- Paired Electrochemical Reactions and the On-Site Generation of a Chemical Reagent
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While the majority of reported paired electrochemical reactions involve carefully matched cathodic and anodic reactions, the precise matching of half reactions in an electrolysis cell is not generally necessary. During a constant current electrolysis almost any oxidation and reduction reaction can be paired, and in the presented work we capitalize on this observation by examining the coupling of anodic oxidation reactions with the production of hydrogen gas for use as a reagent in remote, Pd-catalyzed hydrogenation and hydrogenolysis reactions. To this end, an alcohol oxidation, an oxidative condensation, intramolecular anodic olefin coupling reactions, an amide oxidation, and a mediated oxidation were all shown to be compatible with the generation and use of hydrogen gas at the cathode. This pairing of an electrolysis reaction with the production of a chemical reagent or substrate has the potential to greatly expand the use of more energy efficient paired electrochemical reactions.
- Wu, Tiandi,Nguyen, Bichlien H.,Daugherty, Michael C.,Moeller, Kevin D.
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supporting information
p. 3562 - 3565
(2019/02/20)
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- Enantioselective and Diastereoselective Construction of Chiral Amino Alcohols by Iridium-f-Amphox-Catalyzed Asymmetric Hydrogenation via Dynamic Kinetic Resolution
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The iridium-f-amphox-catalyzed asymmetric hydrogenation of racemic α-amino β-unfunctionalized ketones proceeds via a DKR (dynamic kinetic resolution) process for the construction of various chiral N,N-disubstituted α-amino β-unfunctionalized alcohols in quantitative yields with excellent enantioselectivities and diastereoselectivities (all products >99% ee and >99:1 dr, TON up to 100 000). Importantly, this catalytic asymmetric hydrogenation with a DKR process provided a highly efficient and powerful synthetic strategy for the preparation of key chiral intermediates of the preclinical antitumor agent (S,S)-R116010.
- Wu, Weilong,You, Cai,Yin, Congcong,Liu, Yuanhua,Dong, Xiu-Qin,Zhang, Xumu
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supporting information
p. 2548 - 2551
(2017/05/24)
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- A five coordination Cu(II) cluster-based MOF and its application in the synthesis of pharmaceuticals: Via sp3 C-H/N-H oxidative coupling
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Herein, a copper metal-organic framework, termed as VNU-18, containing penta-coordinated sites was successfully synthesized and fully characterized. This material was demonstrated to be an efficient heterogeneous catalyst for the oxidative C-H activation via N-H bonds. The optimized conditions are applicable for the synthesis of pharmaceuticals constructed by α-amino carbonyl skeletons.
- Tran, Thuan V.,Le, Hanh T. N.,Ha, Hiep Q.,Duong, Xuan N. T.,Nguyen, Linh H.-T.,Doan, Tan L. H.,Nguyen, Ha L.,Truong, Thanh
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p. 3453 - 3458
(2017/08/22)
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- Electrochemically Oxidative α-C-H Functionalization of Ketones: A Cascade Synthesis of α-Amino Ketones Mediated by NH4I
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An efficient electrochemical protocol for the synthesis of α-amino ketones via the oxidative cross-dehydrogenative coupling of ketones and secondary amines has been developed. The electrochemistry performs in a simple undivided cell using NH4I
- Liang, Sen,Zeng, Cheng-Chu,Tian, Hong-Yu,Sun, Bao-Guo,Luo, Xu-Gang,Ren, Fa-Zheng
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p. 11565 - 11573
(2016/12/09)
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- N-Bromosuccinimide promoted and base switchable one pot synthesis of α-imido and α-amino ketones from styrenes
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An N-Bromosuccinimide (NBS) promoted one pot strategy for the synthesis of α-amino functionalized aryl ketones starting from commercially available styrenes has been developed. NBS participates in multiple tasks, such as bromonium ion formation, oxidation of bromohydrin and providing a nucleophilic nitrogen source. The reaction can easily be switched between α-imido and α-amino ketones by the choice of base. This one pot strategy was successfully applied for the synthesis of psychoactive drug candidates, amfepramone, mephedrone and 4-MEC.
- Shinde, Mahesh H.,Kshirsagar, Umesh A.
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supporting information
p. 858 - 861
(2016/01/15)
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- A two-step continuous synthesis of α-ketoamides and α-amino ketones from 2° benzylic alcohols using hydrogen peroxide as an economic and benign oxidant
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A practical two-step synthesis of α-ketoamides and α-amino ketones via direct oxidative coupling between 2° benzylic alcohols and amines was developed. Hydrogen peroxide, an economic and environmentally friendly oxidant, was used, and a metal catalyst was unnecessary. Moreover, the continuous-flow technique was employed to increase the functional group tolerance, efficiency and safety.
- Liu, Chengkou,Fang, Zheng,Yang, Zhao,Li, Qingwen,Guo, Shiyu,Guo, Kai
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p. 25167 - 25172
(2016/03/22)
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- A versatile and one-pot strategy to synthesize ?±-amino ketones from benzylic secondary alcohols using N -bromosuccinimide
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A metal-free one-pot strategy has been developed for the first time to synthesize pharmaceutically important ?±-amino ketones from readily available benzylic secondary alcohols and amines using N-bromosuccinimide. This new reaction proceeds via three consecutive steps involving oxidation of alcohols, ?±-bromination of ketones, and nucleophilic substitution of ?±-bromo ketones to give ?±-amino ketones. Importantly, this novel one-pot greener reaction avoids direct usage of toxic and corrosive bromine. This methodology has been employed efficiently to synthesize pharmaceutically important amfepramone and pyrovalerone in a single step.
- Guha, Somraj,Rajeshkumar, Venkatachalam,Kotha, Surya Srinivas,Sekar, Govindasamy
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p. 406 - 409
(2015/03/04)
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- Synthesis and characterization of bisoxazolines- and pybox-copper(II) complexes and their application in the coupling of α-carbonyls with functionalized amines
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Binuclear complexes [{(DMOX)CuCl}2(μ-Cl)2] (1), mononuclear complexes [(DMOX)CuBr2] (2) (DMOX = 4,5-dihydro-2-(4,5- dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyloxazole) and the pybox Cu(ii) complex [(Dm-Pybox)CuBr2/
- Jia, Wei-Guo,Li, Dan-Dan,Dai, Yuan-Chen,Zhang, Hui,Yan, Li-Qin,Sheng, En-Hong,Wei, Yun,Mu, Xiao-Long,Huang, Kuo-Wei
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supporting information
p. 5509 - 5516
(2014/07/21)
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- Transition-metal-free oxidative α-C-H amination of ketones via a radical mechanism: Mild synthesis of α-amino ketones
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A transition-metal-free direct α-C.H amination of ketones has been developed using commercially available ammonium iodide as the catalyst and sodium percarbonate as the co-oxidant. A wide range of ketone ((hetero)aromatic or nonaromatic ketones) and amine (primary/secondary amines, anilines, or amides) substrates undergo cross-coupling to generate synthetically useful α-amino ketones. The mechanistic studies indicated that a radical pathway might be involved in the reaction process. The utility of the method is highlighted through a concise one-step synthesis of the pharmaceutical agent amfepramone.
- Jiang, Qing,Xu, Bin,Zhao, An,Jia, Jing,Liu, Tian,Guo, Cancheng
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p. 8750 - 8756
(2015/01/08)
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- Simple catalytic mechanism for the direct coupling of α-carbonyls with functionalized amines: A one-step synthesis of plavix
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The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino-substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst is reconstituted. The practical value of this transformation is highlighted through one-step syntheses of two high-profile pharmaceutical agents, Plavix and amfepramone.
- Evans, Ryan W.,Zbieg, Jason R.,Zhu, Shaolin,Li, Wei,Macmillan, David W. C.
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supporting information
p. 16074 - 16077
(2013/11/19)
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- NIS-catalyzed reactions: Amidation of acetophenones and oxidative amination of propiophenones
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Single-step amination: The N-iodosuccinimide (NIS)-catalyzed amidation of acetophenone derivatives by using tert-butylhydroperoxide (TBHP) as an oxidant is presented. A variety of acetyl derivatives of heterocyclic compounds were easily converted to their corresponding ketoamides under these conditions. A new, NIS-catalyzed amination of propiophenone and its derivatives in the presence of TBHP to furnish the corresponding 2-aminoketone derivatives is the first reported single-step amination of propiophenone derivatives. Copyright
- Lamani, Manjunath,Prabhu, Kandikere Ramaiah
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supporting information
p. 14638 - 14642
(2013/01/15)
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- Substituent Effects on the Strength of C-C Bonds, 14. - Kinetic and Thermodynamic Stability of 2,3-Bis(dialkylamino)-1,4-diketones - Energy of Stabilization of α-Dialkylamino α-Carbonylalkyl Radicals with Capto-dative Substituents
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The equilibrium constants and rate constants for the dissociation of the 2,3-bis(dialkylamino)-1,4-diketone diastereomers meso- and DL-7a and 7b were measured over a temperature range of 40 deg C.From the enthalpies of dissociation ΔHDiss and ethalpies of activation ΔH(excit.) and the strain enthalpies of 7 the bond dissociation enthalpies BDE(C-C) of 7 were determined.By comparison with the dissociation enthalpies of Ct-Ct alkanes the change of these BDEs(C-C) by the capto-dative substitution was determined to be 85.4 kJ mol-1 (20.4 kcal mol-1).The heats of formation ΔHf0(g) of a series of amino ketones 8 were determined from their heats of combustion and their heats of evaporation.From the ΔHf0(g) values in combination with MM2 calculations of their strain enthalpies strain-free increments CHn2-n> with n = 0, 1, 2 were derived and geminal interaction enthalpies in the ground states were obtained thereof.The radical stabilization enthalpy RSE of 6 was deduced from the ΔBDE(C-C) values and the ground state effect to be 73.6 kJ mol-1 (17.6 kcal mol-1).From these data and the radical stabilization enthalpies RSE of α-aminoalkyl radicals (4.2 kJ mol-1) and α-carbonyl radicals (28.9 kJ mol-1) a synergetic radical stabilization enthalpy of 40.5 kJ mol-1 (9.7 kcal mol-1) is deduced.This number combines "extra" resonance stabilization and general inductive or anomeric geminal substituent interaction in the radicals.The crystal structure of meso-7a has been determined by X-ray diffraction methods. - Key Words: C-C Bond cleavage, kinetics of / Heats of formation / Radicals, stability of / Capto-dative effect / Geminal substituents, energetic interaction of
- Welle, Frank,Verevkin, Sergej P.,Keller, Manfred,Beckhaus, Hans-Dieter,Ruechardt, Christoph
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p. 697 - 710
(2007/10/02)
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