- Catalyst-free photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines
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Due to the directional nature of sp3-hybridized orbitals and the absence of π-orbitals, the oxidative cleavage of the kinetically and thermodynamically stable C(sp3)-C(sp3) bond is extremely difficult and remains scarcely explored. In this work, under the double argument of quantum mechanics (QM) computations and meticulous experiments on our well-designed C-C single bond cleavage mechanism, we discovered a means of photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines, easily achieved by simple visible light irradiation using O2as a benign oxidant under very mild conditions. The utility of our methodology was demonstrated by the C(sp3)-C(sp3) bond cleavage in morpholine/piperazine arylamines with excellent functional group tolerance. Importantly, our methodology is noteworthy, not only in that it does not require any catalysts, but also in that it provides valuable possibilities for the scalable functionalization of clinical drugs and natural products.
- Duan, Wentao,Lian, Qi,Wang, Songping,Wei, Wentao,Zhou, Jingwei
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supporting information
p. 3261 - 3267
(2021/05/21)
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- Electrochemical Activation of Diverse Conventional Photoredox Catalysts Induces Potent Photoreductant Activity**
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Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)?N and C(sp2)?O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile.
- Chernowsky, Colleen P.,Chmiel, Alyah F.,Wickens, Zachary K.
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p. 21418 - 21425
(2021/08/25)
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- Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents
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The nickel-catalyzed hydrodeoxygenation of aryl sulfamates has been developed with alcohols as mild reductants. A variety of functional groups and heterocycles were tolerated in this reaction system to give the desired products in high yields. In addition, the gram-scale process and stepwise cine-substitution were also achieved with high efficiency.
- Matsuo, Kasumi,Kuriyama, Masami,Yamamoto, Kosuke,Demizu, Yosuke,Nishida, Koyo,Onomura, Osamu
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p. 4449 - 4460
(2021/08/25)
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- Mn(II)-Catalyzed N -Acylation of Amines
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A practical protocol has been developed here for the Mn(II)-catalyzed N -acylation of amines with high yields using N, N -dimethylformamide and other amides as the carbonyl source. The protocol is simple, does not require any acid, base, ligand, or other additives, and encompasses a broad substrate scope for primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Jingyu,Gong, Hang
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p. 693 - 703
(2019/01/23)
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- Cobalt(II)-Catalyzed N-Acylation of Amines through a Transamidation Reaction
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A practical protocol has been developed for a Co(OAc)2·4H2O-catalyzed transamidation reaction. The reaction gives high yields and uses N,N-dimethylformamide and other amides as carbonyl sources. The protocol is rapid and simple, and it does not require any acids, bases, ligands, or other additives. It works well for a wide range of primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Feng,Zhang, Jingyu,Gong, Hang
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p. 4940 - 4948
(2018/09/25)
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- Protection of COOH and OH groups in acid, base and salt free reactions
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We report an iron-catalyzed general functional group protection method with inexpensive reagents. This environmentally benign process does not use acids or bases, and does not produce waste products. Further purification beyond filtration and evaporation is, in most cases, unnecessary. Free COOH and OH groups can be protected in a one-pot reaction.
- Zhu, Xiaotao,Qian, Bo,Wei, Rongbiao,Huang, Jian-Dong,Bao, Hongli
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supporting information
p. 1444 - 1447
(2018/04/12)
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- A novel and green method for N-acylation of amines and sulfonamides under ultrasound irradiation
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A facile and versatile method for acylation of structurally diverse amines and sulfonamides under focused ultrasonic irradiation in catalyst-free and solvent-free conditions is reported. There are several advantages to this approach such as simple and eas
- Bouasla, Radia,Bechlem, Khaoula,Belhani, Billel,Grib, Ismahene,Aouf, Nour-Eddine,Berredjem, Malika
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p. 1454 - 1460
(2017/08/01)
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- An eco-friendly and highly efficient route for N-acylation under catalyst-free conditions
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An eco-friendly, simple, mild, chemoselective and highly efficient procedure for the acylation of primary and secondary amine function in various structurally and electronically aliphatic and aromatic compounds affording their corresponding N-Ac derivatives is developed. Mild conditions, simplicity and easier work-up are the main advantages of this method.
- Ouarna, Souad,K'tir, Hacène,Lakrout, Salah,Ghorab, Hamida,Amira, A?cha,Aouf, Zineb,Berredjem, Malika,Aouf, Nour-Eddine
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p. 913 - 919
(2015/10/28)
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- Convenient N-acetylation of amines in N,N-dimethylacetamide with N,N-carbonyldiimidazole
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Dimethylacetamide (DMAc) acts as an efficient source of acetyl and dimethylamine gas in the presence of N,N-carbonyldiimidazole (CDI). Addition of amines to the reaction mixture delivers the corresponding amides in good to excellent yields. The acetylation of amines reported herein, which relies on the in situ generation of N-acetylimidazole on warming of DMAc with CDI at 120-125 °C, serves as a convenient alternative to other acetylation methods.
- Chikkulapalli, Anil,Aavula, Sanjeev Kumar,Mona Np, Rifahath,Karthikeyan, Karthikeyan,Kumar C.H., Vinodh,Sulur G., Manjunatha,Sumathi, Shanmugam
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supporting information
p. 3799 - 3803
(2015/06/08)
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- Photoinitiated carbonylation with [11C]carbon monoxide using amines and alkyl iodides
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Photoinitiated radical carbonylation with [11C]carbon monoxide at low concentration was employed in syntheses of carbonyl-11C- labeled amides using alkyl iodides and amines as precursors. Eleven 11C-amides were synthesized
- Itsenko, Oleksiy,Kihlberg, Tor,Langstroem, Bengt
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p. 4356 - 4360
(2007/10/03)
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