- C-H Amination via Electrophotocatalytic Ritter-Type Reaction
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A method for C-H bond amination via an electrophotocatalytic Ritter-Type reaction is described. The reaction is catalyzed by a trisaminocyclopropenium (TAC) ion in an electrochemical cell under irradiation. These conditions convert benzylic C-H bonds to acetamides without the use of a stoichiometric chemical oxidant. A range of functionality is shown to be compatible with this transformation, and several complex substrates are demonstrated.
- Lambert, Tristan H.,Shen, Tao
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supporting information
p. 8597 - 8602
(2021/06/28)
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- Manganese(III) acetate catalyzed oxidative amination of benzylic C(sp3)-H bonds with nitriles
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Mn-Catalyzed oxidative amination of benzylic C(sp3)-H bonds with nitriles is disclosed, which enables the synthesis of a broad range of secondary amides in moderate to excellent yields under mild conditions. The interaction between Mn(iii) and DDQ facilitates the oxidation and makes it highly efficient and selective.
- Zhang, Yaxing,Dong, Jianyu,Liu, Lixin,Liu, Long,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 2897 - 2901
(2017/04/11)
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- Method for preparing amide from aryl methane derivative and nitrile
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The invention provides a simple and efficient method for directly preparing an amide compound from an aryl methane derivative and nitrile. In the method, manganese triacetate dihydrate is used as a catalyst, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) is used as an oxidizing agent. The method has the characteristics that raw materials are cheap and easy to obtain, the source of the nitrile is wide, reaction conditions are mild, the applicability is wide and the like. The method solves the problems that ceric ammonium nitrate (CAN) and a fluorine agent which are used by a method for directly synthesizing amide by using aryl methane and nitrile compounds are hard to treat, atomic economy is poor, the source of the nitrile is narrow and the like.
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Paragraph 0029-0031
(2017/05/10)
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- Hypervalent Iodine(III)-Mediated Decarboxylative Ritter-Type Amination Leading to the Production of α-Tertiary Amine Derivatives
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α-Tertiary amines (ATAs) are attractive structural motifs that are frequently found in biologically active molecules. Therefore, the development of an efficient method for the synthesis of ATAs represents an important research topic in the field of medicinal chemistry as well as organic chemistry. Although the Ritter reaction is a reliable approach for preparing α-tertiary amine derivatives via intermolecular amination reactions, the typical methods suffer from disadvantages such as harsh reaction conditions and the use of strong acids. Because of this, it has been of limited use in the synthesis of ATAs. We report here on the decarboxylative Ritter-type amination of carboxylic acids bearing an α-quaternary carbon center using a combination of PhI(OAc)2 and molecular iodine (I2) to produce the corresponding α-tertiary amine derivatives. This reaction proceeded at ambient temperature on the benchtop with a fluorescent light. Mechanistic investigations suggest that the reaction proceeds via the formation of an alkyl iodide and a higher oxidation state iodine(III) species as key intermediates. Similarly, a stepwise protocol for the Ritter-type amination of alcohols via the formation of oxalic acid monoalkyl esters was also achieved. The present methods represent a useful tool for the synthesis of ATAs that are difficult to prepare by conventional methods.
- Kiyokawa, Kensuke,Watanabe, Tomoki,Fra, Laura,Kojima, Takumi,Minakata, Satoshi
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p. 11711 - 11720
(2017/11/27)
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- The ritter reaction under truly catalytic bronsted acid conditions
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Simple organic acids like 2,4-dinitrobenzenesulfonic acid (DNBSA) catalyze the Ritter reaction of secondary benzylic alcohols giving rise to the corresponding N-benzylacetamides in usually high yields. Reactions can be conducted without exclusion of oxygen and without the need of dry solvents. With tertiary α,α-dimethylbenzylic alcohols a different pathway involving a formal dimerization reaction takes place under the acid-catalytic conditions used. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Sanz, Roberto,Martinez, Alberto,Guilarte, Veronica,Alvarez-Gutierrez, Julia M.,Rodriguez, Felix
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p. 4642 - 4645
(2008/03/12)
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- ARYLCYCLOPROPANES IN THE RITTER REACTION
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N-(1-Arylpropyl)acetamides were obtained by the reaction of arylcyclopropanes with acetonitrile in the presence of concentrated sulfuric acid.
- Kutateladze, T. G.,Mironova, A. A.,Mochalov, S. S.,Shabanov, Yu. S.
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p. 1650 - 1653
(2007/10/02)
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- Preparation and Reactivities of Hexakisacetonitrile Iron(III) Perchlorate and Related Complexes as Strong Oxidizing Reagents
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The iron(III) complexes Fe(S)6(ClO4)3, S=solvent, were prepared from Fe(H2O)6(ClO4)3 in the donor solvents.Reactions of alkylbenzenes with Fe(AN)6(ClO4)3 (AN=acetonitrile) were explored because the AN complex has the highest formal redox potential, E0=1.73 V vs.SCE, among these complexes.Oxidation of the primary alkylbenzenes by the iron(III) AN complex gave the corresponding acetamides (Table II).Oxidation of the secondary alkylbenzenes, namely, cumene, 2-phenylbutane, and 2-exo-phenylnorbornane, afforded the corresponding acetates and acetamides (Charts 2 and 3), consuming over 4-mol eq of reagent.Reactions of p-xylene and hexamethylbenzene with Fe(CH2=CHCN)6(ClO4)3 also yielded the amides 31a and 31b.These results demonstrate the applicability of the iron(III) AN complexes as a powerful reagent to oxidize organic substrates which have onset potentials of anodic current of ca. 2.0 V vs.SCE.Keywords - oxidation; primary alkylbenzene; secondary alkylbenzene; oxidizing reagent; iron(III) perchlorate solvate; hexakisacetonitrile iron(III) perchlorate; hexakisacrylonitrile iron(III) perchlorate
- Kotani,Eiichi,Kobayashi, Shigeki,Ishii, Yoko,Tobinaga, Seisho
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p. 4281 - 4291
(2007/10/02)
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