- Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
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Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
- Yi, Jaeeun,Kim, Hyun Tae,Jaladi, Ashok Kumar,An, Duk Keun
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supporting information
p. 129 - 132
(2021/11/17)
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- Method for synthesizing amide by using methyl arene and amine in water phase
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The invention provides a high-efficient method of synthesizing amide with methyl aromatics and amine. In the method, with the methyl aromatics and the amine as the raw materials in the water phase and TBHP and TBAI respectively as an oxidizing agent and a catalyst, a sp3 C-H bond and a sp3 N-H bond are broken and a C-N bond is formed. Compared with a conventional method of synthesizing the amide from oxidized amide, in which an activated acyl group or amine is required, the method is carried out with water as the solvent so that the method is not only economical but also environmental-protective. The method has a very good application prospect in the field of synthesizing polypeptide, protein and drugs in future.
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Paragraph 0015; 0053-0056
(2021/03/06)
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- Generation of alkyl radicals from alkylsilyl peroxides and their applications to C-N or C-O bond formations
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This article describes a novel method for the generation of alkyl radicals from alkylsilyl peroxides and their applications to the Cu-catalyzed mono-N-alkylation of amides or arylamines, and to the O-alkylation of carboxylic acids. The use of alkylsilyl peroxides as alkyl radical sources includes the following synthetic advantages: i) various alkylsilyl peroxides can be readily synthesized from the corresponding alcohols and be stored at bench, and ii) a variety of alkyl radicals can be generated efficiently under mild conditions.
- Sakurai, Shunya,Kato, Terumasa,Sakamoto, Ryu,Maruoka, Keiji
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p. 172 - 179
(2018/12/11)
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- Visible-Light-Driven Oxidation of N -Alkylamides to Imides Using Oxone/H 2 O and Catalytic KBr
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Imides are prepared conveniently by visible-light-driven oxidations of various N -alkylamides under mild conditions. The majority of the reactions proceed efficiently by using Oxone as the oxidant in the presence of a catalytic amount of KBr in H 2 O/CH 2 Cl 2 under irradiation by an 8 W white LED at room temperature. Experimental studies suggest that an imine, obtained from the substrate amide via a radical process, is the key intermediate.
- Mei, Chong,Hu, Yixin,Lu, Wenjun
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supporting information
p. 2999 - 3005
(2018/05/25)
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- Metal-Free Thermal Activation of Molecular Oxygen Enabled Direct α-CH2-Oxygenation of Free Amines
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Direct oxidation of α-CH2 group of free amines is hard to achieve due to the higher reactivity of amine moiety. Therefore, oxidation of amines involves the use of sophisticated metallic reagents/catalyst in the presence or absence of hazardous oxidants under sensitive reaction conditions. A novel method for direct C-H oxygenation of aliphatic amines through a metal-free activation of molecular oxygen has been developed. Both activated and unactivated free amines were oxygenated efficiently to provide a wide variety of amides (primary, secondary) and lactams under operationally simple conditions without the aid of metallic reagents and toxic oxidants. The method has been applied to the synthesis of highly functionalized amide-containing medicinal drugs, such as O-Me-alibendol and -buclosamide.
- Ghosh, Santanu,Jana, Chandan K.
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p. 260 - 266
(2018/02/19)
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- Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-: N -alkylation of primary amides
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The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.
- Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
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supporting information
p. 6484 - 6487
(2017/07/10)
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- Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines
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The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides.
- Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
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supporting information
p. 9030 - 9033
(2017/07/11)
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- Aminofluorene-Mediated Biomimetic Domino Amination-Oxygenation of Aldehydes to Amides
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A conceptually novel biomimetic strategy based on a domino amination-oxygenation reaction was developed for direct amidation of aldehydes under metal-free conditions employing molecular oxygen as the oxidant. 9-Aminofluorene derivatives acted as pyridoxamine-5′-phosphate equivalents for efficient, chemoselective, and operationally simple amine-transfer oxygenation reaction. Unprecedented RNH transfer involving secondary amine to produce secondary amides was achieved. In the presence of 18O2, 18O-amide was formed with excellent (95%) isotopic purity.
- Ghosh, Santanu,Jana, Chandan K.
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supporting information
p. 5788 - 5791
(2016/11/29)
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- Direct oxidative amidation between methylarenes and amines in water
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An environmentally friendly direct oxidative amidation between methylarenes and free amines was developed. The aromatic amide could be prepared efficiently from raw chemicals by employing TBHP as a "green" oxidant with co-catalysis of TBAI and FeCl3 in water.
- Wang, Tao,Yuan, Lin,Zhao, Zhenguang,Shao, Ailong,Gao, Meng,Huang, Yangfei,Xiong, Fei,Zhang, Huali,Zhao, Junfeng
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supporting information
p. 2741 - 2744
(2015/05/27)
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- Metal-Free Synthesis of Dibenzoxazepinones via a One-Pot SNAr and Smiles Rearrangement Process: Orthogonality with Copper-Catalyzed Cyclizations
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Reported is the transition-metal-free synthesis of substituted dibenzoxazepinones using a convergent domino SNAr-Smiles rearrangement-SNAr process. Substrate-scope investigations demonstrated the critical importance of ring electroni
- Hurst, Timothy E.,Kitching, Matthew O.,Da Frota, Lívia C. R. M.,Guimar?es, Keller G.,Dalziel, Michael E.,Snieckus, Victor
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p. 1455 - 1460
(2015/06/30)
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- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
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A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1 and cyclic and acyclic 2 amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
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supporting information
p. 1006 - 1010
(2014/02/14)
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- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
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A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2°amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
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supporting information
p. 1006 - 1010
(2015/02/19)
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- The α-effect in hydrazinolysis of 4-chloro-2-nitrophenyl x-substituted-benzoates: Effect of substituent x on reaction mechanism and the α-effect
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Second-order rate constants (kN) have been measured spectrophotometrically for the reaction of 4-chloro-2- nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % H2O/20 mol % DMSO at 25.0°C. The Bronsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with βnuc = 0.74 when hydrazine is excluded from the correlation. Such a linear Bronsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ?X = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the α-effect). The α-effect increases as the substituent X in the benzoyl moiety becomes a stronger electronwithdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent α-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the α-effect observed in this study.
- Kim, Min-Young,Kim, Tae-Eun,Lee, Jieun,Um, Ik-Hwan
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p. 2271 - 2276
(2014/09/29)
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- Highly selective palladium-catalysed aminocarbonylation of aryl iodides using a bulky diphosphine ligand
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An efficient methodology for the synthesis of amides via palladium-catalysed aminocarbonylation of aryl iodides is reported using the bulky cis-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane ligand under atmospheric pressure of carbon monoxide. Excellent conversions (up to 99%) and chemoselectivities (up to 99%) were obtained for a range of aryl iodides and amine nucleophiles. The effect of the substituents on the substrate and nucleophiles on the catalytic performance was investigated. An NMR study was also carried out and key intermediates of the catalytic cycle were detected and characterised. Copyright
- De La Fuente, Veronica,Godard, Cyril,Claver, Carmen,Castillon, Sergio
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experimental part
p. 1971 - 1979
(2012/09/22)
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- Copper-catalyzed cross-coupling interrupted by an opportunistic smiles rearrangement: An efficient domino approach to dibenzoxazepinones
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Unexpected Smiles! An unusual and highly regioselective synthesis of dibenzoxazepinones by a domino sequence assisted by an unexpected Smiles rearrangement is reported. The process is effective on electronically differentiated phenols and shows a high tolerance to variation in the benzamide substituents. A plausible path for the reaction, supported by preliminary mechanistic data, is offered. Copyright
- Kitching, Matthew O.,Hurst, Timothy E.,Snieckus, Victor
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supporting information; experimental part
p. 2925 - 2929
(2012/05/04)
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- Rhodium(iii)-catalyzed oxidative carbonylation of benzamides with carbon monoxide
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An efficient strategy for the oxidative carbonylation of aromatic amides via C-H/N-H activation to form phthalimides using an Rh(iii) catalyst has been developed. The reaction shows a preference for C-H bonds of electron-rich aromatic amides and tolerates a variety of functional groups. The Royal Society of Chemistry 2011.
- Du, Ya,Hyster, Todd K.,Rovis, Tomislav
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p. 12074 - 12076
(2011/12/14)
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- IMPROVED METHOD FOR THE PRODUCTION OF N-SUBSTITUTED AMIDES FROM NITRILES
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An improved method for the production of N-substituted amides of formula RCONHR1 (I) wherein R represents an optionally monosubstituted or polysubstituted C1-C20-alkyl-, C5 -C20-aryl- or C5-C20--heterocyclic radical and R1 represents an optionally monosubstituted or polysubstituted C1-C20-alkyl- or C5-C20-aryl radical from corresponding nitriles of formula RCN (II) wherein R1 is defined as above, wherein a nitril of formula (II) is reacted in polyphosphoric acid with an alcohol of formula R10H (III) wherein R1 is as defined above, in the presence of a compound from the group consisting of phosphorpentoxide, phosphoroxychloride, sulfurylchloride, dialkylcarbonate and dialkylsulfate at a temperature of 80 -190 °C to form the corresponding N-substituted amide.
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Page/Page column 10
(2010/02/06)
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- Effects of amine nature and nonleaving group substituents on rate and mechanism in aminolyses of 2,4-dinitrophenyl x-substituted benzoates
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Second-order rate constants have been measured for the reactions of 2,4-dinitrophenyl X-substituted benzoates (1a-f) with a series of primary amines in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Bronsted-type plot for the reactions of 1d with primary amines is biphasic with slopes β1 = 0.36 at the high pKa region and β2 = 0.78 at the low pKa region and the curvature center at pKa° = 9.2, indicating that the reaction proceeds through an addition intermediate with a change in the rate-determining step as the basicity of amines increases. The corresponding Bro nsted-type plot for the reactions with secondary amines is also biphasic with β1 = 0.34, β2 = 0.74, and pKa° = 9.1, indicating that the effect of amine nature on the reaction mechanism and pKa° is insignificant. However, primary amines have been found to be less reactive than isobasic secondary amines. The microscopic rate constants associated with the aminolysis have revealed that the smaller k 1 for the reactions with primary amines is fully responsible for their lower reactivity. The electron-donating substituent in the nonleaving group exhibits a negative deviation from the Hammett plots for the reactions of 1a-f with primary and secondary amines, while the corresponding Yukawa-Tsuno plots are linear. The negative deviation has been ascribed to stabilization of the ground state of the substrate through resonance interaction between the electron-donating substituent and the carbonyl functionality.
- Um, Ik-Hwan,Kim, Kyung-Hee,Park, Hye-Ran,Fujio, Mizue,Tsuno, Yuho
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p. 3937 - 3942
(2007/10/03)
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- Rhodium-catalyzed Beckmann rearrangement
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equation presented Beckmann rearrangement of oxime is catalyzed by [RhCl(cod)]2, trifluoromethanesulfonic acid, and tris(p-tolyl)phosphine in refluxing dichloroethane, giving the corresponding amide in good yield. Product/acid ratios of 10:20 can be attained in the reaction of benzophenone oximes.
- Arisawa, Mieko,Yamaguchi, Masahiko
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p. 311 - 312
(2007/10/03)
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- An unusual ground-state stabilization effect and origins of the α- effect in aminolyses of Y-substituted phenyl X-substituted benzoates
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Second-order rate constants have been measured spectrophotometrically for the reactions of X-C6H4CO2C6H4-Y with a series of primary amines in H2O containing 20 mol% DMSO at 25.0 ± 0.1°C. The reactivity increases as the substituent (X and Y) becomes a stronger electron-withdrawing group. The σ+ constants give better Hammett correlation than σ constants for the reactions of 4-nitrophenyl X-substituted benzoates with glycylglycine (glygly) and hydrazine (NH2NH2), indicating that the ground-state stabilization effect is unusually significant on the reaction rates. The reactions of X-C6H4CO2C6H4-Y with glygly and NH2NH2 appear to proceed through the same mechanism, but the degree of leaving-group departure and the negative charge developed in the acyl moiety at the rate-determining TS is considered to be more significant for the glygly system than the NH2NH2 system based on β(1g) and ρ(x) values. The magnitude of the α-effect is observed to be not always dependent on the β(nuc) value but dependent on the electronic nature of the substituent X and Y, i.e., an electron-donating substituent increases the α-effect, while an electron-withdrawing one decreases the α-effect. The present study has led to the conclusion that the ground-state effect is important for the reaction rates but it is not solely responsible for the α-effect, and the intramolecular H-bonding interactions (4) are proposed for the cause of the increasing or decreasing α-effect trends observed in the present system.
- Um, Ik-Hwan,Chung, Eun-Kyung,Lee, So-Mi
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p. 729 - 737
(2007/10/03)
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- Aminolysis of Benzoyl Fluorides in Water
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The reactions of benzoyl fluorides (p-Me2N, p-MeO, m-Cl) with primary amines of pKa = 3.9-11 in aqueous solution follow a first-order dependence on amine concentration and the addition of 0.83 M potassium phosphate, 10percent dianion, does not
- Song, Byeong Doo,Jencks, William P.
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p. 8479 - 8484
(2007/10/02)
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- 11a-Methano-TXA compounds
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The present invention provides novel 11a-methano-TXA compounds and intermediates and processs for their preparation. Further provided are methods for using these novel TXA analogs as inhibitors of thromboxane synthetase, rendering these analogs useful for a variety of pharmacological purposes. These pharmacological uses include anti-inflammatory, anti-thromobitc, and anti-asthma indications.
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