- COBALT-MEDIATED REACTIONS. A NEW SYNTHETIC APPROACH TO β-, χ- and δ-LACTAMS
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Unsaturated carbamylcobalt salophens, e.g. (2), undergo homolytic cleavage (heating, sunlamp) producing carbamyl radicals , viz (4) which then undergo cyclisation, accompanied by trapping (with CoII or TEMPO) or dehydrocobaltation, leading to functionalised β-, χ-, and δ-lactams e.g. (3), (6), (8), (11), (13) and (16).
- Gill, G. Bryon,Pattenden, Gerald,Reynolds, Stephen J.
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- One-pot synthesis of a highly disperse core-shell CuO-alginate nanocomposite and the investigation of its antibacterial and catalytic properties
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In this study, sodium alginate was extracted from Sargassum algae, collected from coastal waters of Bushehr, Persian Gulf, Iran and used as a stabilizing and wrapping agent for CuO nanoparticles. The synthesized nanocomposite was characterized by some spectroscopic and microscopic techniques, such as IR, XRD, Uv-vis, BET, BJH, zeta potential, SEM, TEM, HR-TEM, and XPS. The antibacterial effects of the CuO-alginate nanocomposite against some bacteria, isolated from a burn wound, were evaluated. The results showed that this nanocomposite had better antibacterial effects than its components onPseudomonas aeruginosaATCC 27853,Staphylococcus aureusATCC 12600,Streptococcus pyogenesATCC 19615, andStaphylococcus epidermidisATCC 49461. Among these,Staphylococcus aureusATCC 12600 was the most sensitive one to this nanocomposite, with the lowest minimum inhibitory concentration (2.08 mg mL?1) observed. Moreover, the synthesized nanocomposite showed good catalytic activity in the oxidative coupling of carboxylic acids withN,N-dialkylformamides toward the synthesis of amides.
- Habibi, Hassan,Mansourinejhad, Sanam,Saberi, Dariush,Shadi, Ahmad
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p. 199 - 211
(2021/12/30)
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- PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
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A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
- Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
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p. 491 - 497
(2021/01/20)
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- Chemoselective reduction of ?,¢-unsaturated carbonyl and carboxylic compounds by hydrogen iodide
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The selective reduction of ?,¢-unsaturated carbonyl compounds was achieved to produce saturated carbonyl compounds with aqueous HI solution. The introduction of an aryl group at an ? or ¢ position efficiently facilitated the reduction with good yield. The reaction was applicable to compounds bearing carboxylic acids and halogen atoms. Through the investigation of the reaction mechanism, it was found that Michael-type addition of iodide occurred to produce ¢-iodo compounds followed by the reduction of C-I bond via anionic and radical paths.
- Matsumoto, Shoji,Marumoto, Hayato,Akazome, Motohiro,Otani, Yasuhiko,Kaiho, Tatsuo
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p. 590 - 599
(2021/03/29)
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- LIPOXYGENASE INHIBITORS
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Various embodiments of the present disclosure are directed to compounds having Formula (I), Formula (IA), Formula (IB), Formula (IC), Formula (ID), Formula (IE), and/or pharmaceutically acceptable salts thereof. The compounds can be suitable for inhibiting lipoxygenases, and/or treating associated diseases, such as Alzheimer's disease. In some embodiments, the compounds may be administered to a patient as part of a pharmaceutical formulation.
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Paragraph 00601-00603
(2021/10/02)
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- Manganese Catalyzed Enantioselective Epoxidation of α,β-Unsaturated Amides with H2O2
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Herewith, we report the enantioselective epoxidation of electron-deficient cis- and trans-α,β-unsaturated amides with the environmentally benign oxidant H2O2. The catalysts - manganese complexes with bis-amino-bis-pyridine and structurally related ligands - exhibit reasonably high efficiency (up to 100 TON) and excellent chemo- and enantioselectivity (up to 100% and 99% ee, respectively). Crucially, the cis-enamides epoxidation enantioselectivity and yield are dramatically enhanced by the presence of NH-moiety, which effect can be explained by the hydrogen bonding interaction between the cis-enamide substrate and the manganese based oxygen transferring species. (Figure presented.).
- Ottenbacher, Roman V.,Kurganskiy, Vladimir I.,Talsi, Evgenii P.,Bryliakov, Konstantin P.
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supporting information
p. 2778 - 2782
(2021/04/29)
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- Palladium-Catalyzed Decarbonylative Heck Coupling of Aromatic Carboxylic Acids with Terminal Alkenes
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A palladium-catalyzed decarbonylative alkenylation of aromatic carboxylic acids was developed. Under the reaction conditions, various benzoic acids including those bearing functional groups coupled to terminal alkenes, producing the corresponding internal alkenes in good to high yields. Cinnamic acids and bioactive benzoic acids such as 3-methylflavone-8-carboxylic acid, probenecid, adapalin, and febuxostat were also applicable to this reaction, demonstrating the potential synthetic value of this new reaction in organic synthesis.
- Chen, Tieqiao,Huang, Tianzeng,Liu, Long,Yu, Wenqing,Zhou, Xiangbing
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supporting information
p. 7123 - 7128
(2020/10/05)
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- Synthesis of Cinnamides via Amidation Reaction of Cinnamic Acids with Tetraalkylthiuram Disulfides Under Simple Condition
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A facile and efficient methodology for the synthesis of cinnamides has been achieved under metal- and additive-free conditions. This method allows the efficient C–N cross-coupling of diverse cinnamic acids with tetraalkylthiuram disulfides through a simply mixing operation in 1,2-dichloroethane at 100 °C. The protocol provides a direct approach to cinnamides and is featured with readily available starting materials and broad substrate scope, which shows its practical synthetic value in organic synthesis.
- Lai, Miao,Wu, Zhiyong,Su, Fangyao,Yu, Yujian,Jing, Yanqiu,Kong, Jinmin,Wang, Zhenteng,Wang, Shuai,Zhao, Mingqin
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p. 198 - 208
(2020/01/22)
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- Palladium-Catalyzed N-Acylation of Tertiary Amines by Carboxylic Acids: A Method for the Synthesis of Amides
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A palladium-catalyzed N-acylation of tertiary amines by carboxylic acids was achieved through C-N cleavage. This reaction showed a wide substrate scope. Both aromatic and aliphatic acids served well as the acylating reagents and coupled with tertiary amines to produce the corresponding amides in good to excellent yields. With the strategy, bioactive carboxylic acids were also efficiently modified, highlighting the synthetic value of the process in organic synthesis.
- Li, Zhaohui,Liu, Long,Xu, Kaiqiang,Huang, Tianzeng,Li, Xinyi,Song, Bin,Chen, Tieqiao
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supporting information
p. 5517 - 5521
(2020/07/14)
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- Radical condensation between benzylic alcohols and acetamides to form 3-arylpropanamides
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A new radical condensation reaction is developed where benzylic alcohols and acetamides are coupled to generate 3-arylpropanamides with water as the only byproduct. The transformation is performed with potassium tert-butoxide as the only additive and gives rise to a variety of 3-arylpropanamides in good yields. The mechanism has been investigated experimentally with labelled substrates, trapping experiments and spectroscopic measurements. The findings indicate a radical pathway where potassium tert-butoxide is believed to serve a dual role as both base and radical initiator. The radical anion of the benzylic alcohol is proposed as the key intermediate, which undergoes coupling with the enolate of the amide to form the new C-C bond. Subsequent elimination to the corresponding cinnamamide and olefin reduction then affords the 3-arylpropanamides.
- Azizi, Kobra,Madsen, Robert
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p. 7800 - 7806
(2020/08/14)
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- Preparation method of cinnamamide (by machine translation)
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The synthesis system disclosed by the invention has the advantages of simple :(1) reaction conditions, wide, reaction conditions, reaction conditions, wide ;(2) substrate range, high yield (1) and wide application range, and the reaction liquid, can be used as an anti-cancer drug, anti-anti-tumor and spice precursor compound in an organic solvent to prepare a corresponding cinnamide compound, product cinnamide . The synthesis system disclosed by the invention has a broad spectrum . The synthesis system disclosed by the invention has a broad spectrum of biological activity, and is suitable for popularization and application, in the following steps, synthesizing cinnamic acid and thiuram disulfide as a raw material, in an organic, solvent, and purifying, parts by mass, separation and purification of the obtained reaction, solution in an organic solvent. (by machine translation)
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Paragraph 0022-0028
(2020/05/01)
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- Copper(I)-Catalyzed Asymmetric 1,4-Conjugate Hydrophosphination of α,β-Unsaturated Amides
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A catalytic asymmetric conjugate hydrophosphination of α,β-unsaturated amides is accomplished by virtue of the strong nucleophilicity of copper(I)-PPh2 species, which provides an array of chiral phosphines bearing an amide moiety in high to excellent yields with excellent enantioselectivity. Furthermore, the dynamic kinetic resolution of unsymmetrical diarylphosphines (HPAr1Ar2) is successfully carried out through the copper(I)-catalyzed conjugate addition to α,β-unsaturated amides, which affords P-chiral phosphines with good-to-high diastereoselectivity and high enantioselectivity. 1H NMR studies show that the precoordination of HPPh2 to copper(I)-bisphosphine complex is critical for the efficient deprotonation by Barton's Base. Moreover, the relative stability of the copper(I)-(R,RP)-TANIAPHOS complex in the presence of excessive HPPh2, confirmed by 31P NMR studies, is pivotal for the high asymmetric induction, as the ligand exchange between bisphosphine and HPPh2 would significantly reduce the enantioselectivity. At last, a double catalytic asymmetric conjugate hydrophosphination furnishes the corresponding product in high yield with high diastereoselectivity and excellent enantioselectivity, which is transformed to a chiral pincer palladium complex in moderate yield. This chiral palladium complex is demonstrated as an excellent catalyst in the asymmetric conjugate hydrophosphination of chalcone.
- Li, Yan-Bo,Tian, Hu,Yin, Liang
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supporting information
p. 20098 - 20106
(2021/01/01)
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- Donor-acceptor fluorophores as efficient energy transfer photocatalysts for [2 + 2] photodimerization
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Mild [2 + 2] photodimerization of enone substrates was induced by donor-acceptor fluorophores. Enone substrates were activated efficiently for anti-head to head dimerizations with a high yield (up to 83%) and high selectivity. The adjustable excited state potential also allows donor-acceptor fluorophores to be used for isomerization of the above substrates, confirming the potential of donor-acceptor fluorophores as energy transfer photocatalysts.
- Chen, Feng,Chen, Hao,Liu, Xue-Fen,Luo, Shu-Ping,Ren, Chen-Chao,Wu, Qing-An,Xu, Liang-Xuan,Yu, Xiao-Cong
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p. 3707 - 3716
(2020/06/03)
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- Visible-Light-Enabled Oxidative Coupling of Alkenes with Dialkylformamides to Access Unsaturated Amides
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A practical and direct method for oxidative cross-coupling of alkenes with dialkylformamides is established employing visible-light-enabled photoredox catalysis. This strategy allows efficient access to diverse unsaturated amides under mild reaction conditions. The application of an appropriate diaryliodonium salt was demonstrated to be critical to the success of this process. This catalyst system is well tolerant of a variety of useful functional groups.
- Lu, Maojian,Lin, Zhaowei,Chen, Shanyi,Chen, Hongyou,Huang, Mingqiang,Cai, Shunyou
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supporting information
p. 9929 - 9933
(2019/12/24)
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- Bidentate Ru(II)-NC Complexes as Catalysts for α-Alkylation of Unactivated Amides and Esters
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Five Ru(II)-NC complexes were tested as catalysts for α-alkylation of unactivated amides using alcohols as alkylating agents, and complex {(C5H4N)-(C6H4)}RuCl(CO)(PPh3)2 (1) showed the highest activity. With 0.5 mol% catalyst loading, a series of α-alkylated amides were isolated at 80 °C within 6 hours. Furthermore, under similar conditions, complex 1 was also active for α-alkylation of unactivated esters with alcohols, and the reaction time was shortened to 1.5 hours. The catalytic performance of 1 is comparable to the best reported catalyst.
- Gong, Dawei,Hu, Bowen,Yang, Weiwei,Chen, Dafa
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p. 4841 - 4847
(2019/11/05)
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- Radical α,β-Dehydrogenation of Saturated Amides via α-Oxidation with TEMPO under Transition Metal-Free Conditions
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A transition metal-free radical process for the selective α,β-dehydrogenation of saturated amides under mild conditions is developed. Utilizing radical activation strategy, the challenging issue associated with the low α-acidity of amides is resolved. For the first time, α,β-unsaturated Weinreb amides and acrylamides could be efficiently prepared directly from corresponding saturated amides. Mechanistic studies confirm the radical nature of this transformation. Two gram scale α,β-dehydrogenation have also been performed to demonstrate the utility of this method.
- Wang, Mei-Mei,Sui, Guo-Hui,Cui, Xian-Chao,Wang, Hui,Qu, Jian-Ping,Kang, Yan-Biao
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p. 8267 - 8274
(2019/06/27)
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- Chemoselective α,β-Dehydrogenation of Saturated Amides
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We report a method for the selective α,β-dehydrogenation of amides in the presence of other carbonyl moieties under mild conditions. Our strategy relies on electrophilic activation coupled to in situ selective selenium-mediated dehydrogenation. The α,β-unsaturated products were obtained in moderate to excellent yields, and their synthetic versatility was demonstrated by a range of transformations. Mechanistic experiments suggest formation of an electrophilic SeIV species.
- Teskey, Christopher J.,Adler, Pauline,Gon?alves, Carlos R.,Maulide, Nuno
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p. 447 - 451
(2019/01/04)
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- POCl3 promoted metal-free synthesis of tertiary amides by coupling of carboxylic acids and N,N-disubstituted formamides
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Herein we report a robust and synthetically useful catalyst-free amination methodology by the coupling of carboxylic acids and N-substituted formamides using POCl3 as a promoter. Versatile amides with a wide array of substituent groups were prepared within only 1 h in good to excellent yields. And even multi-substituted aromatic carboxylic acids could give the desired products with satisfactory results.
- Bi, Xiaojing,Li, Junchen,Shi, Enxue,Li, Yu,Liu, Ying,Wang, Hongmei,Xiao, Junhua
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supporting information
p. 236 - 240
(2019/04/25)
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- Visible-light-promoted oxidation/condensation of benzyl alcohols with dialkylacetamides to cinnamides
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Oxidative cross-coupling reactions of benzyl alcohols with N,N-dialkylacetamides were developed only employing oxygen as the terminal oxidant, efficiently providing a new, novel protocol for the construction of multifunctionalized cinnamides with the synergistic effects of KOH, organic photocatalyst eosin Y, and visible light irradiation at room temperature. A broad substrate scope and mild reaction conditions are the prominent features of this transformation.
- Yang, Tianlong,Lu, Maojian,Lin, Zhaowei,Huang, Mingqiang,Cai, Shunyou
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supporting information
p. 449 - 453
(2019/01/24)
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- Amidation reaction of carboxylic acid with formamide derivative using SO3?pyridine
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The amidation reaction of carboxylic acid derivatives was developed using sulfur trioxide pyridine complex (SO3?py) as a commercially available and easily handled oxidant. This method could be applied to the reaction of various aromatic and aliphatic carboxylic acids, including optically active ones, with formamide derivatives to afford the corresponding amides in good to high yields.
- Kawano, Shota,Saito, Kodai,Yamada, Tohru
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supporting information
p. 584 - 586
(2018/04/12)
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- A Palladium NNC-Pincer Complex as an Efficient Catalyst Precursor for the Mizoroki?Heck Reaction
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The Mizoroki?Heck reaction of aryl halides (iodides, bromides, or chlorides) with activated alkenes in the presence of a palladium NNC-pincer complex at ppb to ppm loadings gave the corresponding internal alkenes in excellent yields. The total turnover number and turnover frequency reached up to 8.70×108 and 1.21×107 h?1 (3.36×103 s?1), respectively. The catalyst was applied in a ten-gram-scale synthesis of the UV-B sunscreen agent octinoxate (2-ethylhexyl 4-methoxycinnamate). Reaction-rate analyses, transmission electron microscopic examination of the reaction mixture, and poisoning tests suggested that a monomeric palladium species is the catalytically active species in the catalytic cycle. (Figure presented.).
- Hamasaka, Go,Ichii, Shun,Uozumi, Yasuhiro
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supporting information
p. 1833 - 1840
(2018/04/05)
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- Cu(II)-Mediated keto C(sp3)-H bond α-acyloxylation of N, N-dialkylamides with aromatic carboxylic acids
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The selective oxidative coupling of aromatic carboxylic acids with the C(sp3)-H bond adjacent to the keto group of alkylamides has been developed by employing a low cost copper source. This provides an efficient approach for synthesis of O-benzoylglycolamides. The protocol displayed good functional group tolerance. A broad range of benzoic acids directly coupled with alkylamides to afford a variety of O-benzoylglycolamides in moderate to good yields. In addition, a reasonable radical mechanism was proposed based on EPR experiments.
- Li, Wenjing,Yin, Changzhen,Yang, Xiao,Liu, Hailong,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Fu, Haiyan,Chen, Hua
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supporting information
p. 7594 - 7599
(2017/09/27)
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- Oxidative coupling of Michael acceptors with aryl nucleophiles produced through rhodium-catalyzed C-C bond activation
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Utilizing rhodium catalysis, aryl nucleophiles generated via carbon-carbon single bond activation successfully undergo oxidative coupling with Michael acceptors. The reaction scope encompasses a broad range of nucleophiles generated from quinolinyl ketones as well as a series of electron deficient terminal alkenes, illustrating the broad potential of intersecting carbon-carbon bond activation with synthetically useful coupling methodologies. The demonstrated oxidative coupling produces a range of cinnamyl derivatives, several of which are challenging to prepare via conventional routes.
- Gregerson, Caroline E.,Trentadue, Kathryn N.,Phipps, Erik J. T.,Kirsch, Janelle K.,Reed, Katherine M.,Dyke, Gabriella D.,Jansen, Jacob H.,Otteman, Christian B.,Stachowski, Jessica L.,Johnson, Jeffrey B.
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p. 5944 - 5948
(2017/07/25)
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- S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes
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Pd(II)-catalyzed C-H functionalization of nondirected arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is operationally simple, scalable, and can be used in late-stage functionalization of complex molecules. The broad applicability of this catalyst has been showcased in other transformations such as Pd(II)-catalyzed C-H acetoxylation and allylation reactions.
- Naksomboon, Kananat,Valderas, Carolina,Gómez-Martínez, Melania,álvarez-Casao, Yolanda,Fernández-Ibá?ez, M. ángeles
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p. 6342 - 6346
(2017/09/15)
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- Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides
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A palladium-catalyzed fluorosulfonylvinylation reaction of organic iodides is described. Catalytic Pd(OAc)2 with a stoichiometric amount of silver(I) trifluoroacetate enables the coupling process between either an (hetero)aryl or alkenyl iodide with ethenesulfonyl fluoride (ESF). The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds, in up to 99 % yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides and 1,3-dienylsulfonyl fluorides.
- Zha, Gao-Feng,Zheng, Qinheng,Leng, Jing,Wu, Peng,Qin, Hua-Li,Sharpless, K. Barry
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supporting information
p. 4849 - 4852
(2017/04/11)
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- Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation
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A new iridium-catalyzed reductive Strecker reaction for the direct and efficient formation of α-amino nitrile products from a broad range of (hetero)aromatic and aliphatic tertiary amides, and N-alkyl lactams is reported. The protocol exploits the mild and highly chemoselective reduction of the amide and lactam functionalities using IrCl(CO)[P(C6H5)3]2 (Vaska's complex) in the presence of tetramethyldisiloxane, as a reductant, to directly generate hemiaminal species able to undergo substitution by cyanide upon treatment with TMSCN (TMS=trimethylsilyl). The protocol is simple to perform, broad in scope, efficient (up to 99 % yield), and has been successfully applied to the late-stage functionalization of amide- and lactam-containing drugs, and naturally occurring alkaloids, as well as for the selective cyanation of the carbonyl carbon atom linked to the N atom of proline residues within di- and tripeptides.
- Fuentes de Arriba, ángel L.,Lenci, Elena,Sonawane, Mahendra,Formery, Odilon,Dixon, Darren J.
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supporting information
p. 3655 - 3659
(2017/03/21)
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- Pd(PPh3)4 catalyzed amide compound synthesis method
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The invention relates to a Pd(PPh3)4 catalyzed amide compound synthesis method. The synthesis method takes carboxylic acid as the substrate, and adopts N-substituted formamide as the amine source to synthesize an amide compound under the catalysis of Pd(PPh3)4. The method is widely applicable to substrates with different functional groups. The amide compound efficiently constructed by the invention is an important skeleton of many organic molecules, drugs, peptides, bioactive molecules and natural products. The synthesis method provided by the invention provides a widely applicable preparation method for synthesis of the compounds.
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Paragraph 0081; 0082; 0083; 0084; 0085
(2017/12/27)
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- FeCl3 catalyzed amide compound synthesis method
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The invention relates to an FeCl3 catalyzed amide compound synthesis method. According to the synthesis method, carboxylic acid and N-substituted formamide are employed to synthesize an amide compound under the catalysis of FeCl3. The synthesis method provided by the invention has the characteristics of mild conditions, high reaction efficiency, and wide applicability to substrates of different functional groups. The amide compound efficiently constructed by the invention is an important skeleton of many organic molecules, drugs, proteins and bioactive molecules. The synthesis method provided by the invention provides a widely applicable preparation method for synthesis of the compounds.
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Paragraph 0070; 0071; 0072; 0073; 0074
(2018/03/28)
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- Lewis Acid Enabled Copper-Catalyzed Asymmetric Synthesis of Chiral β-Substituted Amides
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Here we report that readily available silyl- and boron-based Lewis acids in combination with chiral copper catalysts are able to overcome the reactivity issues of unactivated enamides, known as the least reactive carboxylic acid derivatives, toward alkyla
- Rodríguez-Fernández, Mamen,Yan, Xingchen,Collados, Juan F.,White, Paul B.,Harutyunyan, Syuzanna R.
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p. 14224 - 14231
(2017/10/17)
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- Borane-Catalyzed Reductive α-Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact
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Described herein is the development of the B(C6F5)3-catalyzed hydrosilylation of α,β-unsaturated esters and amides to afford synthetically valuable α-silyl carbonyl products. The α-silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α-silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4-hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate.
- Kim, Youngchan,Chang, Sukbok
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supporting information
p. 218 - 222
(2016/01/25)
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- Ru-catalyzed direct amidation of carboxylic acids with N-substituted formamides
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The direct amidation of carboxylic acids with N-substituted formamides has been accomplished via ruthenium catalysis. In the presence of ruthenium catalyst, a versatile range of carboxylic acids and N-substituted formamides undergoes amidation reaction to produce synthetically useful amides in good yields. C[dbnd]O in amide product came from benzoic acid but not N-substituted formamides, and which was confirmed by Isotope experiment.
- Bi, Xiaojing,Li, Junchen,Shi, Enxue,Wang, Hongmei,Gao, Runli,Xiao, Junhua
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p. 8210 - 8214
(2016/11/23)
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- Palladium(II) Complexes of the Hemilabile Pincer Ligand PPh(o-C6H4SMe)2as Highly Active and Recyclable -Mizoroki–Heck Catalysts
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PdIIcomplexes with PPh(o-C6H4SMe)2acting as a pincer ligand in an S,S′,P- or S,P-coordination mode have been synthesized. The complexes include [PdCl2{PPh(o-C6H4SMe)2}] (1), [Pd(Me)Cl{PPh(o-C6H4SMe)2}] (2), and [Pd(X){PPh(o-C6H4SMe)2}]A [A = CF3SO3, X = Cl (3); A = CF3SO3, Me (4); A = PF6, X = Me (5)]. Insertion of CO into the Pd–Me bond of these complexes leads to [Pd(COMe)Cl{PPh(o-C6H4SMe)2}] (6) and [Pd(COMe){PPh(o-C6H4SMe)2}]A [A = CF3SO3(7); A = PF6(8)]. Some of these complexes are good Mizoroki–Heck catalysts (for the reactions between iodobenzene and methyl acrylate or styrene). The most active catalyst was found to be [Pd(Me)Cl{PPh(o-C6H4SMe)2}] (2). This catalyst could be retained on a silica gel column, recovered, and reused several times without losing activity.
- Luquin, Asunción,Castillo, Noelia,Cerrada, Elena,Merchan, Francisco L.,Garrido, Julian,Laguna, Mariano
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supporting information
p. 789 - 798
(2017/01/18)
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- Method for synthesizing phosphorus-oxychloride-promoted amide compound
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The invention relates to a method for synthesizing a phosphorus-oxychloride-promoted amide compound. The synthesizing method includes the steps that carboxylic acid serves as one reactant, another reactant (N,N-dialkyl methanamide) serves as a solvent, one equivalent of phosphorus oxychloride is added, and the amide compound is prepared. The reaction substrates are low in price and easy to get, the nature is stable, toxicity is small, the reaction speed is high, conditions are moderate, and the reaction substrates can be widely applied to substrates with different functional groups. The efficiently-constructed amide compound is an important molecular skeleton for many medicines, bioactive molecules and natural products, and the synthesizing method is a widely-applicable preparing method for synthesizing the compound.
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Paragraph 0105; 0106; 0107; 0108; 0109
(2017/01/26)
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- Mild Amide-Cleavage Reaction Mediated by Electrophilic Benzylation
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An extremely mild method for amide-cleavage by using the triazine-based benzylating reagent 4-(4,6-diphenoxy-1,3,5-triazin-2-yl)-4-benzylmorpholinium trifluoromethanesulfonate (DPT-BM), which spontaneously releases benzyl cation species when being dissolved at room temperature, has been developed. O-Benzylation of the amide with DPT-BM and the subsequent hydrolysis of the resulting intermediate benzyl imidate salt afford the corresponding amine and benzyl ester, which can be converted by hydrogenolysis into a carboxylic acid under neutral conditions. O-Benzylation proceeds depending on both steric and electronic factors around the amide group. Thus, some amides have been selectively cleaved over other amides. Furthermore, intramolecular chemoselective cleavage of an amide group in the presence of an ester group was achieved. Such selective hydrolytic reactions cannot be performed with Meerwein reagents as well as under acidic or basic hydrolytic conditions.
- Yamada, Kohei,Karuo, Yukiko,Tsukada, Yuichi,Kunishima, Munetaka
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supporting information
p. 14042 - 14047
(2016/09/21)
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- General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols
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The borrowing hydrogen or hydrogen autotransfer methodology is an elegant and sustainable or green concept to construct carbon-carbon bonds. In this concept, alcohols, which can be obtained from barely used and indigestible biomass, such as lignocellulose, are employed as alkylating reagents. An especially challenging alkylation is that of unactivated esters and amides. Only noble metal catalysts based on iridium and ruthenium have been used to accomplish these reactions. Herein, we report on the first base metal-catalyzed α-alkylation of unactivated amides and esters by alcohols. Cobalt complexes stabilized with pincer ligands, recently developed in our laboratory, catalyze these reactions very efficiently. The precatalysts can be synthesized easily from commercially available starting materials on a multigram scale and are self-activating under the basic reaction conditions. This Co catalyst class is also able to mediate alkylation reactions of both esters and amides. In addition, we apply the methodology to synthesize ketones and to convert alcohols into aldehydes elongated by two carbon atoms.
- Deibl, Nicklas,Kempe, Rhett
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supporting information
p. 10786 - 10789
(2016/09/09)
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- Synthesis of Cinnamanilide Derivatives and Their Antioxidant and Antimicrobial Activity
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The amide derivatives of cinnamic acid were synthesized and their antimicrobial and antioxidant activities were investigated. The investigation of antimicrobial potentials of the compounds demonstrated a strong activity against 21 bacterial strains comprising Gram-positive and Gram-negative bacteria. Compounds 2a, 2b, and 3b showed strong antimicrobial activity against all microorganisms with the pMIC value ranging from 2.45 to 3.68. Compounds 2a, 3a, and 3b demonstrated strong antioxidant activity with % inhibition of the DPPH radical of 51% (±1.14), 41% (±1.01), and 50% (±1.23), respectively. These findings indicate that the amide derivatives of the cinnamic acid possess strong antibacterial and antioxidant activities.
- Nimse, Satish Balasaheb,Pal, Dilipkumar,Mazumder, Avijit,Mazumder, Rupa
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- Potassium tert-Butoxide-Mediated Amine Acyl Exchange Reaction of N,N-Disubstituted Formamides with Aromatic Carbonyl Derivatives via Sequential C-N Bond Cleavage/Formation: An Approach to Aromatic Amides
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A novel potassium tert-butoxide-mediated amine acyl exchange of N,N-disubstituted formamides with aromatic carbonyl derivatives in a sequential C-N bond cleavage/formation process leading to aromatic amides is described. This methodology tolerates a wide range of aromatic carbonyl compounds, including aromatic aldehydes, acyl chlorides, unactivated esters, and acid anhydrides. The usage of inexpensive and readily available reagents, broad substrate scope, and the simple, mild (50°C) and transition metal-free conditions make this protocol very practical. In addition, a plausible reaction mechanism is proposed on the basis of experimental observations.
- Zhang, Ming-Zhong,Guo, Qing-Hu,Sheng, Wen-Bing,Guo, Can-Cheng
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supporting information
p. 2855 - 2861
(2015/09/28)
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- SYNTHESIS OF FUNCTIONALIZED AND UNFUNCTIONALIZED OLEFINS VIA CROSS AND RING-CLOSING METATHESIS
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The invention is directed to the cross-metathesis and ring-closing metathesis reactions between geminal disubstituted olefins and terminal olefins, wherein the reaction employs a Ruthenium or Osmium metal carbene complex. Specifically, the invention relates to the synthesis of alpha-functionalized or unfunctionalized olefins via intermolecular cross-metathesis and intramolecular ring-closing metathesis using a ruthenium alkylidene complex. The catalysts preferably used in the invention are of the general formulawherein:M is ruthenium or osmium;X and Xare each independently an anionic ligand;L is a neutral electron donor ligand; and,R, RR, R, R, and Rare each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl.
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Paragraph 0018; 0024
(2015/11/09)
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- Oxidative coupling of alkenes with amides using peroxides: Selective amide C(sp3)-H versus C(sp2)-H functionalization
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A new oxidative coupling of unactivated terminal alkenes with amides using peroxides is described, in which mono- and difunctionalization of alkenes are selectively achieved. In this reaction with amides, the chemoselectivity toward the functionalization of the C(sp3)-H bonds adjacent to the nitrogen atom or the functionalization of the carbonyl C(sp2)-H bonds across alkenes relies on the reaction conditions. This journal is
- Yang, Xu-Heng,Wei, Wen-Ting,Li, Hai-Bing,Song, Ren-Jie,Li, Jin-Heng
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supporting information
p. 12867 - 12869
(2014/12/11)
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- Functionalization of amides via copper-catalyzed oxyalkylation of vinylarenes and decarboxylative alkenylation of sp3 C-H
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An efficient protocol was developed to prepare a series of derivatives from amides by copper-catalyzed oxyalkylation of vinylarenes and decarboxylative alkenylation of sp3 C-H. This method is simple, practical, and inexpensive.
- Yan, Hong,Lu, Linhua,Rong, Guangwei,Liu, Defu,Zheng, Yang,Chen, Jie,Mao, Jincheng
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p. 7103 - 7111
(2014/08/18)
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- Copper-catalyzed amidation of acids using formamides as the amine source
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Copper-catalyzed amidation of acids with formamides or acetamide for the selective synthesis of amides with the aid of 1,4-diazabicyclo[2.2.2]octane as the ligand and tert-butyl hydroperoxide as the oxidant is presented. This method is highly compatible with a wide range of acids, including alkyl acids, aryl acids, α,β-unsaturated acids, and amino acids. A general and direct route for the synthesis of amides is described. The reaction involves the copper-catalyzed amidation of acids, wherein various formamides and an acetamide are used as the amine source. Importantly, this method represents a new strategy for the direct use of acids in the synthesis of amides. DABCO = 1,4-diazabicyclo[2.2.2]octane, TBHP = tert-butyl hydroperoxide. Copyright
- Xie, Ye-Xiang,Song, Ren-Jie,Yang, Xu-Heng,Xiang, Jian-Nan,Li, Jin-Heng
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p. 5737 - 5742
(2013/09/12)
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- Copper-catalyzed oxidative coupling of carboxylic acids with formamides for the synthesis of α,β-unsaturated amides
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A novel and efficient protocol for the synthesis of α,β- unsaturated amides has been developed using catalytic amount of Cu(OAc) 2 and TBHP as an available oxidant. Oxidative coupling of various unsaturated carboxylic acids with N,N-disubstituted formamides was examined to furnish the desired products in good yields.
- Li, Huamin,Pan, Changduo,Cheng, Yixiang,Zhu, Chengjian
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supporting information
p. 6679 - 6681
(2013/11/19)
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- Copper-catalyzed synthesis of α,β-unsaturated acylamides via direct amidation from cinnamic acids and N-substituted formamides
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A highly effective synthesis of α,β-unsaturated acylamides is reported for the first time via copper-catalyzed direct amidation between readily available cinnamic acids and N-substituted formamides. The protocol was easily accessible and practical.
- Yan, Hong,Yang, Hailong,Lu, Linhua,Liu, Defu,Rong, Guangwei,Mao, Jincheng
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p. 7258 - 7263
(2013/08/23)
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- Copper catalyzed cross-coupling reactions of carboxylic acids: An expedient route to amides, 5-substituted γ-lactams and α-acyloxy esters
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A convenient and recyclable catalytic protocol for the synthesis of N,N-dimethyl substituted amides, 5-substituted γ-lactams and α-acyloxy ethers from carboxylic acids using CuO nanoparticles and TBHP is described.
- Priyadarshini,Amal Joseph,Lakshmi Kantam
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p. 18283 - 18287
(2013/10/21)
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- Synthesis of arylethylene or diarylethylene compounds by Pd-catalyzed heck coupling reaction
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We have developed an effective palladium-catalyzed arylation or diarylation couplings of olefins with various aryl halides in the presence of readily available ligands. This method is simple, economical, and practical for the synthesis of arylethylene and diarylethylene. Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for full experimental and spectral details.
- Yan, Hong,Sun, Peng,Qu, Xiaoming,Lu, Linhua,Zhu, Yan,Yang, Hailong,Mao, Jincheng
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supporting information
p. 2773 - 2783
(2013/08/23)
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- Metal-free n-Bu4NI-catalyzed direct synthesis of amides from alcohols and N,N-disubstituted formamides
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A facile and efficient protocol for the synthesis of amides has been developed in the absence of transition metals. The reaction was performed with a catalytic amount of n-Bu4NI and aqueous TBHP as an oxidant. Various alcohols with N,N-disubstituted formamides were examined to furnish the desired products in good yields.
- Li, Huamin,Xie, Jin,Xue, Qicai,Cheng, Yixiang,Zhu, Chengjian
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supporting information
p. 6479 - 6482,4
(2012/12/12)
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- The ligand and base-free Pd-catalyzed oxidative Heck reaction of arylboronic acids and olefins
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Highly effective Pd-catalyzed Heck-type oxidative couplings between arylboronic acids and terminal olefins were reported. It is noteworthy that such reactions could be carried out in the absence of the base and the ligand.
- Sun, Peng,Zhu, Yan,Yang, Hailong,Yan, Hong,Lu, Linhua,Zhang, Xiang,Mao, Jincheng
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supporting information; experimental part
p. 4512 - 4515
(2012/07/14)
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- Cross coupling of acyl and aminyl radicals: Direct synthesis of amides catalyzed by Bu4NI with TBHP as an oxidant
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A radical solution: A Bu4NI/tert-butyl hydroperoxide (TBHP) catalyzed synthesis of amides through a cross-coupling reaction between acyl and aminyl radicals is described. This method involves the combination of aldehyde C-H bond functionalization and decarbonylation of N,N-disubstituted formamides (see scheme). The cross-coupling is metal-free, has a wide substrate scope, operational simplicity, and gives high yields on scale-up. Copyright
- Liu, Zhaojun,Zhang, Jie,Chen, Shulin,Shi, Erbo,Xu, Yuan,Wan, Xiaobing
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experimental part
p. 3231 - 3235
(2012/05/05)
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- Highly effective recyclable palladium-catalyzed ligand-free heck reactions under aerobic conditions
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An effective protocol was developed for the Heck coupling reactions between various aryl halides and olefins. In the presence of 2 mol% of Pd(OAc) 2, the desired products could be obtained in good yields under ligand-free and aerobic conditions. The catalytic system could be easily recycled for five times with high efficiency. Georg Thieme Verlag Stuttgart. New York.
- Sun, Peng,Qu, Xiaoming,Li, Tingyi,Zhu, Yan,Yang, Hailong,Xing, Zeyong,Mao, Jincheng
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supporting information; experimental part
p. 150 - 154
(2012/02/04)
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- Direct amidation of alcohols with N-substituted formamides under transition-metal-free conditions
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Go tandem! The first example of the direct amidation of alcohols with N-substituted formamides has been developed. A series of tertiary amides, including the challenging N,N-dimethyl-substituted amides, were obtained in moderate to good yields under transition-metal-free conditions (see scheme). TBHP=tert-butyl hydroperoxide. Copyright
- Xu, Kun,Hu, Yanbin,Zhang, Sheng,Zha, Zhenggen,Wang, Zhiyong
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supporting information; experimental part
p. 9793 - 9797
(2012/09/05)
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