- Rh-PVP Catalyzed Reductive Amination of Phenols by Ammonia or Amines to Cyclohexylamines under Solvent-free Conditions
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Colloidal metal nanoparticles were examined for reductive amination of phenol by ammonia under mild reaction conditions. The results showed that Rh-PVP was the most active catalyst for reductive amination reaction. Linear, cyclic, and amino alcohols were used as nucleophiles and converted to primary/secondary/tertiary amines. Using this strategy, the synthesis of an industrially important chemical, N-cyclohexyl- 2-pyrrolidone was explored.
- Chaudhari, Chandan,Nagaoka, Katsutoshi,Nishida, Yoshihide,Rumi, Saeki,Sato, Katsutoshi,Shiraishi, Masaya
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supporting information
p. 81 - 84
(2022/01/12)
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- Synthesis of Lactams by Reductive Amination of Carbonyl Derivatives with ω-Amino Fatty Acids under Hydrosilylation Conditions
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An efficient method for the preparation of lactams from ω-amino fatty acids under hydrosilylation is described. A variety of lactams such as pyrrolidinones, piperidinones and 2-azepanones were selectively synthesised in moderate to excellent yields (29 examples, up to 95 % isolated yields) with a good functional group tolerance. Notably, no metallic based catalyst was required to perform this transformation.
- Tongdee, Satawat,Wei, Duo,Wu, Jiajun,Netkaew, Chakkrit,Darcel, Christophe
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supporting information
p. 5536 - 5539
(2021/08/07)
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- Catalytic Transfer Hydrogenation of Arenes and Heteroarenes
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Transfer hydrogenation reactions are of great interest to reduce diverse molecules under mild reaction conditions. To date, this type of reaction has only been successfully applied to alkenes, alkynes and polarized unsaturated compounds such as ketones, imines, pyridines, etc. The reduction of benzene derivatives by transfer hydrogenation has never been described, which is likely due to the high energy barrier required to dearomatize these compounds. In this context, we have developed a catalytic transfer hydrogenation reaction for the reduction of benzene derivatives and heteroarenes to form complex 3-dimensional scaffolds bearing various functional groups at room temperature without needing compressed hydrogen gas.
- Gelis, Coralie,Heusler, Arne,Nairoukh, Zackaria,Glorius, Frank
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supporting information
p. 14090 - 14094
(2020/10/19)
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- Decarboxylative sp 3 C-N coupling via dual copper and photoredox catalysis
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Over the past three decades, considerable progress has been made in the development of methods to construct sp 2 carbon-nitrogen (C-N) bonds using palladium, copper or nickel catalysis 1,2 . However, the incorporation of alkyl substrates to form sp 3 C-N bonds remains one of the major challenges in the field of cross-coupling chemistry. Here we demonstrate that the synergistic combination of copper catalysis and photoredox catalysis can provide a general platform from which to address this challenge. This cross-coupling system uses naturally abundant alkyl carboxylic acids and commercially available nitrogen nucleophiles as coupling partners. It is applicable to a wide variety of primary, secondary and tertiary alkyl carboxylic acids (through iodonium activation), as well as a vast array of nitrogen nucleophiles: nitrogen heterocycles, amides, sulfonamides and anilines can undergo C-N coupling to provide N-alkyl products in good to excellent efficiency, at room temperature and on short timescales (five minutes to one hour). We demonstrate that this C-N coupling protocol proceeds with high regioselectivity using substrates that contain several amine groups, and can also be applied to complex drug molecules, enabling the rapid construction of molecular complexity and the late-stage functionalization of bioactive pharmaceuticals.
- Liang, Yufan,Zhang, Xiaheng,MacMillan, David W. C.
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- Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature
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The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for S N2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.
- Do, Hien-Quang,Bachman, Shoshana,Bissember, Alex C.,Peters, Jonas C.,Fu, Gregory C.
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supporting information
p. 2162 - 2167
(2014/03/21)
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- Transition Metal-Catalyzed C-H Amination Using Unactivated Amines
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One aspect of the invention relates to a method of animation or amidation, comprising the step of combining a substrate, comprising a reactive C—H bond, and an amine or amide, comprising a reactive N—H bond, in the presence of an oxidizing agent and a metal-containing catalyst, thereby forming a product with a covalent bond between the carbon of the reactive C—H bond and the nitrogen of the reactive N—H bond.
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Page/Page column 3; 27
(2011/09/20)
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- Rh-catalyzed intramolecular debenzylative cyclization of amines. Butyrolactams from benzylamines having a chloroacetylene moiety
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When benzylamines having a chloroacetylene moiety were heated in wet toluene with a catalytic amount of rhodium trifluoroacetate dimer, intramolecular debenzylative cyclization took place to give butyrolactams. This method is a new entry to selective debenzylation of amines.
- Oh, Yun Taek,Senda, Kousuke,Hata, Takeshi,Urabe, Hirokazu
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p. 2458 - 2461
(2011/05/16)
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- Fast, acid-free, and selective lactamization of lactones in ionic liquids
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(Chemical Equation Presented) A fast and acid-free one-pot 0.2-30 mmol microwave methodology for direct ionic liquid-mediated preparation of lactams from lactones and primary amines has been developed. The protocol was investigated with a wide range of primary amines and a handful of lactones, including substrates with acid-sensitive substituents. Both γ-lactams and δ-lactams were, despite the complete absence of a Bronsted acid, obtained in useful to excellent yields after only 35 min of microwave processing.
- Orrling, Kristina M.,Wu, Xiongyu,Russo, Francesco,Larhed, Mats
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supporting information; experimental part
p. 8627 - 8630
(2009/04/11)
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- Ring-expanding reaction of cyclopropyl amides with triphenylphosphine and carbon tetrahalide
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We succeeded in activating cyclopropyl amides (monoactivated cyclopropane) through the corresponding imidoyl halides prepared in situ in the presence of 2 equiv of PPh3 and 1 equiv of CX4, and the ring-expanding products (N-substituted pyrrolidin-2-ones) were obtained in good yields. The reaction mechanism was investigated on the basis of oxygen-18 tracer experiment.
- Yang, Yong-Hua,Shi, Min
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p. 8645 - 8648
(2007/10/03)
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- A study on pyrrolidone derivatives as selective precipitant for uranyl ion in HNO3
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We have found out that N-cyclohexyl-2-pyrrolidone (NCP) can selectively precipitate UO22+ ions in HNO3 solutions. In order to investigate factors of such a specific property of NCP, we have examined reactions of NCP with UO22+ ions in HCl, HClO4, or H2SO4, and the precipitation abilities of pyrrolidone derivatives other than NCP for UO2 2+ in HNO3 solutions. As a result, it was found that UO22+ ions in HCl, HClO4, or H 2SO4 are not precipitated by NCP, that N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP) with lower hydrophobicity than NCP do not precipitate UO22+, and that hydrophobic N-dodecyl-2-pyrrolidone can precipitate UO2 2+. Furthermore, we have investigated the crystal structures of UO2(NO3)2(L)2 (L = NMP, NEP) complexes to compare with that of UO2(NO3) 2(NCP)2. The bond distance between uranium and carbonyl oxygen of NCP in UO2(NO3)2(NCP)2 was found to be shorter than those in UO2(NO3) 2(L)2 (L = NMP, NEP). From these results, it is proposed that the specific property of NCP is ascribed to its relatively high hydrophobicity owing to cyclohexyl group, to its strong coordination ability to UO22+ for forming the symmetrical complex accompanied by two bidentate NO3-, and to the surface of UO 2(NO3)2(NCP)2 which is surrounded by the hydrophobic cyclohexyl groups of coordinated NCP.
- Ikeda, Yasuhisa,Wada, Emiko,Harada, Masayuki,Chikazawa, Takahiro,Kikuchi, Toshiaki,Mineo, Hideaki,Morita, Yasuji,Nogami, Masanobu,Suzuki, Kazunori
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p. 420 - 425
(2008/10/09)
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- PRODUCTION OF N-ARYL-2-LACTAM AND N-CYCLOALKYL-2-LACTAM BY REDUCTIVE AMINATION OF LACTONES WITH ARYL AMINES
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This invention relates to a process for producing N-aryl-2-lactams and N-cycloalkyl-2-lactams by reductive amination of lactones with aryl amines utilizing a metal catalyst, which is optionally supported.
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- Synthesis of Pyrrolidines and Pyrrolidinones by the Rhodium Complex Catalyzed Cyclization of Unsaturated Amines
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N-Allylic arylamines react with carbon monoxide, sodium borohydride, 2-propanol, and catalytic amounts of the zwitterionic complex η6-C6H6BPh3-Rh(COD)+ (1), to form pyrrolidines as the main products in most cases.Pyrrolidinones result from N-allylic alkylamines.An alternate route to the lactams from N-allylic alkylamines involves synthesis gas instead of CO/NaBH4, together with the dual catalytic system 1/2.Complementary to the N-allylic arylamine route to pyrrolidines with NaBH4 and 1 is the use of synthesis gas, 1, and 1,4-bis(diphenylphosphino)butane.
- Zhou, Jian-Qiang,Alper, Howard
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p. 3328 - 3331
(2007/10/02)
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- EFFICIENT SYNTHESIS OF N-SUBSTITUTED LACTAMS FROM (N-ARYLSULFONYLOXY)AMINES AND CYCLIC KETONES
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A new method is reported for the direct preparation of N-substituted lactams from cycloalkanones.N-(p-nitrobenzenesulfonoxyl) methylamine 1a (CH3NH-OSO2C6H4NO2) was reacted with a series of cycloalkanones to give good yields of N-methyl lactams.An addition-rearrangement pathway accounts for the ring-expanded lactam products.A series of N-alkyl-N-arylsulfonoxyl amines were generated in situ and reacted with cyclobutanone to give N-alkyl pyrrolidinones in high yields.
- Hoffman, Robert V.,Salvador, James M.
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p. 4207 - 4210
(2007/10/02)
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