- One-pot route to new α,α-difluoroamides and α-ketoamides
-
New α,α-difluoroamides (4a-d, 6a-d) and α-ketoamides (5a-d, 7a-d) result from one-pot reactions of α-ketoacids, RCOCO2H (R = C6H5, CH3, CH3CH2, thienyl) (1a-d) with bis(2-methoxyethyl)aminosulfur trifluoride [(CH3-OCH2CH2)2NSF3] (2) (Deoxofluor) or diethylaminosulfur trifluoride [(CH3CH2)2NSF3)] (3) (DAST). Product yields depend on reaction times and the ratio of reagents used. Longer reaction times (~36 h) with a 1:2 ratio of α-ketoacids and 2 or 3 gave major yields of the α,α-difluoroamides, and shorter reaction times (~1 h) produced α,α-ketoamides as the major products. Reactants in a 1:1 ratio resulted in α-ketoamides only.
- Singh, Rajendra P.,Shreeve, Jean'ne M.
-
-
Read Online
- Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides
-
The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)-complex, Pd-L4. In contrast, analogues L1-L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/di)phosphines. The catalytic system resulting from the complexation of PdCl2(MeCN)2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81-95%) and α-ketoamide selectivity (80-91%), as well as the available recyclability in the RTIL of [Bpy]BF4. The in situ FT-IR analysis reveals that the PdCl2(MeCN)2-L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent CO-insertion steps.
- Yang, Shu-Qing,Yao, Yin-Qing,Chen, Xiao-Chao,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
-
supporting information
p. 1032 - 1041
(2021/05/07)
-
- Diversification of α-ketoamides: Via transamidation reactions with alkyl and benzyl amines at room temperature
-
A wide range of N-tosyl α-ketoamides underwent transamidation with various alkyl amines in the absence of a catalyst, base, or additive. On the other hand, transamidation in N-Boc α-ketoamides was achieved in the presence of Cs2CO3. The reactions proceede
- Junaid, Qazi Mohammad,Kandasamy, Jeyakumar,Popuri, Sureshbabu,Sabiah, Shahulhameed,Singh, Shweta
-
p. 7134 - 7140
(2021/08/30)
-
- K2S2O8activation by glucose at room temperature for the synthesis and functionalization of heterocycles in water
-
While persulfate activation at room temperature using glucose has primarily been focused on kinetic studies of the sulfate radical anion, the utilization of this protocol in organic synthesis is rarely demonstrated. We reinvestigated selected K2S2O8-mediated known organic reactions that invariably require higher temperatures and an organic solvent. A diverse, mild functionalization and synthesis of heterocycles using the inexpensive oxidant K2S2O8 in water at room temperature is reported, demonstrating the sustainability and broad scope of the method. Unlike traditional methods used for persulfate activation, the current method uses naturally abundant glucose as a K2S2O8 activator, avoiding the use of higher temperature, UV light, transition metals or bases.
- Hunjan, Mandeep Kaur,Laha, Joydev K.
-
p. 8437 - 8440
(2021/09/02)
-
- Ligand-free Zn-catalyzed double carbonylation of aryl iodides with secondary amines: A simple and efficient approach to access α-ketoamides
-
Herein, we report a Zinc catalyzed double carbonylation of aryl iodides with secondary amines under CO pressure for the synthesis of α-ketoamides in good to excellent yields. This methodology provides a simple and economic approach to derivatize useful α-
- Chidara, Sridhar,Mogili, Padma,Pitti, Vimala,Sarma Vangala, Markandeya
-
supporting information
(2021/12/22)
-
- Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
-
The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP) with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation reactions. Double carbonylation was found to be the main reaction using different iodoarenes and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles. Recyclability was tested in five successive runs for all of the substrates.
- Nagy, Enik?,Nagy, Petra,Papp, Máté,Skoda-F?ldes, Rita,Urbán, Béla
-
-
- Cu-Catalyzed aerobic oxidative cleavage of C(sp3)–C(sp3) bond: Synthesis of α-ketoamides
-
A novel synthesis of α-ketoamides from Cu-catalyzed aerobic oxidative C(sp3)–C(sp3) bond cleavage of hydrocinnamaldehydes has been developed. Readily available and environmentally benign oxygen is used as the oxidant. This reaction avoids the use of noble metal catalysts or specialized oxidants, and chemoselectively yields α-ketoamide. Moreover, based on various control experiments, a reasonable mechanism is proposed.
- Fang, Zheng,Guo, Kai,Liu, Chengkou,Yang, Man,Zhang, Jingming
-
supporting information
(2020/11/02)
-
- Copper/Iodine-Cocatalyzed C-C Cleavage of 1,3-Dicarbonyl Compounds Toward 1,2-Dicarbonyl Compounds
-
A new, general oxidative route to transformations of 1,3-dicarbonyl compounds to 1,2-dicarbonyl compounds by merging copper and I2 catalysis is described. This method is applicable to broad 1,3-dicarbonyl compounds, including 1,3-diketones, 1,3-keto esters and 1,3-keto amides. Mechanistical studies show that the reaction is achieved via the C–C bond cleavage and CO release cascades.
- Chen, Li-Sha,Zhang, Lu-Bing,Tian, Yue,Li, Jin-Heng,Liu, Yong-Quan
-
supporting information
p. 5523 - 5526
(2020/09/02)
-
- Copper-Mediated Synthesis of Aryl α-Keto Amides from Epoxide Derivatives
-
A novel Cu II -mediated synthesis of aryl α-keto amides from epoxide derivatives is reported. This transformation was conducted by using O 2 as a green oxidant that meets the requirements of sustainable chemistry.
- Cui, Yunjian,Dong, Yi,Liu, Fenghua,Xu, Heng
-
supporting information
p. 1011 - 1014
(2020/06/10)
-
- Dimethyl Sulfoxide as an Oxygen Atom Source Enabled Tandem Conversion of 2-Alkynyl Carbonyls to 1,2-Dicarbonyls
-
A tandem transformation of 2-alkynyl carbonyl compounds by means of a CuBr2/I2/DMSO/water system is developed, enabling the fromation of various functionalized 1,2-dicarbonyl compounds, including 1,2-diketones, α-keto amides and α-keto ester. This Cu-promoted iodine-mediated tandem procedure employs DMSO as the oxygen atom source of the formed carbonyl group through iodonium ion formation, nucleophilic DMSO addition and C?C bond cleavage cascades. (Figure presented.).
- Hu, Ming,Li, Jin-Heng,Li, Yang,Lu, Yuan,Luo, Mu-Jia
-
supporting information
(2020/05/01)
-
- Palladium-Catalyzed Oxidative C≡C Triple Bond Cleavage of 2-Alkynyl Carbonyl Compounds Toward 1,2-Dicarbonyl Compounds?
-
A new, general palladium-catalyzed oxidative strategy for the cleavage of the C≡C triple bond is presented. By employing PdCl2, CuBr2, TEMPO and air as the catalytic system and H2O as the carbonyl oxygen atom source, a wide range of 2-alkynyl carbonyl compounds, including 1,3-disubstituted prop-2-yn-1-ones, propiolamides and propiolates, lost an alkynyl carbon to access various 1,2-dicarbonyl compounds, e.g., 1,2-diones, 2-keto amides and 2-keto esters, through Wacker oxidation, intramolecular cyclization and C—C bond cleavage cascades.
- Hu, Ming,Li, Jin-Heng,Luo, Mu-Jia,Zhou, Ming-Bo
-
p. 553 - 558
(2020/04/20)
-
- Cu(OAc)2 and acids promoted the oxidative cleavage of α-aminocarbonyl compounds with amines: efficient and selective synthesis of 2-t-amino-2-imino-carbonyl and 2-amino-2-oxocarbonyl
-
A novel and efficient method for the synthesis of 2-t-amino-2-imino-carbonyl (C) and 2-amino-2-oxocarbonyl (D) compounds has been discovered through a copper-promoted oxidating amidation reactions between α-amino -carbonyl compounds and amines. Promoted by the crucial copper species, perfect selectivity and good to excellent yields could be achieved. This transformation is achieved through C[sbnd]N bond oxidative cleavage and formation a novel C[sbnd]N bond. This reaction system has a broad reaction scope, providing a facile pathway for the α-functionalization of α-amino ketones.
- Chen, De,Cheng, Chaozhihui,Zeng, Sheng,Luo, Yongyue,Zhang, Jiajia,Deng, Wei,Zeng, Zebing,Wang, Ruijia,Xiang, Jiannan
-
supporting information
(2020/04/15)
-
- Copper-Catalyzed Oxidative Synthesis of α-Ketoamides from Aryl Methyl Ketones and N -Bromobutanimide Using N, N -Dimethylformamide as Dimethylamine Source
-
A novel and practical Cu(OAc) 2 -catalyzed oxidative synthesis of α-ketoamides from aryl methyl ketones and N -bromobutanimide (NBS) using N, N -dimethylformamide (DMF) as dimethylamine (HNMe 2) source and solvent has been developed under mild conditions. DMF was used as a HNMe 2 source and can be easily converted into HNMe 2 by acid hydrolysis. The mechanistic studies indicate that Cu(OAc) 2 plays a dual role in providing both catalyst and oxidant.
- Li, Xiaoyan,Wei, Ying,Yan, Yongxia
-
p. 393 - 397
(2020/02/27)
-
- New palladium (II) complexes containing phosphine-nitrogen ligands and their use as catalysts in aminocarbonylation reaction
-
Aminocarbonylation of aryl halides, homogeneously catalysed by palladium, is an efficient method that can be employed for obtaining amides for pharmaceutical and synthetic applications. In this work, palladium (II) complexes containing P^N ligands were studied as catalysts in the aminocarbonylation of iodobenzene in the presence of diethylamine. Two types of systems were used: a palladium (II) complex formed in situ; and one prepared prior to the catalytic reaction. In general, the palladium complexes studied achieved high conversions in an average reaction time of less than 2 hr, which is less than that for the standard system (Pd (II)/PPh3) used. The pre-synthesized complexes were faster than their in situ counterparts, as the latter require an induction time to form the Pd/P^N species. The structure and electronic properties of the ligand P^N can influence both the activity and the selectivity of the reaction, stabilizing the acyl-palladium intermediates formed in a better manner.
- Aranda, Braulio,Moya, Sergio A.,Vega, Andres,Valdebenito, Gonzalo,Ramirez-Lopez, Sofia,Aguirre, Pedro
-
-
- Cu-Catalysed oxidative amidation of cinnamic acids/arylacetic acids with 2° amines: An efficient synthesis of α-ketoamides
-
A new and convenient copper-catalysed synthesis of α-ketoamides has been accomplished using readily available cinnamic acids/arylacetic acids and 2° amines in an open atmosphere. The reaction between cinnamic acid and amine involves the formation of enamine followed by its aerobic oxidation, whereas the reaction of arylacetic acid with amine involves amide formation followed by benzylic methylene oxidation.
- Sharma, Anup Kumar,Jaiswal, Anjali,Singh, Krishna Nand
-
supporting information
p. 9348 - 9351
(2019/11/11)
-
- Metal-Free C=C Double Bond Cleavage on Enaminones for the Synthesis of α-Ketoamides by Free-Radical Aerobic Oxygenation
-
The tandem oxidation of the enaminone C=C double bond as well as subsequent C-N bond formation are realized under metal-free conditions by thermo-induced free radical transformation. In the presence of benzoyl peroxide (BPO) and N-iodosuccinimide (NIS), a
- Yang, Yiming,Zhong, Guofeng,Fan, Junfen,Liu, Yunyun
-
supporting information
p. 4422 - 4425
(2019/06/24)
-
- Visible-light-mediated direct access to α-ketoamides by dealkylative amidation of tertiary amines with benzoylformic acids
-
A visible-light induced direct amidation of benzoylformic acids with tertiary amines has been explored. Tertiary amines underwent N-dealkylative amidation with α-keto acid in the presence of [Ir{dFCF3ppy}2(bpy)]PF6 and Cs
- Zhang, Zhiguo,Liu, Fangnan,Chen, Jingwen,Zhou, Kai,Bao, Zongbi,Su, Baogen,Yang, Qiwei,Ren, Qilong,Yang, Yiwen
-
supporting information
(2019/10/02)
-
- Stabilized Cu2O nanoparticles on rGO highly catalyzed direct oxidative coupling synthesis of Α-ketoamides with molecular oxygen
-
In this study, a green, efficient, recyclable Cu2O nanoparticles on reduced graphene oxide (Cu2O-NPs@rGO) carbon-based composite catalyst was synthesized by facile one-pot hydrothermal method. And Cu2O-NPs@rGO catalyst was
- Lu, Weiyang,Sun, Wei,Tan, Xiaofeng,Wang, Bin,Yang, Hua,Gao, Lingfeng,Zheng, Gengxiu
-
-
- Copper-catalyzed oxidative synthesis of 2-oxo-acetamidines from one-pot three-component reaction of aryl methyl ketones, secondary amines and anilines
-
Some novel 2-oxo-acetamidines were synthesized via one-pot three-component reaction of acetophenones, secondary amines and anilines in presence of CuI as catalyst. The reaction involved in a oxidation process of C (sp3)–H bonds of acetophenones
- Dutta, Leema,Bhuyan, Pulak J.
-
p. 5770 - 5778
(2018/08/22)
-
- Double carbonylation of iodoarenes in the presence of reusable palladium catalysts immobilised on supported phosphonium ionic liquid phases
-
The first heterogeneous carbonylation reaction carried out with palladium catalysts immobilised on phosphonium ion modified silica supports is reported. The supported ionic liquid phases were characterised by solid state NMR and FT-IR measurements. The presence of the phosphonium ions on the surface made it possible to carry out double carbonylation in apolar toluene efficiently that resulted in reduced metal leaching. The introduction of dicationic moieties on the solid support has been proved to lead to a further increase in catalyst stability. The catalysts were proved to produce α-ketoamide products with excellent selectivity in the carbonylation of iodoarenes with aliphatic amines while monocarbonylation was the only reaction observed with aniline derivatives. The catalysts could be recycled and used in at least 10 subsequent runs under optimised conditions.
- Urbán, Béla,Szabó, Péter,Srankó, Dávid,Sáfrán, Gy?rgy,Kollár, László,Skoda-F?ldes, Rita
-
p. 195 - 205
(2018/01/05)
-
- Cu(i)/{Nb6O19} catalyzed: N -acylation of arylacetic acids with amines under aerobic conditions
-
The method described herein is a general, efficient and green approach to synthesize α-ketoamides from arylacetic acids and amines. Employing a simple copper(i)/{Nb6O19} catalyst system, the reaction offers a facile process to give functionalized α-ketoamides from readily available arylacetic acids under aerobic conditions. The merit of this new strategy is that it expands the syntheses of α-ketoamides from stable, inexpensive and widely available acylation reagents such as arylacetic acids in one step.
- Li, Pei-He,Wang, Zheng,Fu, Hui,Dai, Qi-Pu,Hu, Chang-Wen
-
supporting information
p. 12471 - 12474
(2018/11/23)
-
- Aerobic oxidative amidation of alkynes using titanium oxide encapsulated cuprous iodide nanoparticles (CuI@TiO2)
-
A catalyst consisting of titanium oxide encapsulated cuprous iodide nanoparticles was prepared via a sol-gel method using inexpensive raw materials and was harnessed successfully in the oxidative amidation of alkynes via an environmentally benign and sustainable protocol. The mechanism of action of this transformation was thoroughly discussed. The robustness of the catalyst was elucidated by the synthesis of diverse analogues of α-ketoarylamide from a variety of electron rich and poor substrates via a simple procedure in moderate to high yields, with no generation of toxic by-products, in good recyclability up to five cycles, under solvent free and aerobic conditions. The chemical nature, morphology and loading of the CuI@TiO2 nanocatalyst were investigated by TEM, SEM, XPS, EDX, powder XRD, BET, TGA and ICP-MS.
- Dutta, Pratip Kumar,Dhar, Basabbijayi,Sen, Subhabrata
-
p. 12062 - 12071
(2018/07/24)
-
- UV Assisted High-Efficient Synthesis of α-Ketoamides using Air Promoted by A Non-Metal Catalyst in Aqueous Solution
-
Presented here is the first example of UV (λ=210 nm) promoted procedure proceeding in aqueous media at room temperature using ambient air as the oxidant for efficient synthesis of an array of α-ketoamides of all types using a non-metal catalyst N-iodosuccinimide with a loading of 20 mol%. With UV, oxygen in the air was efficiently utilized as the green oxidant, some control experiments were carried out and a plausible mechanism was proposed, disclosing that in aqueous solution, the oxidation process was actually triggered by dioxygen radical anion (O2.?), while not molecular oxygen. A variety of secondary amines and primary amines as well as ammonia were employed as the amine moieties, and the desired product primary-, secondary-, and tertiary α-ketoamides were afforded in good to excellent yields of up to 96 %.
- Li, Jianhui,He, Shaopo,Zhang, Kuan,Quan, Ziyi,Shan, Qiheng,Sun, Zhongliang,Wang, Bo
-
p. 4868 - 4873
(2018/10/15)
-
- Mono- and double carbonylation of aryl iodides with amine nucleophiles in the presence of recyclable palladium catalysts immobilised on a supported dicationic ionic liquid phase
-
Silica modified with organic dicationic moieties proved to be an excellent support for palladium catalysts used in the aminocarbonylation of aryl iodides. By an appropriate choice of the reaction conditions, the same catalyst could be used for selective mono- or double carbonylations leading to amide and α-ketoamide products, respectively. The best catalyst could be recycled for at least 10 consecutive runs with a loss of palladium below the detection limit. By the application of the new support, efficient catalyst recycling could be achieved under mild reaction conditions (under low pressure and in a short reaction time). Palladium-leaching data support a mechanism with dissolution - re-precipitation of the active palladium species.
- Papp,Szabó,Srankó,Sáfrán,Kollár,Skoda-F?ldes
-
p. 44587 - 44597
(2017/09/26)
-
- Enantioselective Iridium-Catalyzed Hydrogenation of α-Keto Amides to α-Hydroxy Amides
-
A highly enantioselective iridium-catalyzed hydrogenation of α-keto amides to form α-hydroxy amides has been achieved with excellent results (up to >99% conversion and up to >99% ee, TON up to 100?000). As an example, this protocol was applied to the synthesis of (S)-4-(2-amino-1-hydroxyethyl)benzene-1,2-diol, the enantiomer of norepinephrine, which is widely used as an injectable drug for the treatment of critically low blood pressure. Density functional theory (DFT) calculations were also carried out to reveal the reaction mechanism.
- Gu, Guoxian,Yang, Tilong,Yu, Ouran,Qian, Hua,Wang, Jiang,Wen, Jialin,Dang, Li,Zhang, Xumu
-
supporting information
p. 5920 - 5923
(2017/11/10)
-
- nBu4NI-Mediated oxidation of methyl ketones to α-ketoamides: using ammonium, primary and secondary amine-salt as an amine moiety
-
Presented here is the first example of synthesizing an array of primary-, secondary-, and tertiary-α-ketoamides with a non-metal catalyst nBu4NI from methyl ketones and inexpensive readily available amine/ammonium salts; the reactions proceeded smoothly under mild conditions, TBHP was used as an oxidant and the corresponding α-ketoamides were afforded in moderate to excellent yields.
- Wang, Dan,Zhang, Kuan,Jia, Luhan,Zhang, Danting,Zhang, Yue,Cheng, Yujia,Lin, Chang,Wang, Bo
-
p. 3427 - 3434
(2017/04/24)
-
- Solvent-free one-pot oxidation of ethylarenes for the preparation of α-ketoamides under mild conditions
-
Here we developed a highly efficient solvent-free, one-pot procedure for synthesizing α-ketoamides from ethylarenes and amines, by oxidizing a C-H bond sp3 center. A copper catalyst was employed, and the reactions proceeded smoothly at ambient temperatures. Most of the tested ethylarenes and amines were successfully converted to their corresponding α-ketoamides in moderate to excellent yields of up to 93% with three equivalents of the oxidant tert-butyl hydroperoxide.
- Liu, Fuyan,Zhang, Kuan,Liu, Yanfeng,Chen, Shan,Chen, Yiping,Zhang, Dela,Lin, Chunfu,Wang, Bo
-
p. 7158 - 7162
(2017/02/05)
-
- A METAL FREE PROCESS FOR THE PREPARATION OF ALPHA-SUBSTITUTED CARBONYL COMPOUNDS FROM ALKENES
-
The present invention discloses a novel metal free process for the regioselective synthesis of α-substituted carbonyl compounds of formula I from alkene, X is selected from the following compounds (A, B).
- -
-
Page/Page column 20-21; 23
(2017/06/19)
-
- Palladium supported on triphenylphosphine-functionalized porous organic polymer: An efficient heterogeneous catalyst for aminocarbonylation
-
An efficient route for the catalytic synthesis of aryl amides via the aminocarbonylation of aryl iodides with amines is described using palladium supported on triphenylphosphine-functionalized porous organic polymer (Pd@KAPs(Ph-PPh3)) as the catalyst. Under low carbon monoxide pressure, the catalyst exhibited remarkable activity, and only 0.5 mol% palladium loading was required to achieve moderate to excellent yields (70-97 %) of aryl amides. The catalyst can be easily separated by a simple filtration process and recycled up to seven times with only minor loss of activity. The salient features of this protocol are the simplicity in handling of catalyst, low CO pressure, good functional group tolerance, high catalytic activity, negligible palladium leaching and effective catalyst recyclability.
- Lei, Yizhu,Zhang, Xuefeng,Gu, Yanlong,Hu, Jianglin,Li, Guangxing,Shi, Kaiyi
-
-
- Transition metal-free synthesis of α-ketoamides from arylmethyl ketones and alkylphosphoramides
-
A transition metal-free protocol has been developed for the synthesis of α-ketoamides from aryl methyl ketones and alkylphosphoramides in the presence of oxidant, aqueous tert-butyl hydroperoxide (TBHP). A series of aryl methyl ketones having both electron-donating as well as electron-withdrawing groups were successfully employed for the synthesis of their corresponding α-ketoamides using hexamethylphosphoramide and other alkylphosphoramides.
- Behera, Ahalya,Ali, Wajid,Tripathy, Manisha,Sahoo, Diptimayee,Patel, Bhisma K.
-
p. 91308 - 91313
(2016/10/09)
-
- Room temperature copper-catalyzed oxidative amidation of terminal alkynes for the synthesis of α-ketoamides using: O -benzoyl hydroxylamines as aminating reagent and oxidant
-
A novel and convenient copper-catalyzed oxidative amidation for the synthesis of α-ketoamides has been successfully developed, which uses easily available O-benzoyl hydroxylamines as aminating reagent and oxidant. The reaction proceeds smoothly at room temperature and is compatible with a range of substrates to give the desired products in moderate to good yields.
- Shen, Guodong,Zhao, Lingyu,Wang, Yichen,Zhang, Tongxin
-
p. 78307 - 78310
(2016/09/09)
-
- Copper-TEMPO-catalyzed synthesis of α-ketoamides: Via tandem sp3C-H aerobic oxidation and amination of phenethyl alcohol derivatives
-
An efficient copper-TEMPO-catalyzed one-pot synthesis of α-ketoamides from phenethyl alcohol derivatives was developed firstly. Moreover, molecular oxygen in open air was employed as the oxidant with a broad substrate scope, which makes this methodology more practical. Based on some control experiments, a plausible mechanism was proposed.
- Liu, Chengkou,Yang, Zhao,Guo, Shiyu,Zeng, Yu,Zhu, Ning,Li, Xin,Fang, Zheng,Guo, Kai
-
supporting information
p. 8570 - 8575
(2016/09/28)
-
- 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
-
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
-
p. 25167 - 25172
(2016/03/22)
-
- Copper-catalyzed, hypervalent iodine mediated C=C bond activation of enaminones for the synthesis of α-keto amides
-
An unprecedented C=C bond cleavage of enaminones has been realized by means of copper catalysis in the presence of hypervalent iodine (PhI(OAc)2). The cascade transformation based on this bond cleavage leads to the synthesis of various α-keto amides. Isotope labeling experiments suggest that water has acted as a source of oxygen atoms during the generation of the new carbonyl group.
- Wan, Jie-Ping,Lin, Yunfang,Cao, Xiaoji,Liu, Yunyun,Wei, Li
-
supporting information
p. 1270 - 1273
(2016/01/15)
-
- Regioselective oxo-amination of alkenes and enol ethers with N-bromosuccinimide-dimethyl sulfoxide combination: A facile synthesis of α-amino-ketones and esters
-
An unprecedented conversion of alkenes and enol ethers to the corresponding α-imido carbonyl compounds with excellent regioselectivity and yields has been developed. This oxo-amination process employs readily available N-bromosuccinimide (NBS) and secondary amines as N-sources and dimethyl sulfoxide (DMSO) as the oxidant and also leads to the production of amino alcohols in a single step on reduction, thus broadening the scope of this operationally simple reaction. For the first time, the formation of reactive Me2S+-O-Br species generated by the interaction of NBS with DMSO has been proven.
- Prasad, Pragati K.,Reddi, Rambabu N.,Sudalai, Arumugam
-
supporting information
p. 500 - 503
(2016/02/18)
-
- I2-promoted aerobic oxidative coupling of acetophenes with amines under metal-free conditions: Facile access to α-ketoamides
-
A novel and efficient I2-promoted oxidative coupling of acetophenes with amines to α-ketoamides is presented, which employs O2 as an environmentally friendly oxidant under metal-free conditions. Based on a series of control experimen
- Guo, Shiyu,Fang, Zheng,Yang, Zhao,Liu, Chengkou,Dai, Zhongxue,Zhao, Lihuan,Guo, Kai
-
p. 1503 - 1507
(2016/01/16)
-
- Cu(i)-Functionalized SBA-16: An efficient catalyst for the synthesis of α-ketoamides under moderate conditions
-
An efficient catalyst based on the cage-like mesoporous material SBA-16 as the support and Cu(i) as active sites has been successfully prepared. The catalyst demonstrated high catalytic activity (up to 88%) in the direct oxidative synthesis of α-ketoamides between acetophenone and piperidine, employing O2 from open air as the oxidant without other additives. A heterogeneous catalyst was applied in this reaction for the first time, and the catalyst could be easily separated from the reaction system by filtration and reused several times without a significant loss of activity.
- Zhang, Xueyao,Yang, Honglei,Huo, Yong,Li, Jing,Ma, Jianxin,Ma, Jiantai
-
p. 8972 - 8983
(2016/06/09)
-
- One pot synthesis of α-ketoamides from ethylarenes and amines: a metal free difunctionalization strategy
-
One-pot and metal free synthesis of α-ketoamides has been described through in situ generation of aryl ketones from easily available ethylarenes followed by amidation with various amines. This multiple oxidation protocol involves catalytic I2-pyridine-TBHP (t-butyl hydroperoxide) mediated oxidative benzylic carbonylation and sequential NaI-TBHP mediated oxidative amidation without using any solvent.
- Ramanathan, Mani,Kuo, Chun-Kai,Liu, Shiuh-Tzung
-
p. 11446 - 11453
(2016/12/16)
-
- Phosphine-free atmospheric carbonylation of aryl iodides with aniline derivatives in the presence of a reusable silica-supported palladium catalyst
-
Various palladium catalysts were obtained by the immobilisation of palladium on silica, modified with imidazolium salts. The efficiency of the catalysts was greatly dependent on the choice of the anion of the imidazolium salt, the palladium precursor and on the conditions of heterogenisation. Palladium acetate immobilised on silica with grafted imidazolium chloride moieties was shown to be a selective and recyclable catalyst for atmospheric aminocarbonylation of aryl iodides with aromatic amines in DMF. It was proved that the greater loss of palladium in DMSO can be explained by the formation of soluble palladium complexes.
- Urbán, Béla,Papp, Máté,Srankó, Dávid,Skoda-F?ldes, Rita
-
p. 150 - 157
(2015/02/19)
-
- TBAI-catalyzed synthesis of α-ketoamides via sp3 C-H radical/radical cross-coupling and domino aerobic oxidation
-
A TBAI-catalyzed one-pot synthesis of α-ketoamides via sp3 C-H radical/radical cross-coupling and domino aerobic oxidation was developed. This synthesis is suitable for abroad range of substrates. The control experiments suggested a possible oxidative coupling mechanism.
- Fan, Weizheng,Shi, Dongyang,Feng, Bainian
-
p. 4638 - 4641
(2015/07/02)
-
- Synthesis of α -Ketoamides by Copper-Catalyzed Reactions of Phenylacetic Acids with N,N -Dialkylformamides
-
A new synthetic approach for α-ketoamides was achieved by copper-catalyzed coupling reactions between N,N-dialkylformamides and phenylacetic acids. A variety of substrates were well tolerated to give yields of 46-87% (17 examples). A 13C-labeli
- Zhang, Lanping,Pu, Junnan,Ren, Jiayu,Li, Zhengkai,Xiang, Haifeng,Zhou, Xiangge
-
p. 1848 - 1856
(2015/08/03)
-
- Iodine-promoted oxidative amidation of terminal alkenes - Synthesis of α-ketoamides, benzothiazoles, and quinazolines
-
A novel metal-free strategy for oxidative amidation of terminal alkenes by using I2/DMSO for the synthesis of α- ketoamides has been developed. Intriguingly, the use of tertbutylhydroperoxide (TBHP) as co-oxidant can facilitate the synthesis of α-ketoamides at room temperature without any solvent, thereby making it a green protocol. The reaction with primary amines can be easily achieved by using SeO2 as an oxidizing agent. Besides, the scope of the method was also extended to the synthesis of benzothiazolines and quinazolines.
- Deshidi, Ramesh,Devari, Shekaraiah,Shah, Bhahwal Ali
-
supporting information
p. 1428 - 1432
(2015/03/04)
-
- Stability or flexibility: Metal nanoparticles supported over cross-linked functional polymers as catalytic active sites for hydrogenation and carbonylation
-
A novel cross-linked functional polymer was prepared through copolymerization between 1, 3, 4, 6-tetraallylglycoluril and 4-vinyl pyridine. Pt and Pd nanoparticles supported over this polymeric framework (Pt/CFP and Pd/CFP) were detailedly characterized by TEM, EDS, and XPS. Pt nanoparticles were kept in the monodispersed state with the average size of 1.4 nm. Monodispersed Pd nanoparticles were about 4.5 nm. The hydrogenation of nitrobenzenes over Pt/CFP shows high activity and selectivity with the substrate to Pt ratio of 4000 under mild reactions. Pd/CFP was the catalyst for carbonylation of aryl iodides in the presence of secondary amines and acylhydrazines. Double carbonylation with secondary amines produced α-ketoamides with the selectivity of 80%. Diacylhydrazine molecules were synthesized by the direct carbonylation of aryl iodide with acylhydrazine over Pd/CFP. The recyclability and recoverability of Pt/CFP were investigated through a seven-run recycling test of nitrobenzene hydrogenation. The flexibility of Pd/CFP in the carbonylation process was thoroughly explored by a 12-run recycling test. Supported Pt or Pd nanoparticles showed the macroscopic robustness in their catalytic performance in the catalytic cycle. The flexibility of metal nanoparticles and the polymeric supports guaranteed macroscopic catalytic robustness.
- Chen, Bingfeng,Li, Fengbo,Huang, Zhijun,Lu, Tao,Yuan, Guoqing
-
-
- NHC-Pd complex-catalyzed double carbonylation of aryl iodides with secondary amines to α-keto amides
-
A series of palladium-NHC compounds were prepared and their catalytic activity in the double carbonylation of aryl iodides to synthesize α-keto amides were examined. Palladium complexes bearing mixed NHC-phosphine exhibited high efficiency for the double carbonylation reaction. The effects of different solvents, base, temperature, carbon monoxide (CO), pressure, various amine and aryl iodides were investigated. Both electron-rich and electron-deficient aryl iodides afforded the corresponding substituted α-keto amides in moderate to good yields. A possible mechanism was also proposed. Copyright
- Zheng, Shuzhan,Wang, Yan,Zhang, Chunyan,Liu, Jianhua,Xia, Chungu
-
-
- Palladium-1,10-phenanthroline complex encaged in y zeolite: An efficient and highly recyclable heterogeneous catalyst for aminocarbonylation
-
A promising route for catalytic synthesis of amides by aminocarbonylation of aryl iodides with amines is described using a palladium-1,10-phenanthroline complex encaged in Y zeolite. Complete conversions for aryl iodides and good to excellent yields (71-97%) of various amides were obtained at low Pd loadings of 0.6 mol%. The turnover frequency (TOF) could be up to 139 h-1. A satisfactory yield was obtained even after the catalyst was reused 16 times and the total turnover number (TON) for the 16 cycles was up to 2250. As evidenced by atomic absorption spectrophotometry, UV-vis spectroscopy and X-ray photoelectron spectroscopy, the palladium complex could well nestle down in the supercages of the zeolite without leaching during the recycling process. The significantly enhanced recyclability could be attributed to the double-protection strategy provided by the ligand and the zeolite structure for Pd0 species generated in situ within supercages preventing the migration and leaching of palladium. The supported catalyst has the advantages of easy handing, good to excellent yields, and outstanding recycling capacity for aminocarbonylation reactions of aryl iodides.
- Mei, Hui,Hu, Jianglin,Xiao, Se,Lei, Yizhu,Li, Guangxing
-
-
- A general metal free approach to α-ketoamides via oxidative amidation-diketonization of terminal alkynes
-
A novel catalytic system TMSOTf/I2/DMSO for the oxidative coupling of terminal alkynes with virtually any primary/secondary amine leading to α-ketoamides has been developed. The reaction possibly proceeds via iminium ion formation, wherein DMSO acts as a solvent as well as an oxidizing agent. This journal is the Partner Organisations 2014.
- Deshidi, Ramesh,Kumar, Manjeet,Devari, Shekaraiah,Shah, Bhahwal Ali
-
supporting information
p. 9533 - 9535
(2014/08/18)
-
- The syntheses of α-ketoamides vianBu4NI- catalyzed multiple sp3C-H bond oxidation of ethylarenes and sequential coupling with dialkylformamides
-
The nBu4NI-catalyzed sequential C-O and C-N bond formation via multiple sp3C-H bond activation of ethylarenes, using N,N-dialkylformamide as the amino source, provided α-ketoamides with moderate yields. This journal is
- Du, Bingnan,Jin, Bo,Sun, Peipei
-
supporting information
p. 4586 - 4589
(2014/06/24)
-
- Metal-free oxidative amidation of 2-oxoaldehydes: A facile access to α-ketoamides
-
A novel and efficient method for the synthesis of α-ketoamides, employing a dimethyl sulfoxide (DMSO)-promoted oxidative amidation reaction between 2-oxoaldehydes and amines under metal-free conditions is presented. Furthermore, mechanistic studies supported an iminium ion-based intermediate as a central feature of reaction wherein C1-oxygen atom of α-ketoamides is finally derived from DMSO.
- Mupparapu, Nagaraju,Khan, Shahnawaz,Battula, Satyanarayana,Kushwaha, Manoj,Gupta, Ajai Prakash,Ahmed, Qazi Naveed,Vishwakarma, Ram A.
-
p. 1152 - 1155
(2014/03/21)
-
- Synthesis of thioamides via one-pot A3-coupling of alkynyl bromides, amines, and sodium sulfide
-
We herein describe a novel method for the synthesis of thioamides by a three component condensation of alkynyl bromides, amines, and Na 2S·9H2O. The developed method is applicable for a wide range of amines and alkynyl bromides bearing different functional groups furnishing the corresponding products in moderate to excellent yields. The Royal Society of Chemistry.
- Sun, Yadong,Jiang, Huanfeng,Wu, Wanqing,Zeng, Wei,Li, Jianxiao
-
p. 700 - 707
(2014/01/06)
-
- Mesoporous poly-melamine-formaldehyde stabilized palladium nanoparticle (Pd@mPMF) catalyzed mono and double carbonylation of aryl halides with amines
-
A new mesoporous poly-melamine-formaldehyde material supported Pd nano catalyst (mPMF-Pd0) has been synthesized and characterized by thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflection spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and a N2 adsorption study. The mPMF-Pd0 material showed very good catalytic activity in the field of mono and double amino carbonylation of aryl bromides/iodides. Moreover, the catalyst is easily recoverable and can be reused six times without appreciable loss of catalytic activity in the above reactions. So, the highly dispersed and strongly bound palladium(0) sites in the mPMF-Pd0 could be responsible for the observed high activities. Due to strong binding with the functional groups of the polymer, no evidence of leached Pd from the catalyst during the course of reaction occurred, suggesting true heterogeneity in the catalytic process. This journal is
- Molla, Rostam Ali,Iqubal, Md. Asif,Ghosh, Kajari,Roy, Anupam Singha,Kamaluddin,Islam, Sk. Manirul
-
p. 48177 - 48190
(2014/12/10)
-
- Aryl-palladium-NHC complex: Efficient phosphine-free catalyst precursors for the carbonylation of aryl iodides with amines or alkynes
-
A series of aryl-palladium-NHC compounds was prepared according to the reported methods and their catalytic activity in the carbonylation of aryl iodides to synthesize α-keto amides and alkynones was examined. These practical aryl-palladium-NHC complexes have shown highly efficient catalyzed carbonylation and Sonogashira carbonylation reactions, with high turnover number in synthesis of α-keto amides (TON = 4300) and in synthesis of alkynones (TON = 980).
- Zhang, Chunyan,Liu, Jianhua,Xia, Chungu
-
supporting information
p. 9702 - 9706
(2015/02/19)
-