- Access to multi-functionalized oxazolines via silver-catalyzed heteroannulation of enamides with sulfoxonium ylides
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Disclosed herein is an efficient Ag-catalyzed [4 + 1] heteroannulation reaction of enamides with α-carbonyl sulfoxonium ylides. The diastereoselective transformation provides a practical access to a diverse range of multi-functionalized oxazoline derivatives. The synthetic utility of the resultant tetra-substituted oxazolines is further demonstrated by a series of useful manipulations into valuable building blocks of pharmaceutical relevance.
- Liu, Rui-Hua,Shan, Qi-Chao,Gao, Ya,Loh, Teck-Peng,Hu, Xu-Hong
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p. 1411 - 1414
(2020/10/29)
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- Rhodium(III)-Catalyzed Direct C-H Arylation of Various Acyclic Enamides with Arylsilanes
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The stereoselective β-C(sp2)-H arylation of various acyclic enamides with arylsilanes via Rh(III)-catalyzed cross-coupling reaction was illustrated. The methodology was characterized by extraordinary efficacy and stereoselectivity, a wide scope of substrates, good functional group tolerance, and the adoption of environmentally friendly arylsilanes. The utility of this present method was evidenced by the gram-scale synthesis and further elaboration of the product. In addition, Rh(III)-catalyzed C-H activation is considered to be the critical step in the reaction mechanism.
- Li, Xiaolan,Sun, Kai,Shen, Wenjuan,Zhang, Yong,Lu, Ming-Zhu,Luo, Xuzhong,Luo, Haiqing
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- Visible-light-promoted olefinic trifluoromethylation of enamides with CF3SO2Na
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A visible-light-promoted olefinic C-H trifluoromethylation of enamides was developed by employing cheap and stable Langlois’ reagent as the CF3source. A series of β-CF3enamides were obtained in moderate to good yields with highE-isomer selectivity under mild conditions. Preliminary mechanistic studies suggest that molecular oxygen acts as the terminal oxidant for this net oxidative process, and theEisomer selectivity could be well explained by a base-assisted deprotonation of the cation intermediate.
- Chen, Kai,Chen, Yixuan,Guan, Jianping,Tang, Kai,Wang, Zhujun,Xiang, Haoyue,Yang, Hua
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p. 7475 - 7479
(2021/09/08)
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- Selective Dehydrogenative Acylation of Enamides with Aldehydes Leading to Valuable β-Ketoenamides
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We have presented a unique example of dehydrogenative acylation of enamides with aldehydes enabled by an earth-abundant iron catalyst. The protocol provides the straightforward access to valuable β-ketoenamides with ample substrate scope and excellent functional group tolerance. Notably, distinct C-H acylation of enamide rather than at N-H moiety site occurs with absolute Z-selectivity was observed. Late-stage modifications of complex molecules and versatile synthetic utility of β-ketoenamides further highlight the practicability of this transformation.
- Liu, Rui-Hua,Shen, Zhen-Yao,Wang, Cong,Loh, Teck-Peng,Hu, Xu-Hong
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p. 944 - 949
(2020/02/15)
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- Direct Enamido C(sp2)?H Diphosphorylation Enabled by a PCET-Triggered Double Radical Relay: Access to gem-Bisphosphonates
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Herein we report a novel and straightforward protocol for the construction of valuable gem-BPs by means of proton-coupled electron-transfer (PCET)-triggered enamido C(sp2)?H diphosphorylation. This reaction represents a rare example of realizing the challenging double C?P bond formation at a single carbon atom, thus providing facile access to a broad variety of structurally diverse bisphosphonates from simple enamides under silver-mediated conditions. Initial mechanistic studies demonstrated that the diphosphorylation involves two rounds of PCET-initiated radical relay process.
- Cao, Hao-Qiang,Liu, Hao-Nan,Liu, Zhe-Yuan,Ma, Jun-An,Qiao, Bao-Kun,Zhang, Fa-Guang
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p. 5515 - 5521
(2020/04/27)
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- Efficient and practical synthesis of N-acetyl enamides from ketoximes by unique iron catalytic system
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A new procedure for the iron-catalyzed synthesis of enamides from ketoximes was developed, and its mechanism was proposed. A unique reduction system, with the concerted use of KI and Na2S2O4, was involved. The reaction exhibited a wide substrate scope and gave good yields in a short reaction time. The procedure is operationally simple and also applicable for the large-scale synthesis.
- Kunishige, Takahiro,Sawada, Daisuke
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p. 1562 - 1565
(2019/05/24)
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- The ruthenium-catalyzed C-H functionalization of enamides with isocyanates: Easy entry to pyrimidin-4-ones
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Ruthenium-catalyzed heteroannulation between enamides and isocyanates has been realized as a complementary approach to conventional strategies for the synthesis of pyrimidin-4-ones. High step-A nd atom-economy was achieved for the rapid construction of such privileged scaffolds, which are found in a multitude of pharmaceutical compounds. The generality and practicability of this transformation were reflected by the broad scope of substrates with diverse functional groups, large-scale synthesis, and late-stage diversification.
- Shi, Pengfei,Li, Song,Hu, Lu-Min,Wang, Cong,Loh, Teck-Peng,Hu, Xu-Hong
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p. 11115 - 11118
(2019/09/20)
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- Nickel-Catalyzed Transformation of Diazoacetates to Alkyl Radicals Using Alcohol as a Hydrogen Source
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A nickel-catalyzed transformation of diazoacetates to α-carbonyl methylene radicals has been disclosed in the presence of hyperoxide using ethanol as a hydrogen source and solvent. This strategy is successfully applied in the formation of indolin-2-ones or 1,4-dicarbonyl compounds from acrylamides or enamides in moderate to good yields. These reactions undergo radical addition onto C-C double bonds followed by a cyclization/oxidation or an oxidation/hydrolysis process, respectively.
- Zhao, Jingjing,Li, Pan,Xu, Yaohua,Shi, Yixin,Li, Fuwei
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p. 9386 - 9390
(2019/11/28)
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- Hypervalent iodane mediated reactions of: N -acetyl enamines for the synthesis of oxazoles and imidazoles
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A hypervalent iodane reagent used for the intramolecular cyclization of N-acetyl enamines and intermolecular cyclocondensation of enamines and nitriles was investigated. The reaction was performed under mild conditions and gave oxazoles and imidazoles, respectively, in moderate to excellent yields. This transformation exhibits good reactivity, selectivity and functional group tolerance. The selectivity of the intra- or intermolecular reaction is dependent on the structure of N-acetyl enamines.
- Xu, Kang,Yang, Ruiqi,Yang, Shuang,Jiang, Cheng,Ding, Zhenhua
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supporting information
p. 8977 - 8981
(2019/10/28)
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- Intramolecular Transamidation of Secondary Amides via Visible-Light-Induced Tandem Reaction
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Transformation of secondary amides to N-acylimines was used as an effective strategy to activate otherwise unreactive amide bonds. In this tandem reaction, the Rose Bengal-catalyzed photo-oxidative coupling of arylglycine esters and enamides generates N-acylimines, which undergo intramolecular transamidation and imine hydrolysis to afford bioactive acyl Mannich base derivatives under metal-free and mild conditions.
- Tang, Li,Li, Xing-Meng,Matuska, Jack H.,He, Yan-Hong,Guan, Zhi
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supporting information
p. 5618 - 5621
(2018/09/21)
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- Iron-Catalyzed Radical Cycloaddition of 2H-Azirines and Enamides for the Synthesis of Pyrroles
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A novel and efficient Fe-catalyzed radical cycloaddition of 2H-azirines and enamides for the synthesis of substituted pyrroles has been developed. The radical cycloaddition reaction proceeded through a conceptually new Fe(II)-catalyzed homolytic cleavage of C-N bond of 2H-azirines sequential radical cyclization with enamides. The reaction used readily available starting materials, tolerated various functional groups, and afforded valuable triaryl-substituted pyrroles in good to high yields under mild reaction conditions.
- Zhao, Mi-Na,Ren, Zhi-Hui,Yang, De-Suo,Guan, Zheng-Hui
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supporting information
p. 1287 - 1290
(2018/03/09)
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- Electrochemical oxidative [4 + 2] annulation of tertiary anilines and alkenes for the synthesis of tetrahydroquinolines
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Heterocyclic compounds, especially nitrogen heterocycles, are one of the most important classes of compounds in the pharmaceutical and agrochemical industries. The oxidative [4 + 2] annulation reaction provides a powerful tool for the rapid construction of six-membered heterocycles. Herein, we report a metal- and external oxidant-free method for the uniform synthesis of tetrahydroquinolines through the electrochemical oxidative [4 + 2] annulation of tertiary anilines and alkenes. In this strategy, one partner loses only two hydrogen atoms while another partner reduces one degree of unsaturation, accompanied by the generation of hydrogen. Under the conditions of an undivided cell and room temperature, a series of tetrahydroquinoline derivatives were prepared with good yields.
- Huang, Pengfei,Wang, Pan,Wang, Shengchun,Tang, Shan,Lei, Aiwen
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supporting information
p. 4870 - 4874
(2018/11/21)
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- METHOD FOR PREPARING ENAMIDE COMPOUND AND RUTHENIUM COMPLEX CATALYST USED THEREIN
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Provided is a method for preparing an enamide compound, which includes reacting an organic azide compound having α-hydrogen and an anhydride by addition of a ruthenium complex catalyst in the presence of an ionic liquid, and a ruthenium complex catalyst u
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Paragraph 0127
(2017/10/27)
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- CATALYTIC PREPARATION OF ENAMIDES FROM ALKYL AZIDES AND ACYL DONORS
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The present invention relates to a method to synthesize an enamide compound by generating imine which does not have a substituent group bonded to the nitrogen from an organic azide compound and conducting a reaction of the same with acyl doner. By using t
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Paragraph 0085-0086
(2016/10/10)
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- Synthesis of Enamides by Ruthenium-Catalyzed Reaction of Alkyl Azides with Acid Anhydrides in Ionic Liquid
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Enamides were synthesized by a ruthenium-catalyzed one-pot, one-step procedure from alkyl azides and acid anhydrides. The substrate scope includes not only secondary azides, but also primary aliphatic ones to give a wide range of enamides containing vario
- Pak, Han Kyu,Han, Junghoon,Jeon, Mina,Kim, Yongjin,Kwon, Yearang,Park, Jin Yong,Rhee, Young Ho,Park, Jaiwook
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p. 4030 - 4034
(2015/12/26)
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- One-pot green synthesis of enamides and 1,3-diynes
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A green organic synthetic method combining reductive acylation of ketoximes and oxidative coupling of terminal alkynes was developed. This novel process enables enamides and 1,3-diynes to be synthesized simultaneously in high yields and under mild conditions without the use of terminal reductants/oxidants.
- Liang, Hao,Ren, Zhihui,Wang, Yaoyu,Guan, Zhenghui
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p. 113 - 118
(2015/09/28)
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- Synthesis of diverse di- to penta-substituted 1,2-dihydropyridine derivatives from gold(I)-catalyzed intramolecular addition of tertiary enamides to alkynes
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As 3-aza-1,5-enynes, internal and terminal alkyne-bearing tertiary enamides underwent an efficient Au(I)-catalyzed 6-endo-dig cyclization reaction to afford a variety of di- to penta-substituted 1,2-dihydropyridine derivatives in high yields. The cyclizat
- Zhang, Xingyi,Xu, Xin-Ming,Zhao, Liang,You, Jingsong,Zhu, Jieping,Wang, Mei-Xiang
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p. 3898 - 3901
(2015/06/08)
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- Exploiting the Nucleophilicity of N-H Imines: Synthesis of Enamides from Alkyl Azides and Acid Anhydrides
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The nucleophilicity of N-unsubstituted imines, which were generated from alkyl azides by a ruthenium-catalyzed reaction, was investigated in the reaction with acid anhydrides. The initial products were N-acylimines, which isomerized to the corresponding e
- Han, Junghoon,Jeon, Mina,Pak, Han Kyu,Rhee, Young Ho,Park, Jaiwook
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p. 2769 - 2774
(2016/02/18)
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- Rhodium(iii)-catalyzed olefinic C-H alkynylation of enamides at room temperature
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Rh(iii)-catalyzed C-H olefinic alkynylation of enamides for the stereospecific construction of synthetically useful Z-type enynamides is reported. This protocol displays good functionality tolerance and operational simplicity thus providing an alternative synthetic opportunity for the ease of access to specific 1,3-enyne derivatives.
- Feng, Chao,Feng, Daming,Loh, Teck-Peng
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p. 9865 - 9868
(2014/08/18)
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- Direct oxidative coupling of enamides and 1,3-dicarbonyl compounds: A facile and versatile approach to dihydrofurans, furans, pyrroles, and dicarbonyl enamides
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An efficient manganese(III)-mediated oxidative coupling reaction between α-aryl enamides and 1,3-dicarbonyl compounds has been developed. A series of dihydrofurans and dicarbonyl enamides were synthesized in moderate to good yields. Moreover, these dihydrofurans could be readily transformed into the corresponding furans and pyrroles via the Paal-Knorr reaction.
- Li, Pan,Zhao, Jingjing,Xia, Chungu,Li, Fuwei
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p. 5992 - 5995
(2015/01/08)
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- Copper-promoted oxidative coupling of enamides and alkynes for the synthesis of substituted pyrroles
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An efficient copper-promoted oxidative coupling of enamides with alkynes has been developed for the synthesis of substituted pyrroles. The reaction proceeded through C-H and N-H bond functionalization of enamides under mild conditions.
- Zhao, Mi-Na,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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supporting information
p. 1839 - 1842
(2014/03/21)
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- Pd-catalyzed Oxidative coupling of Enamides and Alkynes for synthesis of substituted Pyrroles
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A novel and efficient palladium(II)-catalyzed alkenyl C-H activation oxidative annulation of enamides with alkynes for the synthesis of substituted pyrroles has been developed. The reaction tolerates a wide range of functional groups and is a reliable method for the synthesis of triaryl-substituted pyrroles in high yields.
- Zhao, Mi-Na,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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supporting information
p. 608 - 611
(2014/04/03)
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- An efficient preparation of N-acetyl enamides catalyzed by Ru(II) complexes
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Reductive acetylation of ketoximes to give the corresponding acyl enamides can be achieved by using 1-3 mol % of [RuCl2(p-cymene)]2 as the catalyst in the presence of KI as the reducing agent in high yields. This procedure has been applied to synthesize N-[1-(1,3-benzodioxol-5-yl)-1-butenyl] acetamide (6), which is the intermediate for the synthesis of DMP 777, an inhibitor of leukocyte elastase.
- Murugan, Kaliyappan,Huang, Da-Wei,Chien, Yu-Ting,Liu, Shiuh-Tzung
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p. 268 - 273
(2013/01/15)
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- The P-chiral phosphane ligand (MeO-BIBOP) for efficient and practical large-scale Rh-catalyzed asymmetric hydrogenation of N-acetyl enamides with high TONs
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A highly electron-rich P-chiral bis(trialkylphosphane) ligand MeO-BIBOP (1) was efficiently synthesized on large scale. The MeO-BIBOP-rhodium complex exhibited remarkably high reactivities (up to 200,000 TON) for the hydrogenation of N-acetyl enamides to
- Li, Wenjie,Rodriguez, Sonia,Duran, Adil,Sun, Xiufeng,Tang, Wenjun,Premasiri, Ajith,Wang, Jun,Sidhu, Kanwar,Patel, Nitinchandra D.,Savoie, Jolaine,Qu, Bo,Lee, Heewon,Haddad, Nizar,Lorenz, Jon C.,Nummy, Larry,Hossain, Azad,Yee, Nathan,Lu, Bruce,Senanayake, Chris H.
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p. 1061 - 1065
(2013/09/12)
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- Direct titanium-mediated conversion of ketones into enamides with ammonia and acetic anhydride
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A one-step conversion of ketones into N-acetyl enamides was developed. The process employs safe and inexpensive reagents, proceeds under mild conditions, and tolerates diverse functional groups. The addition of edte (N,N,N ,N -tetrakis(2-hydroxyethyl)ethy
- Reeves, Jonathan T.,Tan, Zhulin,Han, Zhengxu S.,Li, Guisheng,Zhang, Yongda,Xu, Yibo,Reeves, Diana C.,Gonnella, Nina C.,Ma, Shengli,Lee, Heewon,Lu, Bruce Z.,Senanayake, Chris H.
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supporting information; experimental part
p. 1400 - 1404
(2012/03/26)
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- Coupling of enamides with alkynes or arynes for synthesis of substituted pyridines and isoquinolines via amide activation
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A novel and general procedure for Cu-catalyzed coupling of enamides with alkynes to synthesize substituted pyridines was developed. The chemistry was allowed to extend to the synthesis of substituted isoquinolines by coupling of enamides with arynes under transition-metal-free conditions.
- Zhao, Mi-Na,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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supporting information; experimental part
p. 8105 - 8107
(2012/09/07)
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- Ruthenium-catalyzed hydrovinylation of N-acetylenamines leading to amines with a quaternary carbon center
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A catalytic hydrovinylation of N-acetylenamines with ethylene is reported. This new hydrovinylation reaction is catalyzed by a ruthenium hydride complex, RuHCl(CO)(PCy3)2, providing a series of N-acetylamines with a quaternary carbon center with up to 99% yield.
- Wang, Qiu-Shi,Xie, Jian-Hua,Li, Wei,Zhu, Shou-Fei,Wang, Li-Xin,Zhou, Qi-Lin
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p. 3388 - 3391
(2011/08/21)
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- Synthesis of enamides via CuI-catalyzed reductive acylation of ketoximes with NaHSO33
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CuI-catalyzed reductive acylation of ketoximes for preparation of enamides was reported. A broad scope of enamides was obtained in high yields with NaHSO3 used as the terminal reductant.
- Guan, Zheng-Hui,Zhang, Zhi-Yuan,Ren, Zhi-Hui,Wang, Yao-Yu,Zhang, Xumu
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supporting information; experimental part
p. 339 - 341
(2011/03/20)
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- A facile and practical synthesis of N-acetyl enamides
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(Chemical Equation Presented) A facile and practical method for the synthesis of N-acetyl α-arylenamides has been developed from corresponding ketoximes as the starting materials with ferrous acetate as the reducing reagent. This methodology offers mild reaction conditions, simple purification procedures, and high yields for a variety of N-acetyl enamides.
- Tang, Wenjun,Capacci, Andrew,Sarvestani, Max,Wei, Xudong,Yee, Nathan K.,Senanayake, Chris H.
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supporting information; experimental part
p. 9528 - 9530
(2010/03/24)
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- A complementary method to obtain N-acyl enamides using the Heck reaction: Extending the substrate scope for asymmetric hydrogenation
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A series of N-acyl enamides were prepared using the Heck reaction. Asymmetric hydrogenation provided protected amines in up to 99% ee. A method to prepare N-acyl enamides is reported that is complementary to the existing protocols. Heck reaction of a vari
- Harrison, Paul,Meek, Graham
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p. 9277 - 9280
(2007/10/03)
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