutanil, and belongs to the technical field of pesticide synthesis. In order to solve the existing problem of low activity of nitrile bacteria due to the difficulty of splitting, the preparation method of high activity myclobutanil is provided. The method includes the steps that compound 2 (4-chlorphenyl) hexanenitrile in formula I is added into a dichloromethane solvent under the action of chiral quaternary ammonium salt phase transfer catalyst, inorganic alkali water solution is added under the condition that the temperature is controlled to be 20 DEG C to 30 DEG C, the temperature is raised to 60 DEG C to 80 DEG C, after reaction, S-1-chlorine-2-nitrile base-2-(4-N-chlorophenyl) hexane is obtained; the chiral quaternary ammonium salt phase transfer catalyst is selected from cinchonidine and/or quinine, and the compound in formula II reacts with the dimethyl sulfoxide solution of anhydrous triazole potassium, and the high activity product-type compound in formula III S-type myclobutanil is obtained. The high acitivity reactive S-myclobutanil element in the product is significantly increased, the hydrolysis of cyanide is avoided, and the effects of higher yield and purity are achieved.
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Paragraph 0043; 0046; 0047
(2018/04/02)
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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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
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- Oxidative conversion of α,α-disubstituted acetamides to corresponding one-carbon-shorter ketones using hypervalent iodine (λ5) reagents in combination with tetraethylammonium bromide
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(Chemical Equation Presented) α,α-Disubstituted acetamides undergo oxidative dehomologation to give one-carbon-shorter ketones when reacted with a hypervalent iodine (λ5) reagent in combination with tetraethylammonium bromide (TEAB) in various solvents. In further studies, one such combination of a hypervalent iodine (λ5) reagent, o-iodoxybenzoic acid, and TEAB has been established as a new, mild, efficient, and general method for the transformation.
- Bellale, Eknath V.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
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supporting information; experimental part
p. 9473 - 9475
(2009/04/06)
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