- Enantioconvergent Alkylations of Amines by Alkyl Electrophiles: Copper-Catalyzed Nucleophilic Substitutions of Racemic α-Halolactams by Indoles
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Transition-metal catalysis has the potential to address shortcomings in the classic SN2 reaction of an amine with an alkyl electrophile, both with respect to reactivity and to enantioselectivity. In this study, we describe the development of a user-friendly method (reaction at room temperature, with commercially available catalyst components) for the enantioconvergent nucleophilic substitution of racemic secondary alkyl halides (α-iodolactams) by indoles. Mechanistic studies are consistent with the formation of a copper(I)-indolyl complex that reacts at different rates with the two enantiomers of the electrophile, which interconvert under the reaction conditions (dynamic kinetic resolution). This investigation complements earlier work on photoinduced enantioconvergent N-alkylation, supporting the premise that this important challenge can be addressed by a range of strategies.
- Bartoszewicz, Agnieszka,Matier, Carson D.,Fu, Gregory C.
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supporting information
p. 14560 - 14564
(2019/10/11)
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- Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
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By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.
- Chen, Jiangbo,Wang, Jiaquan,Tu, Tao
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p. 2559 - 2565
(2018/07/30)
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- Visible-Light-Mediated Efficient Metal-Free Catalyst for α-Oxygenation of Tertiary Amines to Amides
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A metal-free system has been discovered for the efficient α-oxygenation of tertiary amines to the corresponding amides using oxygen as an oxidant. This visible-light-mediated oxygenation reaction exhibited excellent substrates scope under mild reaction conditions and generated water as the only byproduct. The synthetic utility of this approach has been demonstrated by applying onto drug molecules. At the end, detailed mechanistic reactions clearly showed the role of oxygen and the photocatalyst.
- Zhang, Yu,Riemer, Daniel,Schilling, Waldemar,Kollmann, Jiri,Das, Shoubhik
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p. 6659 - 6664
(2018/06/25)
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- Copper-Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amides
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Cu2O/N,N′-bis(thiophen-2-ylmethyl)oxalamide is established to be an effective catalyst system for Goldberg amidation with inferior reactive (hetero)aryl chlorides, which have not been efficiently documented by Cu-catalysis to date. The reaction is well liberalized toward a variety of functionalized (hetero)aryl chlorides and a wide range of aromatic and aliphatic primary amides in good to excellent yields. Furthermore, the arylation of lactams and oxazolidinones is achieved. The present catalytic system also accomplished an intramolecular cross-coupling product.
- De, Subhadip,Yin, Junli,Ma, Dawei
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supporting information
p. 4864 - 4867
(2017/09/23)
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- PROCESS FOR THE PREPARATION OF APIXABAN AND INTERMEDIATES THEREOF
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The present invention refers to novel process for the preparation of Apixaban. Further, the invention also related to a process for the preparation of intermediate of Apixaban from very basic and cheap row material i.e. Aniline which is widely commercially available. The present invention provides process for preparation of Apixaban using a different sequence of synthetic steps and does not involve use of Ullmann reaction.
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Paragraph 0137
(2017/06/12)
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- A method of preparing intermediates [...]
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A disclosed preparation method for an apixaban intermediate comprises the following steps: step (1), performing an amidation reaction shown in the specification on a compound 3 and a compound M in an organic solvent under the effect of an organic alkali to obtain a reaction solution containing a compound 3'; and step (2), under the effect of an inorganic base, directly performing an nucleophilic substitution reaction shown in the specification on the reaction solution obtained in the step (1) to prepare a compound 4, and performing a nitration reaction on the compound 4 under the effect of concentrated sulfuric acid and concentrated nitric acid to prepare a compound 5. The preparation method provided by the invention is low in cost, simple in operation and suitable for industrialization.
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- Copper(II) incorporated functionalized polystyrene catalyzed: N -arylation of amides under solvent free condition with broad substrate scope
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We demonstrate here, a new polystyrene supported Cu(ii) catalyzed proficient synthetic methodology for the facile N-arylation of aromatic, aliphatic, cyclic and heterocyclic amides with aryl halides under neat conditions. The catalyst, PS-Cu(ii)-ala, was prepared through the grafting of copper metal on a polystyrene-β-alanine imine network. The catalyst shows a wide range of substrate scope and excellent functional group tolerance, and produces the desired anilides in mostly high yields. The material is thoroughly characterized by DRS-UV, FT-IR, AAS, FE-SEM, TGA analysis and energy dispersive X-ray (EDX) studies. The catalyst can be easily recovered from the reaction medium and reused without significant loss of its catalytic activity suggesting future potential of this catalyst.
- Islam, Md. Mominul,Halder, Mita,Roy, Anupam Singha,Chatterjee, Sauvik,Bhaumik, Asim,Islam, Sk. Manirul
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p. 109692 - 109701
(2016/11/30)
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- CYCLIC AMIDES AS METAP-2 INHIBITORS
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Compounds of the formula (I), in which R1, R3, R5, R6, R7, R, X and Y have the meanings indicated in Claim 1, are inhibitors of methionine aminopeptidase and can be employed for the treatment of tumou
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Paragraph 0283; 0284; 0285; 0286; 0287; 0288; 0289
(2015/02/19)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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- Efficient ligand-free copper-catalyzed N-arylation of amides with aryl halides in water
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A convenient and efficient protocol has been developed for the cross-coupling of amides and aryl iodides using a ligand-free copper(I) oxide catalyst in water. A variety of amide derivatives afforded the corresponding N-arylated products in moderate to good yields (up to 88%).
- Yong, Fui-Fong,Teo, Yong-Chua,Chua, Guan-Leong,Lim, Gina Shiyun,Lin, Yizhen
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supporting information; experimental part
p. 1169 - 1172
(2011/03/21)
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- A highly active catalyst for the hydrogenation of amides to alcohols and amines
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Amide-zing: The reaction between 2 equivalents of Ph2P(CH 2)2NH2 and cis-[Ru(CH3CN) 2(η3-C3H5)(cod)]BF4 (cod=1,5-cyclooctadiene) forms a highly active catalyst precursor for the selective hydrogenation of amides. The reaction proceeds with excellent atom economy, yield, and turnover numbers (TONs) under moderate reaction conditions. The technology offers a greener, practical approach to the use of metal hydride reagents commonly employed in both academia and industry. Copyright
- John, Jeremy M.,Bergens, Steven H.
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supporting information; experimental part
p. 10377 - 10380
(2011/12/04)
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- Copper-catalyzed N-arylation of amides using (S)-N-methylpyrrolidine-2- carboxylate as the ligand
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(S)-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.
- Wang, Chaoyu,Liu, Lijuan,Wang, Wei,Ma, Dong-Sheng,Zhang, Hua
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experimental part
p. 1154 - 1160
(2010/06/13)
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- Copper-catalyzed N-arylation of amides and azoles using phosphine-free hydrazone ligands
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Phosphine-free hydrazone such as 1c was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides and Ullmann-type N-arylation of azoles with aryl halides under mild conditions. A variety of N-arylamides and N-arylazoles were synthesized in good to high yields. Georg Thieme Verlag Stuttgart.
- Mino, Takashi,Harada, Yoshikazu,Shindo, Hiroaki,Sakamoto, Masami,Fujita, Tsutomu
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p. 614 - 620
(2008/12/22)
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- Scope and selectivity in palladium-catalyzed directed C-H bond halogenation reactions
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Palladium-catalyzed ligand directed C-H activation/halogenation reactions have been extensively explored. Both the nature of the?directing group and the substitution pattern on the arene ring of the substrate lead to different reactivity profiles, and often different and complementary products, in the presence and absence of the catalyst.
- Kalyani, Dipannita,Dick, Allison R.,Anani, Waseem Q.,Sanford, Melanie S.
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p. 11483 - 11498
(2007/10/03)
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- The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
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The reactions of the silyllithium reagent with tertiary amides was discussed. The enediamines were easily isomerized from cis to trans, easily oxidized to dienediamines and were hydrolyzed to α-aminoketones. If the two equivalents of the silyllithium reagent were used, the product was an α-silylamine. The results show that each member of the homologous series of amides gives rise to a substantially different product.
- Buswell, Marina,Fleming, Ian,Ghosh, Usha,Mack, Stephen,Russell, Matthew,Clark, Barry P.
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p. 3006 - 3017
(2007/10/03)
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- Copper-catalyzed amidation of aryl iodides using KF/Al2o 3: An improved protocol
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A mild method for the copper-catalyzed amidation of aryl iodides is reported. This simple C-N bond forming procedure shows that the combination of air stable CuI and 1,10-phenanthroline in the presence of KF/Al 2O3 comprises an extremely efficient and general catalyst system for the N-amidation of aryl iodides. Different functionalized aryl iodides were efficiently coupled with amides using this method.
- Hosseinzadeh, Rahman,Tajbakhsh, Mahmood,Mohadjerani, Maryam,Mehdinejad, Hamidreza
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p. 1517 - 1520
(2007/10/03)
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- Pd-catalyzed intermolecular amidation of aryl halides: The discovery that xantphos can be trans-chelating in a palladium complex
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A general method for the intermolecular coupling of aryl halides and amides using a Xantphos/ Pd catalyst is described. This system displays good functional group compatibility, and the desired C-N bond forming process proceeds in good to excellent yields with 1-4 mol % of the Pd catalyst. Additionally, the arylation of sulfonamides, oxazolidinones, and ureas is reported. The efficiency of these transformations was found to be highly dependent on reaction concentrations and catalyst loadings. A Pd complex resulting from oxidative addition of 4-bromobenzonitrile, (Xantphos)Pd(4-cyanophenyl)(Br) (II), was prepared in one step from Xantphos, Pd2(dba)3, and the aryl bromide. Complex II proved to be an active catalyst for the coupling between 4-bromobenzonitrile and benzamide. X-ray crystallographic analysis of II revealed a rare trans-chelating bisphosphine-Pd(II) structure with a large bite angle of 150.7°.
- Yin, Jingjun,Buchwald, Stephen L.
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p. 6043 - 6048
(2007/10/03)
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- Palladium-catalyzed intermolecular coupling of aryl halides and amides
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The first general intermolecular C-N bond-forming reactions between aryl halides and amides were realized using a palladium catalyst with Xantphos as the ligand. Aryl triflates, carbamates, and sulfonamides are also viable substrates for the amidations, which proceed at 45-110 °C with 1-4 mol% of Pd catalyst in 66-99% yields and exhibit good functional group compatibility.
- Yin, Jingjun,Buchwald, Stephen L.
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p. 1101 - 1104
(2007/10/03)
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- A new synthesis of N-phenyl lactams
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The synthesis of N-phenyl lactams by phase transfer oxidation of N,N- (polymethylene) anilines with potassium permanganate is reported.
- Markgraf, J. Hodge,Stickney, Carolyn A.
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p. 109 - 110
(2007/10/03)
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- Palladium-catalyzed coupling of lactams with bromobenzenes
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An efficient method for the coupling of lactams with bromobenzenes mediated by palladium acetate and DPPF is presented. The reaction proceeds efficiency with a variety of lactams and both electron-rich and poor substituted bromobenzenes.
- Shakespeare, William C.
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p. 2035 - 2038
(2007/10/03)
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- INHIBITORS OF FARNESYL-PROTEIN TRANSFERASE
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The present invention is directed to compounds which inhibit farnesyl-protein transferase (FTase) and the farnesylation of the oncogene protein Ras. The invention is further directed to chemotherapeutic compositions containing the compounds of this invention and methods for inhibiting farnesyl-protein transferase and the farnesylation of the oncogene protein Ras
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- Unusual synthesis of new glycine antagonists via sequential aldol condensation-lactonization-elimination reaction
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Compounds 2 and 3 were designed in order to probe the North-East region of the strichnine-insensitive glycine binding site of the NMDA receptor. The two products were obtained readily by a tandem aldol condensation- lactonization-elimination step which af
- Giacobbe, Simone A.,Baraldi, Davide,Di Fabio, Romano
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p. 1689 - 1692
(2007/10/03)
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- Reaction of β-, γ-, and δ-chloroalkanamides with potassium tert-butoxide in tetrahydrofuran: Elimination, and lactamization
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γ- and δ-Chloroalkanamides were found to undergo lactamization readily when treated with potassium tert-butoxide in tetrahydrofuran. Raising the reaction temperature may encourage SN2 displacement reaction. On the other hand β-chloroalkanamides only undergo elimination, followed by dimerization and trimerization of the acrylamide initially formed.
- Wang, Eng Chi,Lin, Huey-Jen
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p. 481 - 489
(2007/10/03)
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- Synthesis of lactams by regioselective reduction of cyclic dicarboximides
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Lactams can be obtained by the monothionation of imides with Lawesson's reagent followed by the desulfurization of resulted monothioimides with Raney nickel.
- Milewska, Maria J.,Bytner, Tomasz,Polonski, Tadeusz
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p. 1485 - 1488
(2007/10/03)
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- Metalloporphyrin-catalysed rearrangement of oxaziridines: An efficient and regioselective synthesis of lactams using ring-enlargement of N-phenyl-spirooxaziridines
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Manganese(III) tetraphenylporphyrin, Mn(tpp)Cl, is a new and specific catalyst for stereo- and regio-selective rearrangement of N-phenyl-spirooxaziridines into lactams.
- Suda,Sashima,Izutsu,Hino
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p. 949 - 950
(2007/10/02)
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- Photolyse d'oxaziridines. 10. Photolyse et thermolyse d'oxaziridines N-arylees
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The nature of the nitrogen substituent does not affect the regioselectivity of lactams derived from photolysis or thermolysis of spirooxaziridines.The thermolysis of N-arylspirooxaziridines is a very good synthetic method to obtain N-aryl heterocycles.
- Oliveros, Esther,Riviere, Monique,Lattes, Armand
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p. 1025 - 1027
(2007/10/02)
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