- Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
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We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.
- Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
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supporting information
p. 3575 - 3580
(2019/04/14)
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- C1-Symmetric 1,2-Diaminobicyclo[2.2.2]octane Ligands in Copper-Catalyzed Asymmetric Henry Reaction: Catalyst Development and DFT Studies
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Chiral tetra- and bidentate ligands derived from the (R)-1,2-diaminobicyclo[2.2.2]octane scaffold were synthesized, and the influence of the N,N′-substituents of the ligand on the catalytic activity of their corresponding copper(II) complexes toward the n
- Milbeo, Pierre,Moulat, Laure,Didierjean, Claude,Aubert, Emmanuel,Martinez, Jean,Calmès, Monique
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p. 178 - 187
(2018/01/26)
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- Diamine-Tethered Bis(thiourea) Organocatalyst for Asymmetric Henry Reaction
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We have developed a novel multifunctional C2-symmetric biphenyl-based diamine-tethered bis(thiourea) organocatalyst, which was tested in the asymmetric Henry reaction. Under thoroughly optimized conditions, the catalyst provided exceptionally high yields and excellent enantioselectivities especially for electron-deficient aromatic and heterocyclic substrates. Due to a high affinity of the catalyst to silica gel, a simple chromatography-free nitroaldol isolation procedure was feasible. Preliminary kinetic and spectroscopic experiments were performed in order to complete the mechanistic picture of the organocatalyzed nitroaldolization process. Finally, the developed synthetic strategy was successfully applied to the catalytic enantioselective syntheses of enantiopure (S)-econazole and (R)-mirabegron a late-stage intermediate.
- Otevrel, Jan,Bobal, Pavel
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supporting information
p. 8342 - 8358
(2017/08/23)
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- The synthesis of chiral tridentate ligands from L-proline and their application in the copper(II)-catalyzed enantioselective Henry reaction
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A series of chiral tridentate ligands derived from readily available enantiopure L-proline were designed and synthesized. The ligands together with Cu(OAc)2 were successfully used in asymmetric Henry reactions. Various structurally divergent aldehydes and nitromethane were converted into versatile β-nitro alcohols in MeOH at room temperature with very good yields (up to 85%) and enantioselectivities (up to 86%).
- Xu, Daqian,Sun, Qiangsheng,Quan, Zhengjun,Sun, Wei,Wang, Xicun
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p. 954 - 963
(2017/07/11)
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- Mining catalytic promiscuity from: Thermophilic archaea: An acyl-peptide releasing enzyme from Sulfolobus tokodaii (ST0779) for nitroaldol reactions
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This work demonstrates that the thermophiles can be a rich source to mine catalytic promiscuity, whereby an acyl-peptide releasing enzyme from Sulfolobus tokodaii (ST0779) is identified to be a promising biocatalyst to mediate the Henry (nitroaldol) react
- Yu, Xiaoxiao,Pérez, Bianca,Zhang, Zhefei,Gao, Renjun,Guo, Zheng
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p. 2753 - 2761
(2016/05/24)
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- Probing the evolution of an Ar-BINMOL-derived salen-Co(iii) complex for asymmetric Henry reactions of aromatic aldehydes: Salan-Cu(ii) versus salen-Co(iii) catalysis
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A new type of chiral salen-Co catalyst that features aromatic π-walls and an active Co(iii) center has been developed for enantioselective Henry/nitroaldol reactions on the basis of salen-Cu catalysis. The asymmetric Henry reaction of aromatic aldehydes a
- Wei, Yun-Long,Yang, Ke-Fang,Li, Fei,Zheng, Zhan-Jiang,Xu, Zheng,Xu, Li-Wen
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p. 37859 - 37867
(2014/11/07)
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- Probing the evolution of an Ar-BINMOL-derived salen-Co(iii) complex for asymmetric Henry reactions of aromatic aldehydes: Salan-Cu(ii) versus salen-Co(iii) catalysis
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A new type of chiral salen-Co catalyst that features aromatic π-walls and an active Co(iii) center has been developed for enantioselective Henry/nitroaldol reactions on the basis of salen-Cu catalysis. The asymmetric Henry reaction of aromatic aldehydes a
- Wei, Yun-Long,Yang, Ke-Fang,Li, Fei,Zheng, Zhan-Jiang,Xu, Zheng,Xu, Li-Wen
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p. 37859 - 37867
(2014/12/11)
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- Asymmetric henry reaction catalyzed by chiral schiff base
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Four chiral Schiff bases were synthesized conveniently from chiral amino alcohol and 2-hydroxynaphthalene-1-carbaldehyde. These ligands were used to catalyze the addition of nitroalkanes to aldehydes under ambient conditions in good yields with up to 91%
- Ran, De-Qiang,Shen, Tian-Hua,Zhou, Xiao-Cong,Li, Jun-Qi,Cui, Fu-Na,Ma, Chun-An,Song, Qing-Bao
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p. 849 - 852
(2013/07/26)
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- Synthesis and computation of diastereomeric phenanthroline-quinine ligands and their application in asymmetric Henry reaction
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A class of chiral ligands has been developed by combining phenanthroline with quinine in a one-step method that does not require resolution. The synthesized three ligands were then coordinated with Cu(II) and the performance of the resultant ch
- Zhang, Lili,Wu, Hao,Yang, Zhongyue,Xu, Xiufang,Zhao, Haitao,Huang, Yaodong,Wang, Yongmei
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p. 10644 - 10652
(2013/11/19)
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- Catalytic effect and recyclability of imidazolium-tagged bis(oxazoline) based catalysts in asymmetric Henry reactions
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Functional imidazolium ionic liquids have been developed as a new class of versatile catalysts. C2-symmetric imidazolium-tagged bis(oxazoline) ligands were prepared, and the anions of the ligands were altered. The catalysts based on the new lig
- Zhou, Zhi-Ming,Li, Zhi-Huai,Hao, Xiao-Yan,Zhang, Jun,Dong, Xiao,Liu, Ying-Qiang,Sun, Wen-Wen,Cao, Dan,Wang, Jin-Liang
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supporting information; experimental part
p. 2113 - 2118
(2012/04/11)
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- Recyclable copper catalysts based on ionic-tagged C2-symmetric Indabox ligands and their application in asymmetric Henry reactions
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New imidazolium/pyrrolidinium-tagged Indabox ligands were designed and prepared. Catalysts based on these ligands with Cu(OAc)2· H2O were applied to the asymmetric Henry reaction using various aldehydes and CH3NO2/su
- Li, Zhi-Huai,Zhou, Zhi-Ming,Hao, Xiao-Yan,Zhang, Jun,Dong, Xiao,Liu, Ying-Qiang,Sun, Wen-Wen,Cao, Dan
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experimental part
p. 28 - 34
(2012/07/01)
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- Asymmetric henry reaction catalyzed by novel chiral bioxazolines from tartaric acid
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Novel C2-symmetric chiral bioxazolines were synthesized in good yields by the fusion of optically active acids with a tartaric acid derivative. Complexes of these products with copper(II) acetate monohydrate were found to be excellent catalysts
- Balaraman, Kaluvu,Vasanthan, Ravichandran,Kesavan, Venkitasamy
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supporting information; experimental part
p. 2455 - 2462
(2012/09/21)
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- Synthesis of planar chiral [2.2]paracyclophane Schiff bases for the enantioselective Henry reaction
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A series of diastereomerically pure Schiff base ligands based on [2.2]paracyclophane backbones were synthesized and separated. The new planar chiral [2.2]paracyclophane Schiff bases were used as ligands in Cu-catalyzed asymmetric Henry reactions with high
- He, Fuyan,Ma, Yudao,Zhao, Lei,Duan, Wenzeng,Chen, Jianqiang,Zhao, Zhongxi
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experimental part
p. 809 - 817
(2012/09/25)
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- Synthesis of C 1-symmetric chiral secondary diamines and their applications in the asymmetric copper(II)-catalyzed Henry (Nitroaldol) reactions
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A small library of C1-symmetric chiral diamines (L1-L9) was constructed via condensing exo-(-)-bornylamine or (+)-(1S,2S,5R)-menthylamine with various Cbz-protected amino acids. Among them, ligand L1/CuCl 2?2H2O complex (2.5 mol %) shows outstanding catalytic efficiency for Henry reaction between a variety of aldehydes and nitroalkanes to afford the expected products in high yields (up to 98%) with excellent enantioselectivities (up to 99%) and moderate to good diastereoselectivities (up to 90:10). This process is air-and moisture tolerant and has been applied to the synthesis of (S)-2-amino-1-(3,4-dimethoxyphenyl) ethanol (9), a key intermediate for (S)-epinephrine and (S)-norepinephrine. On the basis of HRMS and X-ray diffraction analysis of the L1/CuCl2 complex, a transition-state model was proposed to explain the origin of asymmetric induction. The low catalyst loading, excellent yields and enantioselectivities, inexpensive copper salt, and mild reaction conditions make our catalytic system to be practically useful.
- Zhou, Yirong,Dong, Junfang,Zhang, Fanglin,Gong, Yuefa
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experimental part
p. 588 - 600
(2011/03/20)
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- Asymmetric Copper(II)-catalysed nitroaldol (Henry) reactions utilizing a chiral C1-symmetric dinitrogen ligand
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A series of stable chiral C1-symmetric dinitrogen ligands were conveniently synthesized in high yields by condensation of chiral amines [(-)-exo-bornylamine or (+)-(1S,2S,5R)-menthylamine] with various substituted imidazolecarbaldehydes. With the assistance of base, the ligand L1 in combination with CuCl2·2H2O (2.5 mol-% or 5.0 mol-%) can efficiently promote nitroaldol (Henry) reactions between a variety of aldehydes and nitromethane. Both aromatic and aliphatic aldehydes were tolerated in our catalytic system, affording the expected nitroalcohol products in high yields (up to 97%) and with good enantioselectivities (up to 96%) under mild reaction conditions. A series of chiral C1-symmetric dinitrogen ligands were conveniently synthesized in high yields by condensations of chiralamines with various substituted imidazolecarbaldehydes. The ligand L1 in conjunction with CuCl2·2H2O can efficiently promote nitroaldol (Henry) reactions between various aldehydes and nitromethane in high yields (up to 97%) and with good enantioselectivities (up to 96%).
- Zhou, Yirong,Gong, Yuefa
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supporting information; experimental part
p. 6092 - 6099
(2011/11/29)
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- Enantioselective Henry reaction catalyzed by a copper(II) glucoBOX complex
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A highly enantioselective Henry reaction has been developed using a chiral copper(II)-glucoBOX complex. The catalytic system works well with a wide range of aromatic, aliphatic and heteroaromatic aldehydes to afford the corresponding nitroalkanols with hi
- Reddy, B.V.Subba,George, Jimil
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experimental part
p. 1169 - 1175
(2011/10/17)
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- New highly asymmetric henry reaction catalyzed by CuII and a C1-symmetric aminopyridine ligand, and its application to the synthesis of miconazole
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A new catalytic asymmetric Henry reaction has been developed that uses a C1 -symmetric chiral aminopyridine ligand derived from camphor and picolylamine. A variety of aromatic, heteroaromatic, aliphatic, and unsaturated aldehydes react with nit
- Blay, Gonzalo,Domingo, Luis R.,Hernandez-Olmos, Victor,Pedro, Jose R.
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supporting information; experimental part
p. 4725 - 4730
(2009/05/07)
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- A new copper (I)-tetrahydrosalen-catab zed asymmetric henry reaction and its extension to the synthesis of (S)-norphenylephrine
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A new chiral hydrogenated salen catalyst has been developed for the asymmetric Henry reaction which produces the expected products in moderate to high yields (up to 98%) with excellent enantioselectivities (up to 96% ee). A variety of aromatic, heteroarom
- Xiong, Yan,Wang, Fei,Huang, Xiao,Wen, Yuehong,Feng, Xiaoming
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p. 829 - 833
(2007/10/03)
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- Enantioselective Henry reaction catalyzed by salen-cobalt complexes
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The enantioselective Henry reaction catalyzed by the optically active salen-cobalt complexes, proceeded to afford β-hydroxynitroalkanes in good-to-high yields with high enantioselectivity.
- Kogami, Youichi,Nakajima, Takahiro,Ikeno, Taketo,Yamada, Tohru
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p. 1947 - 1950
(2007/10/03)
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