- P-Chirogenic Triazole-Based Phosphine: Synthesis, Coordination Chemistry, and Asymmetric Catalysis
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Herein we report the synthesis of a new P-chirogenic triazole-based phosphine according to the ephedrine methodology. Upon reaction with late transition-metal derivatives, RhI and PdII, phosphine-triazole forms complexes with bidenta
- Bayardon, Jér?me,Rousselle, Benjamin,Rousselin, Yoann,Bonnin, Quentin,Malacea-Kabbara, Raluca
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- Extensive re-investigations of pressure effects in rhodium-catalyzed asymmetric hydrogenations
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The catalytic hydrogenation of three prochiral substrates methyl Z-α-acetamidocinnamate (MAC), methyl 2-acetamidoacrylate (M-Acrylate) and ethyl 4-methyl-3-acetamido-2-propanoate (EEMAP) with rhodium precursors complexed with chiral diphosphines is report
- Alame, Mohamad,Pestre, Nathalie,De Bellefona, Claude
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- Phosphorus-Chiral Analogues of 1,1′-Bis(diphenylphosphino)ferrocene: Asymmetric Synthesis and Application in Highly Enantioselective Rhodium-Catalyzed Hydrogenation Reactions
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Five new ferrocene ligands 1a-e (1 = 1,1′-bis(aryl-phenylphosphino)ferrocene with aryl residues a = 1-naphthyl, b = 2-naphthyl, c = 2-anisyl, d = 2-biphenylyl, and e = 9-phenanthryl) bearing stereogenic phosphorus atoms have been prepared in enantiomerica
- Nettekoven, Ulrike,Kamer, Paul C.J.,Van Leeuwen, Piet W.N.M.,Widhalm, Michael,Spek, Anthony L.,Lutz, Martin
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- Evidence for the importance of conformational equilibria in Rh-diphosphine complexes for the enantioselection in Rh-catalyzed asymmetric hydrogenation
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The conformations of the chelate cycles in the X-ray structures of norbornadiene- and cyclooctadiene-rhodium complexes of (R,R)-1,2-bis[(o- methylphenyl)phenylphosphino]ethane are dramatically different. Nevertheless, they demonstrate the same sense of enantioselection in asymmetric hydrogenation of dehydroamino acids.
- Tsuruta, Hideyuki,Imamoto, Tsuneo,Yamaguchi, Kentaro,Gridnev, Ilya D.
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- Synthesis of (-)-(4R,5R)-4,5-bis[di-3',(2',6'- dimethoxypyridyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxolane and its application in the Rh-catalyzed asymmetric hydrogenation reactions
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The chiral ligand (-)-(4R,5R)-4,5-bis[di-3'-(2',6'- dimethoxypyridyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxolane 3 [(R,R)-Py*- DIOP] was synthesized via a key intermediate bis[3-(2,6- dimethoxypyridyl)]phosphineborane 9. The asymmetric hydrogenation of pr
- Hu, Wenhao,Chen, Chih-Chiang,Xue, Guoping,Chan, Albert S. C.
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- Further insight in the minor/major concept using hydrogen pressure effect in asymmetric hydrogenation
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The catalytic system prepared from [Rh(COD)2]BF4 and (R,R)-Me-BPE provides a spectacular detrimental hydrogen pressure effect on ee from 94% down to 56% in the hydrogenation of methylacrylate, whereas it has a strong beneficial effect on the hydrogenation of E-emap (from 42% up to 72%). The kinetic parameters have been determined for both systems and have helped to identify the most enantioselective controlling steps (MECS). Accordingly, further explanations for the structure-ee and hydrogen pressure relationship are proposed.
- Aloui, A.,De Bellefon, C.,Delbecq, F.,Sautet, P.
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- Influence of different types of amphiphiles on the rhodium(I) complex-catalyzed asymmetric hydrogenation of (Z)-methyl-α-acetamidocinnamate in aqueous medium
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The homogeneous asymmetric hydrogenation of (Z)-methyl-α-acetamidocinnamate catalyzed by the system [Rh(COD)2]BF4 + 1.1 BPPM could be effected in water as medium in the presence of micelle-forming amphiphiles. Both activity and enant
- Grassert,Paetzold,Oehme
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- Hydrophosphination of Bicyclo[1.1.0]butane-1-carbonitriles
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Hydrophosphination of bicyclo[1.1.0]butyl nitriles with phosphine boranes and phosphites provided novel cyclobutyl-P derivatives. The reaction generally favors the syn-diastereomer, and the nitrile can be reduced and converted to other functional groups, thus enabling the preparation of bidentate ligands that access new conformational space by virtue of their attachment to the torsionally malleable but sterically restrictive cyclobutane scaffold. The enantioselective hydrogenation of dehydrophenylalanine using a bidentate phosphine-phosphite ligand illustrates the synthetic utility of the newly prepared scaffold.
- Milligan, John A.,Busacca, Carl A.,Senanayake, Chris H.,Wipf, Peter
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- A one-step, modular route to optically-active diphos ligands
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A chlorosilane elimination reaction has been developed that allows the efficient synthesis of optically pure C1-symmetric, C1-backboned diphosphines with a wide variety of stereoelectronic characteristics.
- Louise Hazeland,Chapman, Andy M.,Pringle, Paul G.,Sparkes, Hazel A.
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- Synthesis of a new bulky phosphite ligand and its application in the enantioselective hydrogenation
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A new bulky phosphite ligand was synthesized and tested in the asymmetric Rh-catalyzed hydrogenation of a series of substrates, including dimethyl itaconate (up to 95% ee), α- and β-dehydroamino acid derivatives (up to 88% and 76% ee, respectively). In th
- Sokolovskaya, Marina V.,Lyubimov, Sergey E.,Mikhel, Igor S.,Birin, Kirill P.,Davankov, Vadim A.
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- Enantiomerically pure 1,2,5-triphenylphospholane through the synthesis and resolution of the chiral trans-(2,5)-diphenylphospholanic acid
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The synthesis and resolution of trans-(2,5)-diphenylphospholanic acid 7 is described. The phosphinic acid 7 was converted into optically active (1,2,5)-triphenylphospholane 5 which was used as a chiral ligand in Rh- catalyzed hydrogenation of N-acetyl deh
- Guillen, Frederic,Fiaud, Jean-Claude
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- Asymmetric hydrogenation of enamides with catalysts containing chiral thiourea ligands
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The asymmetric reduction of enamides with molecular hydrogen and catalytic amounts of rhodium, iridium or ruthenium complexes containing chiral N,S-ligands is reported. Various enantiomerically pure mono- and dithioureas were examined. The C2-s
- Tommasino,Casalta, Magali,Breuzard, Jeremy A.J,Lemaire, Marc
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- Parallel synthesis and screening of polymer-supported phosphorus- stereogenic aminophosphane-phosphite and -phosphinite ligands
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(Chemical Equation Presented) Bound to Ps: An efficient, rapid, parallel solid-phase synthesis of a series of resin-bound P-stereogenic aminophosphane-phosphinite and -phosphite ligands is developed (see scheme).The ligands form active hydrogenation catal
- Den Heeten, Rene,Swennenhuis, Bert H. G.,Van Leeuwen, Piet W. N. M.,De Vries, Johannes G.,Kamer, Paul C. J.
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- Scorpio-Ligand: Synthesis of Biphenyl-Dihydroazepine Phosphoramidite Ligands for Asymmetric Hydrogenation
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A novel dihydroazepine-bridged BIPHEP phosphoramidite ligand with an amino acid moiety in the backbone was synthesized and evaluated in the Rh-catalyzed asymmetric hydrogenation. The scorpion tail-like amino acid backbone is capable of hydrogen bond forma
- Auras, Stefanie,Trapp, Oliver
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- Rhodium-catalyzed reduction of α-amino acid precursors using chiral 4-(diphenylphosphanyl)-1-(dialkylamino)butane ligands
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The enantioselectivity of the hydrogenation of some unsaturated amino acids using rhodium complexes in association with chiral 4-(diphenylphosphanyl)-1-(dialkylamino)butane ligands is higher (ee values of up to 60%) in water as the solvent in the presence
- Robert, Fabien,Sinou, Denis
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- Rhodium/olefin-catalyzed reaction of arylboronic acids with an α-acetamido acrylic ester: Mizoroki-Heck-type reaction versus asymmetric conjugate addition
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In this paper we present our results concerning the rhodium/olefin-catalyzed reaction of arylboronic acids with an α-acetamido acrylic ester. With a chiral norbornadiene ligand rather low enantioselectivities (up to 21% ee) were obtained. Besides the expected conjugate adduct, we also observed the formation of a significant amount of Mizoroki-Heck-type product. The ratio of the conjugate adduct/Mizoroki-Heck product could be adjusted by a proper choice of the olefin ligand.
- Noel, Timothy,Goek, Yasar,Eycken, Johan Van der
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- Mono- versus bidentate ligands in rhodium-catalyzed asymmetric hydrogenation. A comparative rate study
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(Matrix presented) Bidentate chiral phosphines are no longer essential for achieving a fast and highly enantioselective hydrogenation of α- or β-dehydroamino acid derivatives. In particular, a readily accessible and stable monodentate phosphoramidite can
- Pena, Diego,Minnaard, Adriaan J.,De Vries, Andre H. M.,De Vries, Johannes G.,Feringa, Ben L.
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- Mixtures of ionic liquids and water as a medium for efficient enantioselective hydrogenation and catalyst recycling
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In a screening of ligands, ionic liquids and reaction conditions in the Rh-catalyzed hydrogenation of enamides, a novel multi-phase reaction system consisting of an ionic liquid (IL) and water (wet ILs) was found to give the most promising results. In many cases such IL/water combinations were superior compared to conventional organic solvents and biphasic ILs/organic co-solvents media with respect to catalytic performance as well as to catalyst separation and recycling. So far, the best results were obtained with Rh-ferrocenyl- diphosphine catalysts (>99% ee). Generally, somewhat lower ees were observed at higher pressure. However, this effect was less pronounced with wet ILs than with conventional solvents. It is shown that IL/water combination allow repeated catalyst recycling without significant loss of activity and that industrially relevant turnover numbers of > 10,000 can be obtained.
- Pugin,Studer,Kuesters,Sedelmeier,Feng
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- PHIP NMR spectroscopy in ionic liquids: Influence of salts on the intensity of polarization signals
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Parahydrogen-induced dynamic nuclear polarization NMR spectroscopy (PHIP) in ionic liquids leads to weak or no polarization signals, depending on the type of experiment. We demonstrate that the intensity of polarization is directly correlated to the concentration of the ionic liquids. High ion concentration is connected to fast T1 relaxation, resulting in annihilation of the polarization signals.
- Br?hl, Andreas,Giernoth, Ralf
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- Rapid Synthesis of Chiral 1,2-Bisphosphine Derivatives through Copper(I)-Catalyzed Asymmetric Conjugate Hydrophosphination
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1,2-Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)-catalyzed asymmetric hydrophosphination of α,β-unsaturated phosphine sulfides was developed wi
- Xiao, Jun-Zhao,Yin, Liang,Yue, Wen-Jun,Zhang, Shuai
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- Optically active 1,1′-di-tert-butyl-2,2′-dibenzophosphetenyl: A highly strained P-stereogenic diphosphine ligand
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Both enantiomers of 1,1′-di-tert-butyl-2,2′-dibenzophosphetenyl were prepared from 2-bromobenzyl chloride and tert-butyldichlorophosphine. These ligands exhibited excellent enantioselectivity in the rhodium catalyzed asymmetric hydrogenation of methyl α-a
- Imamoto, Tsuneo,Crepy, Karen V.L.,Katagiri, Kosuke
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- A novel approach for investigating enantioselectivity in asymmetric hydrogenation
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A new and convenient method for investigating the relationship between the position of the enantiodetermining sites in chiral phosphine ligands and enantioselectivity in asymmetric hydrogenation is proposed. We have also synthesized four new diphosphine l
- Shimizu, Hideo,Ishizaki, Takero,Fujiwara, Takahiro,Saito, Takao
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- Mechanistically Guided One Pot Synthesis of Phosphine-Phosphite and Its Implication in Asymmetric Hydrogenation
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Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an O-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72 %). When L1 was treated with [Rh], 31P NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92 %). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1–2 bar H2 pressure, at room temperature. The practical relevance of L1 is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.
- Sen, Anirban,Kumar, Rohit,Pandey, Swechchha,Vipin Raj,Kumar, Pawan,Vanka, Kumar,Chikkali, Samir H.
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supporting information
(2022/01/11)
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- Chiral phosphine-phosphoramidite ester ligand as well as preparation method and application thereof
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The invention provides a method for preparing a phosphine-phosphoramidite ester ligand from a chiral beta-aminophosphine intermediate and an application of the phosphine-phosphoramidite ester ligand in an asymmetric reaction. Chiral N-(2-(phosphoryl)-1-phenethyl) amide is prepared from the chiral beta-aminophosphine intermediate through an asymmetric hydrogenation reaction of (Z)-(alpha-aryl-beta-phosphoryl) alkenyl amide, and then hydrolysis reduction. The preparation method comprises the following steps: dissolving newly-prepared chlorinated phosphite in toluene, adding a solution formed by dissolving the chiral phosphine-amine compound and triethylamine in toluene into an ice-water bath according to a molar ratio of the chiral phosphine-amine compound to the chlorinated phosphite to the triethylamine of 1: (1-2): (3-5), heating the reaction solution to 18-25 DEG C, stirring and reacting for 10-30 hours, filtering, and carrying out column chromatography to remove the solvent, and recrystallizing to obtain the required phosphine-phosphoramidite ligand. According to the present invention, the asymmetric hydrogenation reaction of the catalyst formed by the ligand and the metal precursor on the double bonds such as C = C, C = N, C = O and the like can achieve the enantioselectivity of 99%; the catalyst is high in activity, and TON reaches up to 10000.
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Paragraph 0054-0057; 0081-0086
(2021/05/22)
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- Concise synthesis and applications of enantiopure spirobiphenoxasilin-diol and its related chiral ligands
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The development of chiral architectures for chiral ligand and catalyst discovery is essential for asymmetric catalysis. Herein, we report the concise synthesis of a Si-centered spirocyclic skeleton, spirobiphenoxasilin-diol (SPOSiOL), and its derived chiral ligands. Using the chemical resolution method, the optical SPOSiOL could be obtained in high yield on a gram scale. Preliminary studies indicated that this ligand scaffold has great potential in transition metal-catalyzed asymmetric reactions. This finding further highlights that the Si-centered spirocyclic scaffolds are of great value in asymmetric catalysis. This journal is
- Liu, Tao,Wang, Biqin,Wang, Peng,Wu, Yichen,Xu, Wen-Qiang,Yang, Lei
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supporting information
p. 13365 - 13368
(2021/12/17)
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- SPHENOL, A New Chiral Framework for Asymmetric Synthesis
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Privileged chiral catalysts have found tremendous applications and thus immensely advanced asymmetric synthesis in the past few decades. However, truly privileged chiral frameworks are still extremely limited. Thus, the search for and development of new v
- Zhang, Ronghua,Ge, Shulin,Sun, Jianwei
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supporting information
p. 12445 - 12449
(2021/08/30)
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- Chiral spiro compound and preparation method and application thereof
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The invention relates to the technical field of organic chemistry, in particular to a chiral spiro compound as well as a preparation method and application thereof. The chiral spiro compounds include the compounds or enantiomers or racemates of the formul
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Paragraph 0208-0217
(2021/10/27)
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- Sustainable System for Hydrogenation Exploiting Energy Derived from Solar Light
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Herein described is a sustainable system for hydrogenation that uses solar light as the ultimate source of energy. The system consists of two steps. Solar energy is captured and chemically stored in the first step; exposure of a solution of azaxanthone in ethanol to solar light causes an energy storing dimerization of the ketone to produce a sterically strained 1,2-diol. In the second step, the chemical energy stored in the vicinal diol is released and used for hydrogenation; the diol offers hydrogen onto alkenes and splits back to azaxanthone, which is easily recovered and reused repeatedly for capturing solar energy.
- Ishida, Naoki,Kamae, Yoshiki,Ishizu, Keigo,Kamino, Yuka,Naruse, Hiroshi,Murakami, Masahiro
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supporting information
p. 2217 - 2220
(2021/02/16)
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- Asymmetric Reduction of Aromatic α-Dehydroamino Acid Esters with Water as Hydrogen Source
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The asymmetric reduction of aromatic α-dehydroamino acid esters with water as the hydrogen source was developed by a Rh/Cu co-catalytic system. The reaction tolerates various functional groups, providing a valuable synthetic tool to access chiral α-amino acid esters readily. Moreover, the present methodology also was applied in the cost-effective and easy to handle preparation of chiral deuterated α-amino esters by using D2O.
- Dai, Yuze,Chen, Jingchao,Wang, Zheting,Wang, Ting,Wang, Lin,Yang, Yong,Qiao, Xingfang,Fan, Baomin
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supporting information
p. 7141 - 7147
(2021/05/29)
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- OPTICALLY ACTIVE BISPHOSPHINO METHANE AND PRODUCTION METHOD THEREFOR, AND TRANSITION METAL COMPLEX AND ASYMMETRIC CATALYST
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PROBLEM TO BE SOLVED: To provide a novel optically active bisphosphine methane that is useful as a ligand for an asymmetric catalyst, has excellent oxidation resistance in the air, and is easy to handle, and to provide a transition metal complex using, as
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Paragraph 0071-0073
(2021/02/10)
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- 2,3-BISPHOSPHINOPYRAZINE DERIVATIVE, METHOD FOR PRODUCING SAME, TRANSITION METAL COMPLEX, ASYMMETRIC CATALYST, AND METHOD FOR PRODUCING ORGANIC BORON COMPOUND
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Provided is a 2,3-bisphosphinopyrazine derivative represented by the following general formula (1), wherein R1, R2, R3, and R4 represent an optionally substituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group, an optionally substituted adamantyl group, or an optionally substituted phenyl group, R5 represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group, each R5 may be the same group or a different group, R6 represents a monovalent substituent, n denotes an integer of 0 to
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Paragraph 0262-0264; 0270-0271
(2021/02/19)
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- Ferrocene boron-containing chiral diphosphine ligand as well as preparation method and application thereof
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The invention relates to a ferrocene boron-containing chiral diphosphine ligand and a preparation method and application thereof. The ferrocene boron-containing chiral diphosphine ligand is a compound shown in the formula (I), and the ligand can be comple
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Paragraph 0099-0101
(2021/07/17)
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- Chiral polycyclic tropane compound as well as preparation method and application thereof
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The invention provides a chiral polycyclic tropane compound as well as a preparation method and application thereof. The invention specifically relates to a tropane compound shown as a formula I, or a salt thereof, or a stereoisomer thereof, or a crystal form thereof, and a preparation method and application thereof. The preparation method disclosed by the invention is simple in process, mild in reaction condition and high in yield, and the obtained product has excellent enantioselectivity and diastereoselectivity. Experiments prove that the tropane compound can effectively inhibit various tumor cells, especially lung cancer cells, melanoma cells, breast cancer cells, in-situ pancreatic cancer cells and pancreatic cancer cells, so that the compound has a wide prospect in preparation of drugs for preventing and/or treating tumors.
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- Asymmetric Full Saturation of Vinylarenes with Cooperative Homogeneous and Heterogeneous Rhodium Catalysis
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Homogeneous and heterogeneous catalyzed reactions can seldom operate synergistically under the same conditions. Here we communicate the use of a single rhodium precursor that acts in both the homogeneous and heterogeneous phases for the asymmetric full saturation of vinylarenes that, to date, constitute an unmet bottleneck in the field. A simple asymmetric hydrogenation of a styrenic olefin, enabled by a ligand accelerated effect, accounted for the facial selectivity in the consecutive arene hydrogenation. Tuning the ratio between the phosphine ligand and the rhodium precursor controlled the formation of homogeneous and heterogeneous catalytic species that operate without interference from each other. The system is flexible in terms of both the chiral ligand and the nature of the external olefin. We anticipate that our findings will promote the development of asymmetric arene hydrogenations.
- Andersson, Pher G.,Massaro, Luca,Peters, Bram B. C.,Wu, Haibo,Yang, Jianping,Zheng, Jia
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supporting information
p. 20377 - 20383
(2021/12/03)
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- Prolinol as a Chiral Auxiliary in Organophosphorus Chemistry
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Several strategies for the development of the synthesis of P-chiral organophosphorus compounds with (L)-prolinol as a source of chirality have been examined. A reaction of L-prolinol with a set of different alkyl/arylphosphonous acid diamides led in most of the cases to the quantitative formation of the appropriate bicyclic oxazaphospholidines with complete diastereo and enantioselectivity. The latter were reacted with BH3 complex and the formed borane analogues were submitted to structural modifications leading to tertiary phosphine-boranes. Additionally, the effectiveness of oxazaphospholidines as ligands in transition metal asymmetric catalysis has been tested in hydrogenation of dehydroaminoacid esters and imine.
- Kozio?, Anna E.,W?odarczyk, Adam
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p. 1931 - 1941
(2021/04/06)
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- P-chirogenic diphosphazanes with axially chiral substituents and their use in rh-catalyzed asymmetric hydrogenation
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A convenient synthesis of enantiopure P-chirogenic diphosphazanes incorporating bulky bisphenol and 1,1′-bi-2-naphtholderived substituents via the functionalization of a readily accessible enantiopure lithium phosphinoamide with chlorophosphoridites was developed. Since the product requires no subsequent deprotection, the protocol provides an easy, convenient synthesis of P-chirogenic ligands on the gram scale. The ligands were applied in the Rh-catalyzed asymmetric hydrogenation of benchmark substrates furnishing enantiomeric excess values up to 96%.
- Moritz, Jan-Ole,Chakrabortty, Soumyadeep,Bernd H. Mu.ller,Spannenberg, Anke,Kamer, Paul C. J.
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p. 14537 - 14544
(2020/12/29)
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- P-Stereogenic N-Phosphine-Phosphite Ligands for the Rh-Catalyzed Hydrogenation of Olefins
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We have identified a successful family of simple P-stereogenic N-phosphine-phosphite ligands for the Rh-catalyzed asymmetric hydrogenation of olefins. These catalysts show excellent enantiocontrol for α-dehydroamino acid derivatives and α-enamides (ee's u
- Biosca, Maria,De La Cruz-Sánchez, Pol,Diéguez, Montserrat,Pàmies, Oscar
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p. 4730 - 4739
(2020/05/08)
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- Diaza-Crown Ether-Bridged Chiral Diphosphoramidite Ligands: Synthesis and Applications in Asymmetric Catalysis
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A small library of diaza-crown ether-bridged chiral diphosphoramidite ligands was prepared. In the rhodium-catalyzed asymmetric hydrogenation and hydroformylation reactions, these ligands exhibited distinct properties in catalytic activity and/or enantioselectivity. Hydrogenated products with opposite absolute configurations could be obtained in high yields with excellent ee values by utilizing (S,S)-L1 and (S,S)-L3, respectively. Meanwhile, the addition of alkali metal cations caused variations in catalytic outcomes, showing the supramolecular tunability of these Rh/diphosphoramidite catalytic systems.
- Luo, Yier,Ouyang, Guanghui,Tang, Yuping,He, Yan-Mei,Fan, Qing-Hua
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p. 8176 - 8184
(2020/07/15)
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- BISPHOSPHINOHEXAFLUOROCYCLOPENTENE DERIVATIVE, MANUFACTURING METHOD THEREOF, TRANSITION METAL COMPLEX, AND ORGANIC COMPOUND MANUFACTURING METHOD BASED ON THE SAME
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PROBLEM TO BE SOLVED: To provide an asymmetric catalyst allowing synthesis of an organic compound having appealing properties absent in existing organic compounds. SOLUTION: The invention provides an asymmetric catalyst comprising a transition metal compl
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Paragraph 0181-0185
(2020/08/29)
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- Development of robust heterogeneous chiral rhodium catalysts utilizing acid?base and electrostatic interactions for efficient continuous-flow asymmetric hydrogenations
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Heterogeneous chiral Rh catalysts based on acid?base and electrostatic interactions have been developed. The robust catalysts demonstrate high activity and selectivity in the continuous-flow asymmetric hydrogenation of a wide variety of enamides and dehyd
- Saito, Yuki,Kobayashi, Shu
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supporting information
p. 16546 - 16551
(2020/11/09)
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- Topology-Based Functionalization of Robust Chiral Zr-Based Metal-Organic Frameworks for Catalytic Enantioselective Hydrogenation
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The design and development of robust and porous supported catalysts with high activity and selectivity is extremely significant but very challenging for eco-friendly synthesis of fine chemicals and pharmaceuticals. We report here the design and synthesis of highly stable chiral Zr(IV)-based MOFs with different topologies to support Ir complexes and demonstrate their network structures-dependent asymmetric catalytic performance. Guided by the modulated synthesis and isoreticular expansion strategy, five chiral Zr-MOFs with a flu or ith topology are constructed from enantiopure 1,1′-biphenol-derived tetracarboxylate linkers and Zr6, Zr9, or Zr12 clusters. The obtained MOFs all show high chemical stability in boiling water, strongly acidic, and weakly basic aqueous solutions. The two flu MOFs featuring the dihydroxyl groups of biphenol in open and large cages, after sequential postsynthetic modification with P(NMe2)3 and [Ir(COD)Cl]2, can be highly efficient and recyclable heterogeneous catalysts for hydrogenation of α-dehydroamino acid esters with up to 98% ee, whereas the three ith MOFs featuring the dihydroxyl groups in small cages cannot be installed with P(NMe2)3 to support the Ir complex. Incorporation of Ir-phosphorus catalysts into Zr-MOFs leads to great enhancement of their chemical stability, durability, and even stereoselectivity. This work therefore not only advances Zr-MOFs as stable supports for labile metal catalysts for heterogeneous asymmetric catalysis but also provides a new insight into how highly active chiral centers can result due to the framework topology.
- Jiang, Hong,Zhang, Wenqiang,Kang, Xing,Cao, Ziping,Chen, Xu,Liu, Yan,Cui, Yong
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p. 9642 - 9652
(2020/07/02)
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- Nickel-Catalyzed Asymmetric Hydrogenation of 2-Amidoacrylates
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Earth-abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2-amidoacrylates, affording the chiral α-amino acid esters in quantitative yields and excellent enantioselectivity (up to 96 % ee). The active catalyst component was studied by NMR and HRMS, which helped us to realize high catalytic efficiency on a gram scale with a low catalyst loading (S/C=2000). The hydrogenated products could be simply converted into chiral α-amino acids, β-amino alcohols, and their bioactive derivatives. Furthermore, the catalytic mechanism was investigated using deuterium-labeling experiments and computational calculations.
- Chen, Jianzhong,Gridnev, Ilya D.,Hu, Yawen,Li, Bowen,Zhang, Wanbin,Zhang, Zhenfeng
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p. 5371 - 5375
(2020/02/15)
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- A Bulky Three-Hindered Quadrant Bisphosphine Ligand: Synthesis and Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes
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A bulky three-hindered quadrant bisphosphine ligand, di-1-adamantylphosphino(tert-butylmethylphosphino)methane, named BulkyP*, has been synthesized via a convergent short pathway with chromatography-free procedures. The ligand is a crystalline solid and can be readily handled in air. Its rhodium(I) complex exhibits very high enantioselectivities and catalytic activities in the asymmetric hydrogenation of functionalized alkenes.
- Sawatsugawa, Yuuki,Tamura, Ken,Sano, Natsuhiro,Imamoto, Tsuneo
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supporting information
p. 8874 - 8878
(2019/11/03)
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- Enantioselective Synthesis of 3,3′-Diaryl-SPINOLs: Rhodium-Catalyzed Asymmetric Arylation/BF3-Promoted Spirocyclization Sequence
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The enantioselective synthesis of a series of C2-symmetric 3,3′-diarylated 1,1′-spirobiindane-7,7′-diols (3,3′-diaryl-SPINOLs) was developed by sequential Rh-catalyzed twofold asymmetric conjugate arylation/BF3-promoted diastereoselective spirocyclization (>20:1 d.r. and >99 % ee for all examples). Some phosphoramidite ligands were prepared from the 3,3′-Ph-SPINOL and applied to several catalytic asymmetric reactions, and the 3,3′-diarylated ligands showed higher enantioselectivities than the privileged nonsubstituted ligands.
- Yin, Long,Xing, Junhao,Wang, Yuhan,Shen, Yue,Lu, Tao,Hayashi, Tamio,Dou, Xiaowei
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supporting information
p. 2474 - 2478
(2019/01/30)
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- EBINOL axial chiral compound as well as synthesis method and application thereof
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The invention belongs to the field of axial chiral compounds, and discloses an EBINOL axial chiral compound. The EBINOL axial chiral compound has the following general formula(the formula is shown inthe description), wherein R and R are respectively
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Paragraph 0238; 0246-0249
(2019/08/02)
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- Phosphite-thioether/selenoether Ligands from Carbohydrates: An Easily Accessible Ligand Library for the Asymmetric Hydrogenation of Functionalized and Unfunctionalized Olefins
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A large family of phosphite-thioether/selenoether ligands has been easily prepared from accessible L-(+)-tartaric acid and D-(+)-mannitol and applied in the M-catalyzed (M=Ir, Rh) asymmetric hydrogenation of a broad number of substrates (46 in total). Its highly modular architecture has been crucial to maximize the catalytic performance. Improving most of the reported approaches, this ligand family presents a broad substrate scope. By selecting the ligand parameters high enantioselectivities (ee's up to 99 %) have therefore been achieved in a broad range of both, functionalized and unfunctionalized substrates. Interestingly, both enantiomers of the hydrogenation products can be usually achieved by changing the ligand parameters.
- Margalef, Jèssica,Borràs, Carlota,Alegre, Sabina,Alberico, Elisabetta,Pàmies, Oscar,Diéguez, Montserrat
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p. 2142 - 2168
(2019/04/13)
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- ENANTIOPURE TERPHENYLS WITH TWO ORTHO-ATROPISOMERIC AXES
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Enantiopure terphenyl presenting two ortho-located chiral axes having the following structural formula (I) : their process of synthesis and their use as mono or bidentate ligands for asymmetric organometallic reactions, as organocatalysts, as chiral base
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Page/Page column 29-30
(2019/07/19)
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- Inducing Enantioselectivity in a Dynamic Catalyst by Supramolecular Interlocking
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The design of a new class of fluxional biphenyl bisphosphinite (BIBIPHOS) ligands decorated with amino acid-based diamide interaction sites is reported that undergo spontaneous desymmetrization. Hydrogenation of prochiral alkenes using Rh-BIBIPHOS results
- Scholtes, Jan Felix,Trapp, Oliver
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supporting information
p. 6306 - 6310
(2019/04/03)
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- Enantioselectivity Induced by Stereoselective Interlocking: A Novel Core Motif for Tropos Ligands
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Well-defined supramolecular interactions are a powerful tool to control the stereochemistry of a catalytic reaction. In this paper, we report a novel core motif for fluxional 2,2′-biphenyl ligands carrying (S)-amino acid-derived interaction sites in 5,5′-
- Scholtes, Jan Felix,Trapp, Oliver
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p. 11707 - 11714
(2019/08/16)
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- Chiral bisphosphine ligands based on quinoline oligoamide foldamers: application in asymmetric hydrogenation
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A series of chiral bisphosphine ligands were designed and synthesized based on single-handed quinoline oligoamide foldamers. The bisphosphine ligands can coordinate with Rh(cod)2BF4 in a 1 : 1 stoichiometry and the resulted chiral Rh(i) catalysts were applied in the asymmetric hydrogenation of α-dehydroamino acid esters, in which excellent conversions and promising levels of enantioselectivity were achieved.
- Zheng, Lu,Zheng, Dan,Wang, Yanru,Yu, Chengyuan,Zhang, Kun,Jiang, Hua
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supporting information
p. 9573 - 9577
(2019/11/20)
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- “Backdoor Induction” of Chirality: Trans-1,2-cyclohexanediamine as Key Building Block for Asymmetric Hydrogenation Catalysts
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This paper describes the synthesis and characterization of 21 chiral monodentate ligands L, assembled of three building blocks utilizing amide bonds: a metal binding triphenylphosphine, a chiral cyclic diamine and an additional substituent for fine-tuning the steric and/or electronic properties. Cis square-planar metal complexes of RhI and PtII with ML2 stoichiometry have been prepared and characterized by spectroscopic methods (NMR, IR, UV-Vis, CD) and DFT calculations. A key feature of the metal complexes is a prochiral metal coordination sphere and “backdoor induction” of chirality from a distant chiral source via an outer-coordination sphere, well-defined by aromatic stacking and hydrogen-bonding. The rhodium complexes were used as catalysts in asymmetric hydrogenation of α,β-dehydroamino acids with excellent yield and selectivity (up to 97 % ee), strongly supporting the “backdoor induction” hypothesis.
- Glasovac, Zoran,Kirin, Sre?ko I.,Kokan, Zoran,Opa?ak, Sa?a,Peri?, Berislav
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supporting information
p. 2115 - 2128
(2019/01/04)
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- Organophosphorus compound based on [2, 2] paracycloalkane skeleton and intermediate thereof, and preparation method and application thereof
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The invention discloses an organophosphorus compound based on [2, 2] paracycloalkane skeleton and intermediates thereof, a preparation method and an application thereof. The organophosphorus compoundincluding phosphinate ligands, phosphite ligands, phosph
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Paragraph 0044; 0096-0098
(2019/05/08)
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- Electrochemical Hydrogenation with Gaseous Ammonia
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As a carbon-free and sustainable fuel, ammonia serves as high-energy-density hydrogen-storage material. It is important to develop new reactions able to utilize ammonia as a hydrogen source directly. Herein, we report an electrochemical hydrogenation of alkenes, alkynes, and ketones using ammonia as the hydrogen source and carbon electrodes. A variety of heterocycles and functional groups, including for example sulfide, benzyl, benzyl carbamate, and allyl carbamate were well tolerated. Fast stepwise electron transfer and proton transfer processes were proposed to account for the transformation.
- Li, Jin,He, Lingfeng,Liu, Xu,Cheng, Xu,Li, Guigen
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supporting information
p. 1759 - 1763
(2019/01/16)
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- Asymmetric Synthesis of Functionalized Phenylalanine Derivatives via Rh-Catalyzed Conjugate Addition and Enantioselective Protonation Cascade
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The asymmetric conjugate addition of arylboronic acids to N-phthalimidodehydroalanine 1i catalyzed by Rh(I)/L1a enables the facile preparation of chiral functionalized phenylalanines. The reaction proceeds by a conjugate addition and enantioselective protonation cascade, affording a rhodium enolate that undergoes re-face protonation. The reaction tolerates various arylboronic acids and can be used in the gram-scale synthesis of (S)-phenylalanine hydrochloride, demonstrating the reaction scope and the synthetic feasibility of the process.
- Jian, Jia-Hong,Zeng, Hao-Wei,Kuo, Ting-Shen,Wu, Ping-Yu,Wu, Hsyueh-Liang
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supporting information
p. 9468 - 9472
(2019/11/28)
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- An Atropos Chiral Biphenyl Bisphosphine Ligand Bearing Only 2,2′-Substituents and Its Application in Rh-Catalyzed Asymmetric Hydrogenation
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An atropos chiral biphenyl bisphosphine ligand bearing only 2,2′-substituents was rationally designed and easily synthesized utilizing a bulky chiral t-butylmethylphosphino block. Computational results showed a large difference in the free energies betwee
- Jia, Jia,Ling, Zheng,Zhang, Zhenfeng,Tamura, Ken,Gridnev, Ilya D.,Imamoto, Tsuneo,Zhang, Wanbin
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supporting information
p. 738 - 743
(2017/12/26)
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- Structural Investigations on Enantiopure P–OP Ligands: A High-Performing P–OP Ligand for Rhodium-Catalysed Hydrogenations
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A second generation of phosphine–phosphite (P–OP) ligands, incorporating a more sterically bulky phosphite group than previous P–OP ligand designs, gave very efficient catalysts for the Rh-catalysed asymmetric hydrogenation of a diverse array of substrate
- Fernández-Pérez, Héctor,Balakrishna, Bugga,Vidal-Ferran, Anton
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p. 1525 - 1532
(2018/04/20)
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- Two Stereoinduction Events in One C?H Activation Step: A Route towards Terphenyl Ligands with Two Atropisomeric Axes
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Herein we disclose the synthesis of original chiral scaffolds—ortho-orientated terphenyls presenting two atropisomeric Ar–Ar axes. These unusual structures were built up by using the C?H activation approach, and remarkably, both chiral axes were controlled with excellent stereoselectivity in a single transformation. During the reaction, not only does atroposelective functionalization of a biaryl precursor occur to establish one stereogenic axis, but an unprecedented atropo-stereoselective C?H arylation also takes place to generate the second stereogenic element. These enantiomerically pure ortho-terphenyls show an original tridimensional structure and thus constitute a unique foundation for building up a library of enantiomerically pure bidentate ligands, such as the new ligands S/N-Biax and diphosphine BiaxPhos.
- Dherbassy, Quentin,Djukic, Jean-Pierre,Wencel-Delord, Joanna,Colobert, Fran?oise
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supporting information
p. 4668 - 4672
(2018/03/21)
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- Modular 1,1′-Ferrocenediyl-cored P-Stereogenic Diphosphines: ′′JDayPhos′′ Series and its Use in Rhodium(I)-Catalyzed Hydrogenation
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A novel ferrocene-based P-stereogenic diphospine ligand series dubbed JDayPhos was developed, which rhodium(I) complexes of some of its members exhibited excellent enantioselectivity (up to >99% ee) and high activity in asymmetric hydrogenation of β-unsubstituted or -substituted itaconates and α-methylene-γ-oxo-carboxylates. (Figure presented.).
- Poklukar, Ga?per,Stephan, Michel,Mohar, Barbara
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supporting information
p. 2566 - 2570
(2018/05/16)
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- A versatile biosynthetic approach to amide bond formation
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The development of versatile and sustainable catalytic strategies for amide bond formation is a major objective for the pharmaceutical sector and the wider chemical industry. Herein, we report a biocatalytic approach to amide synthesis which exploits the diversity of Nature's amide bond forming enzymes, N-acyltransferases (NATs) and CoA ligases (CLs). By selecting combinations of NATs and CLs with desired substrate profiles, non-natural biocatalytic pathways can be built in a predictable fashion to allow access to structurally diverse secondary and tertiary amides in high yield using stoichiometric ratios of carboxylic acid and amine coupling partners. Transformations can be performed in vitro using isolated enzymes, or in vivo where reactions rely solely on cofactors generated by the cell. The utility of these whole cell systems is showcased through the preparative scale synthesis of a key intermediate of Losmapimod (GW856553X), a selective p38-mitogen activated protein kinase inhibitor.
- Philpott, Helena K.,Thomas, Pamela J.,Tew, David,Fuerst, Doug E.,Lovelock, Sarah L.
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supporting information
p. 3426 - 3431
(2018/08/07)
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- METHOD FOR SYNTHESISING AMIDES
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The present invention relates to a method for synthesising amides that is of general applicability. The method may be performed in vitro or in vivo. Cell lines for use in the in vivo methods also form aspects of the invention. The method for synthesising a non-natural amide comprises: a. reaction of a carboxylic acid with a naturally occurring CoA ligase or a variant thereof; and b. reaction of the product of step a with an amine in the presence of a naturally occurring acyltransferase or a variant thereof; with the proviso that where the CoA ligase and acyltransferase are both naturally occurring, they are not derived from the same source species and do not act sequentially in a metabolic pathway; and with the proviso that the non-natural product is not N-(E)-p-coumaroyl-3-hydroxyanthranilic acid or N-(E)-p-caffeoyl-3-hydroxyanthranilic acid. Further, a method for producing an active pharmaceutical ingredient by the aforementioned method and host cells for carrying out said methods are envisaged.
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Page/Page column 41-42
(2018/03/06)
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- Chiral spirodihydroindene skeleton compound and preparation method thereof
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The invention discloses a chiral spirodihydroindene skeleton compound and a preparation method thereof. The chiral spirodihydroindene skeleton compound is represented by formula I or I'. The preparation method of the chiral spirodihydroindene skeleton compound is characterized in that an intramolecular Friedel-Crafts reaction of a compound represented by formula III is carried out in a solvent under the action of a catalyst to prepare the compound represented by formula I, and the catalyst is a Bronsted acid or a Lewis acid. The preparation method has the advantages of no chiral initial raw material or chiral resolution reagent, no chiral resolution steps, simplicity, simplicity in post-treatment, good economic property, environmental protection, high product yield, and realization of high optical purity and high chemical purity of the product. Transition metal catalyzed asymmetric reaction catalysts prepared by adopting the chiral spirodihydroindene skeleton compound have a substantial catalysis effect, the product yield is greater than 99%, and the ee value of the product higher than 99%.
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Paragraph 0338-0341
(2017/02/28)
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- 2-(1S)-Camphanoyloxy-2′-phosphanylbiphenyl Ligands – Synthesis, Structure, and Preliminary Tests in Transition-Metal Catalysis
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Diastereoisomer separation of the (1S)-camphanic acid 2-isopropylphenylphosphanyl-phenyl ester 1 exemplifies the potential of (1S)-camphanoyl chloride for enantiomer separation of hydroxyl-functional asymmetric phosphanes. Esterification of lithium 2′-phosphanylbiphenyl-2-olates, generated from the respective 2-OH or 2-OSiMe3 precursors 2aOH and 2b–fSi, furnished the 2-(1S)-camphanoyloxy-biphenylphosphanes 3a–c as 1:1 mixtures of diastereomers with low barriers for interconversion by rotation around the C–C axis (ΔG# = 70–73 kJ mol–1 for 3a and 3c by 31P VT NMR spectroscopy). The P-asymmetric compounds 3d–f form 1:1 mixtures of stereoisomers. There is a tendency to cocrystallization of two preferred diastereoisomers, as shown by the crystal structure analyses of 3dD and 3fD, and in solution, there is a tendency toward partial isomerization to the sterically less-favored atropisomers. The [RhCl(cod)(3dD)] complex 4dD, however, seems stable in solution. Excess 2dLi reacted with (1S)-camphanoyl chloride preferentially to form the (SP,Rax,1S) isomer, which was separated by crystallization as enantiopure 3dE, characterized by single-crystal XRD. Preliminary screening tests of this ligand in Rh-catalyzed asymmetric hydrogenations of N-(1-phenylvinyl)acetamide allowed high conversion and up to 59 % ee. Hydrosilylation of acetophenone proceeded with 78 % conversion and 48 % ee; Suzuki–Miyaura couplings of 1-bromo-2-naphthol with PhB(OH)2, in the presence of 3b/[Pd(OAc)2], gave yields up to 98 %.
- Wawrzyniak, Piotr,Kindermann, Markus K.,Thede, Gabriele,Thede, Richard,Jones, Peter G.,Enthaler, Stephan,Junge, Kathrin,Beller, Matthias,Heinicke, Joachim W.
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supporting information
p. 2762 - 2773
(2017/06/06)
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- Pyrene-tagged carbohydrate-based mixed P/S ligand: Spacer effect on the Rh(i)-catalyzed hydrogenation of methyl α-acetamidocinnamate
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The post-functionalization of a chiral catalyst offers the advantage of providing it with additional physical characteristics that, together with its enantioselective capacity, increase its overall synthetic value. Taking advantage of the modularity and p
- Moya, Juan Francisco,Rosales, Christian,Fernández, Inmaculada,Khiar, Noureddine
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p. 5772 - 5780
(2017/07/22)
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- Mechanochemical Encapsulation of Fullerenes in Peptidic Containers Prepared by Dynamic Chiral Self-Sorting and Self-Assembly
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Molecular capsules composed of amino acid or peptide derivatives connected to resorcin[4]arene scaffolds through acylhydrazone linkers have been synthesized using dynamic covalent chemistry (DCC) and hydrogen-bond-based self-assembly. The dynamic character of the linkers and the preference of the peptides towards self-assembly into β-barrel-type motifs lead to the spontaneous amplification of formation of homochiral capsules from mixtures of different substrates. The capsules have cavities of around 800 ?3 and exhibit good kinetic stability. Although they retain their dynamic character, which allows processes such as chiral self-sorting and chiral self-assembly to operate with high fidelity, guest complexation is hindered in solution. However, the quantitative complexation of even very large guests, such as fullerene C60 or C70, is possible through the utilization of reversible covalent bonds or the application of mechanochemical methods. The NMR spectra show the influence of the chiral environment on the symmetry of the fullerene molecules, which results in the differentiation of diastereotopic carbon atoms for C70, and the X-ray structures provide unique information on the modes of peptide-fullerene interactions.
- Szymański, Marek,Wierzbicki, Micha?,Gilski, Miros?aw,J?drzejewska, Hanna,Sztylko, Marcin,Cmoch, Piotr,Shkurenko, Aleksander,Jaskólski, Mariusz,Szumna, Agnieszka
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p. 3148 - 3155
(2016/03/23)
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- A supramolecularly tunable chiral diphosphine ligand: Application to Rh and Ir-catalyzed enantioselective hydrogenation
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A supramolecularly tunable chiral bisphosphine ligand bearing two pyridyl-containing crown ethers, (-) or (+)-Xyl-P16C6-Phos, was fabricated and utilized in the Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acid esters and Ir-catalyzed asymmetric hydrogenation of quinolines in high yields with excellent enantioselectivities (90-99% ee). Up to a 22% enhancement in enantioselectivity was achieved by the addition of certain amounts of alkali ions (Li+, Na+ or K+), which could be selectively recognized and effectively complexed by the crown ethers on the chiral Xyl-P16C6-Phos.
- Zhang, Xi-Chang,Hu, Yi-Hu,Chen, Chuan-Fu,Fang, Qiang,Yang, Li-Yao,Lu, Ying-Bo,Xie, Lin-Jie,Wu, Jing,Li, Shijun,Fang, Wenjun
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p. 4294 - 4299
(2016/07/06)
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- Modular solid-phase synthesis, catalytic application and efficient recycling of supported phosphine-phosphite ligand libraries
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In spite of decades of research in the field of homogeneous asymmetric catalysis the discovery of new high performance catalysts still relies heavily on trial-and-error. There is still a lack of efficient combinatorial methods which enable the synthesis and screening of vast ligand libraries, especially for bidentate phosphorus ligands. Here we present a highly modular solid-phase synthetic approach which provides facile access to libraries of phosphine-phosphite ligands in quantitative yield requiring only minimal work-up. The obtained library of supported phosphine-phosphites was successfully applied in rhodium catalyzed asymmetric hydrogenation obtaining high enantioselectivities up to 98%. Also, these polymer supported ligands could be successfully recycled under batch conditions exhibiting only a small decline of activity and no loss of selectivity.
- Heutz, Frank J. L.,Kamer, Paul C. J.
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supporting information
p. 2116 - 2123
(2016/02/09)
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- Designing P-Chirogenic 1,2-Diphosphinobenzenes at Both P-Centers Using P(III)-Phosphinites
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A new enantiodivergent synthesis of P-chirogenic 1,2-diphosphinobenzenes (DP?B) bearing the chirality on one or both phosphorus centers is reported using aryne chemistry. The principle is based on successive reactions of 1,2-dibromobenzene with sec-phosphide boranes, then DABCO to remove the borane, and finally with chlorophosphines or P(III)-chirogenic phosphinites. The efficiency of this synthesis was demonstrated by the stereoselective preparation of (S,S)-1,2-bis(o-anisylphenylphosphino)benzene. A comparison of DIPAMP and homochiral DP?B ligands in asymmetric Rh- or Pd-catalyzed reactions was reported.
- Bayardon, Jér?me,Rousselin, Yoann,Jugé, Sylvain
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supporting information
p. 2930 - 2933
(2016/07/06)
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