- Nickel-catalyzed enantioselective umpolung hydrogenation for stereoselective synthesis of β-amido esters
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Nickel complexes ligated by strongly donating diphosphines catalyze enantioselective hydrogenation for the preparation of acyclic and cyclic β-amido esters. A combination of acetic acid and indium powder provides protons and electrons to form nickel hydrido complexes under umpolung hydrogenation conditions.
- Zhou, Jianrong Steve,Guo, Siyu,Zhao, Xiaohu,Chi, Yonggui Robin
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supporting information
p. 11501 - 11504
(2021/11/16)
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- Nickel-catalyzed enantioselective hydrogenation of β-(acylamino)acrylates: Synthesis of chiral β-amino acid derivatives
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The nickel-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates has been developed, affording chiral β-amino acid derivatives with excellent yields (95-99% yield) and enantioselectivities (97-99% ee). With the Ni-Binapine system, high enantioselectivities (98-99% ee) have also been obtained in the hydrogenation of Z/E isomeric mixtures of β-alkyl and β-aryl β-(acylamino)acrylates. The synthesis of chiral β-amino acid derivatives on a gram scale has also been achieved with 0.2 mol % catalyst loading.
- Li, Xiuxiu,You, Cai,Li, Shuailong,Lv, Hui,Zhang, Xumu
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supporting information
p. 5130 - 5133
(2017/11/06)
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- Nickel-catalyzed asymmetric transfer hydrogenation of olefins for the synthesis of α- And β-amino acids
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The field of asymmetric (transfer) hydrogenation of prochiral olefins has been dominated by noble metal catalysts based on rhodium, ruthenium, and iridium. Herein we report that a simple nickel catalyst is highly active in the transfer hydrogenation using
- Yang, Peng,Xu, Haiyan,Zhou, Jianrong
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supporting information
p. 12210 - 12213
(2016/02/18)
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- Highly efficient iridium-catalyzed asymmetric hydrogenation of unprotected β-enamine esters
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A highly efficient and enantioselective hydrogenation of unprotected β-enamine esters catalyzed by Ir-(S,S)-f-Binaphane complex has been developed. This methodology provides straightforward access to free β-amino acids in high yields with excellent enantioselectivities up to 97% ee and high reactivities (TON > 5000).
- Hou, Guohua,Zhang, Xumu,Li, Wei,Ma, Miaofeng,Zhang, Xiaowei
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supporting information; experimental part
p. 12844 - 12846
(2010/11/05)
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- Readily available chiral phosphine-aminophosphine ligands derived from 1-phenylethylamine for Rh-catalyzed enantioselective hydrogenations
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A series of new chiral phosphine-aminophosphine ligands have been prepared via a two- or three-step transformation from commercially available and inexpensive (S)-1-phenylethylamine, and successfully used in the rhodium-catalyzed asymmetric hydrogenation
- Zhou, Xiao-Mao,Huang, Jia-Di,Luo, Li-Bin,Zhang, Cheng-Lu,Zheng, Zhuo,Hu, Xiang-Ping
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experimental part
p. 420 - 424
(2010/07/02)
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- Chiral 1-phenylethylamine-derived phosphine-phosphoramidite ligands for highly enantioselective Rh-catalyzed hydrogenation of β-(acylamino) acrylates: Significant effect of substituents on 3,3′-positions of binaphthyl moiety
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A series of new chiral phosphine-phosphoramidite ligands with a 3,3′-substituted binaphthyl moiety were prepared from 1-phenylethylamine, and successfully applied in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates. The research disclosed that the substituents on the 3,3′-positions of binaphthyl moiety significantly influenced the enantioselectivity.
- Zhou, Xiao-Mao,Huang, Jia-Di,Luo, Li-Bin,Zhang, Chen-Lu,Hu, Xiang-Ping,Zheng, Zhuo
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supporting information; experimental part
p. 2320 - 2322
(2010/07/07)
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- Electron-donating and rigid p-stereogenic bisphospholane ligands for highly enantioselective rhodium-catalyzed asymmetric hydrogenations
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More electron donating, more rigid: A new highly electron-donating P-stereogenic bisphospholane ligand (ZhangPhos) was synthesized in a practical and highly enantioselective manner from a commercially available chiral source. Better or comparable enantioselectivities and reactivities than TangPhos were achieved in rhodium-catalyzed hydrogenation of various functionalized olefins (see scheme; nbd=3,5-norbornadiene). Copyright
- Zhang, Xiaowei,Huang, Kexuan,Hou, Guohua,Cao, Bonan,Zhang, Xumu
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supporting information; experimental part
p. 6421 - 6424
(2010/12/19)
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- Modular phosphine-aminophosphine ligands based on chiral 1,2,3,4-tetrahydro-1-naphthylamine backbone: A new class of practical ligands for enantioselective hydrogenations
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A series of new chiral phosphine-aminophosphine ligands [(R)-HW-Phos] has been prepared from (R)-1,2,3,4-tetrahydro-1-naphthylamine through a two-step procedure, and successfully applied in the rhodium-catalyzed asymmetric hydrogenation of various functionalized olefins such as α-enol ester phosphonates, α-enamido phosphonates, (Z)-β-(acylamino)acrylates and so on. Excellent enantioselectivities have been achieved in the hydrogenation of most substrates tested, demonstrating the high potential of these newly developed phosphine-aminophosphine ligands in asymmetric catalysis. The present research also discloses that these newly developed phosphine-aminophosphine ligands are more efficient than that derived from (S)-1-phenylethylamine, suggesting that the increased rigidity conferred by a cyclohexyl fragment in these phosphine-aminophosphine ligands has a positive effect in the asymmetric induction.
- Qiu, Min,Hu, Xiang-Ping,Huang, Jia-Di,Wang, Dao-Yong,Deng, Jun,Yu, Sai-Bo,Duan, Zheng-Chao,Zheng, Zhuo
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experimental part
p. 2683 - 2689
(2009/10/14)
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- Practical P-chiral phosphane ligand for Rh-catalyzed asymmetric hydrogenation
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A highly electron-donating and conformationally rigid P-chiral bis(trialkylphospholane) ligand 2 (DuanPhos) has been prepared in both enantiomeric forms through a concise synthesis. Rh-2 complex has exhibited remarkably high enantio-selectivities (up to >99% ee) and reactivities (up to 10,000 TON) for the hydrogenation of a wide variety of functionalized prochiral alkenes (5 different types), which provides a very practical catalytic system for the preparation of various synthetically useful chiral compounds. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Liu, Duan,Zhang, Xumu
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p. 646 - 649
(2007/10/03)
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- Practical Rh(I)-catalyzed asymmetric hydrogenation of β-(acylamino) acrylates using a new unsymmetrical hybrid ferrocenylphosphine-phosphoramidite ligand: Crucial influence of an N-H proton in the ligand
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(Chemical Equation Presented) Excellent enantioselectivities and high turnovers (S/C = 5000) were achieved in the Rh(I)-catalyzed asymmetric hydrogenation of both β-aryl-and β-alkyl-β-(acylamino)acrylates with a new unsymmetrical hybrid ferrocenylphosphine-phosphoramidite ligand, and the presence of an N-H proton in the ligand was demonstrated to have a crucial role in the enantioselectivity.
- Hu, Xiang-Ping,Zheng, Zhuo
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p. 419 - 422
(2007/10/03)
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- Synthesis of monodentate chiral spiro phosphonites and the electronic effect of ligand in asymmetric hydrogenation
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New monodentate chiral phosphonites were synthesized from enantiomerically pure 1,1′-spirobiindane-7,7′-diol. The phosphonites 2 were efficient ligands for the Rh-catalyzed asymmetric hydrogenation of α- and β-dehydroamino acid derivatives, providing the
- Fu, Yu,Hou, Guo-Hua,Xie, Jian-Hua,Xing, Liang,Wang, Li-Xin,Zhou, Qi-Lin
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p. 8157 - 8160
(2007/10/03)
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- Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands
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Novel chiral monodentate phosphorus ligands, SIPHOS, were conveniently synthesized from 1,1′-spirobiindane-7,7′-diol. The Rh complexes of SIPHOS can catalyze the hydrogenation of α-dehydroamino esters in mild conditions, providing α-amino acid derivatives
- Fu, Yu,Guo, Xun-Xiang,Zhu, Shou-Fei,Hu, Ai-Guo,Xie, Jian-Hua,Zhou, Qi-Lin
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p. 4648 - 4655
(2007/10/03)
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- A bisphosphepine ligand with stereogenic phosphorus centers for the practical synthesis of β-aryl-β-amino acids by asymmetric hydrogenation
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Excellent enantioselectivities and reactivities were observed in the hydrogenation of a variety of methyl (Z)-β-aryl-β-(acetyl-amino)acrylates in the presence of a rhodium catalyst with the chiral ligand binapine (see scheme). This bisbinaphthophosphepine
- Tang, Wenjun,Wang, Weimin,Chi, Yongxiang,Zhang, Xumu
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p. 3509 - 3511
(2007/10/03)
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- Preparation and asymmetric hydrogenation of β-aryl-substituted β-acylaminoacrylates
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The Rh-catalyzed asymmetric hydrogenation of β-aryl-substituted (E)-β-acylaminoacrylates, which were isolated for the first time, with, for example [Rh{(R,R)- (Et-FerroTANE)}(nbd)]+ as catalyst (see picture) proceeds under very mild conditions
- You, Jingsong,Drexler, Hans-Joachim,Zhang, Songlin,Fischer, Christine,Heller, Detlef
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p. 913 - 916
(2007/10/03)
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- Highly effective chiral ortho-substituted BINAPO ligands (o-BINAPO): Applications in Ru-catalyzed asymmetric hydrogenations of β-aryl-substituted β-(acylamino)acrylates and β-keto esters
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A novel family of chiral ortho-substituted BINAPO ligands (o-BINAPO) were synthesized from BINOL, and their Ru complexes were highly efficient catalysts for asymmetric hydrogenation of β-aryl-substituted β-(acylamino)acrylates and β-aryl-substituted β-keto esters. The Ru-bisphosphinite catalysts can tolerate an E/Z mixture of β-aryl-substituted β-(acylamino)acrylates. These highly enantioselective hydrogenations provide a useful way to prepare β-aryl-substituted β-amino acids and β-hydroxyl acids. Copyright
- Zhou, Yong-Gui,Tang, Wenjun,Wang, Wen-Bo,Li, Wenge,Zhang, Xumu
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p. 4952 - 4953
(2007/10/03)
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- Highly efficient synthesis of chiral β-amino acid derivatives via asymmetric hydrogenation
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(Formula Presented) The Rh-TangPhos complex is an efficient hydrogenation catalyst for making chiral β-amino acid derivatives. With the Rh-TangPhos system, high enantioselectivities (up to 99.6%) and turnover numbers have been obtained in the hydrogenatio
- Tang, Wenjun,Zhang, Xumu
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p. 4159 - 4161
(2007/10/03)
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