- Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?
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The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.
- Lang, Qiwei,Yang, Huaxin,Gu, Guoxian,Feng, Qiang,Wen, Jialin,Zhang, Xumu
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supporting information
p. 933 - 936
(2021/03/03)
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- Enantioselective Conjugate Addition of Stabilized Arylzinc Iodide to Enones: an Improved Protocol of the Hayashi Reaction
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Stabilised arylzinc iodide, prepared by direct insertion of zinc into aryl iodides, were used as nucleophiles in the Hayashi Rh-catalysed enantioselective conjugate addition to enones. The reaction conditions were optimized in the addition of phenylzinc i
- Casotti, Gianluca,Rositano, Vincenzo,Iuliano, Anna
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p. 1126 - 1131
(2020/12/17)
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- Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones
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Chiral N-aryl sulfinamide-olefins which are readily synthesized via C-N coupling and nucleophilic substitution have been used as chiral ligands, which demonstrate moderate to excellent asymmetric catalytic performance in the rhodium-catalyzed asymmetric 1
- Yuan, Shuai,Zeng, Qingle,Wang, Jiajun,Zhou, Lihong
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supporting information
p. 32 - 42
(2021/02/09)
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- Organic Solvent-free Asymmetric 1,4-Addition in Liquid- or Solid-State using Conventional Stirring Catalyzed by a Chiral Rhodium Complex Developed as a Homogeneous Catalyst
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Organic solvent-free asymmetric 1,4-addition of arylboronic acids to enone substrates was performed by using a chiral rhodium complex catalyst developed as a homogeneous catalyst. Reactions catalyzed by [RhOH(cod)]2 with chiral diphosphine ligands in liquid- or solid-state proceeded to give chiral 1,4-adducts in high yield with enantioselectivities up to ca. 100 % ee by conventional stirring without mechanochemistry such as ball milling. The solid-state reactions under a static condition also proceeded, but with a slight decrease in enantioselectivity of the 1,4-adduct. SEM observations of the solid-state reactions indicated that no nanoparticles catalyst was generated. The organic solvent-free reaction could be applied to gram-scale synthesis by performing a greener purification using a minimum necessary organic solvent.
- Korenaga, Toshinobu,Kori, Hiroto,Asai, Shota,Kowata, Ryo,Shirai, Masayuki
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p. 6059 - 6066
(2020/10/28)
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- Enantioselective Conjugate Addition of Aryl Halides and Triflates to Electron-Deficient Olefins via Nickel- And Rhodium-Catalyzed Sequential Relay Reactions
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Asymmetric conjugate addition of aryl halides or aryl triflates to electron-deficient olefins was realized by sequential Miyaura borylation and Hayashi-Miyaura conjugate addition in one pot. A nickel-catalyzed borylation of aryl halides or triflates and a rhodium-chiral diene complex catalyzed enantioselective conjugate addition was executed as a pair of relay reactions as a more efficient and greener protocol.
- Fan, Chenrui,Wu, Qixu,Zhu, Chengfeng,Wu, Xiang,Li, Yougui,Luo, Yunfei,He, Jian-Bo
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p. 8888 - 8892
(2019/10/14)
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- Asymmetric Baeyer-Villiger oxidation: Classical and parallel kinetic resolution of 3-substituted cyclohexanones and desymmetrization of: Meso -disubstituted cycloketones
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Regioselectivity is a crucial issue in Baeyer-Villiger (BV) oxidation. To date, few reports have addressed asymmetric BV oxidation of 3-substituted cycloketones due to the high difficulty of controlling regio- and stereoselectivity. Herein, we report the asymmetric BV oxidation of 3-substituted and meso-disubstituted cycloketones with chiral N,N′-dioxide/Sc(iii) catalysts performed in three ways: classical kinetic resolution, parallel kinetic resolution and desymmetrization. The methodology was applied in the total and formal synthesis of bioactive compounds and natural products. Control experiments and calculations demonstrated that flexible and adjustable catalysts played a significant role in the chiral recognition of substrates.
- Wu, Wangbin,Cao, Weidi,Hu, Linfeng,Su, Zhishan,Liu, Xiaohua,Feng, Xiaoming
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p. 7003 - 7008
(2019/07/31)
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- CHIRAL RHODIUM COMPLEX, AND METHOD FOR PRODUCING β-SUBSTITUTED CARBONYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a chiral complex which, when used as a catalyst, can make an aromatic boronic acid undergo asymmetric 1,4-addition to a conjugated enone in an aqueous solvent under relatively mild conditions and can be recovered by filtration; and a method for producing an optically active β-substituted carbonyl compound using the same as the catalyst. SOLUTION: Provided is a chiral rhodium complex represented by the following formula (α). [In the formula (α), A represents a polystyrene-polyethylene glycol copolymer resin.] SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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-
Paragraph 0033-0035
(2021/05/26)
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- Steric Tuning of Sulfinamide/Sulfoxides as Chiral Ligands with C1, Pseudo-meso, and Pseudo-C2 Symmetries: Application in Rhodium(I)-Mediated Arylation
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A new family of sulfinamide/sulfoxide derivatives was synthesized as chiral bidentate ligands by stereoselective additions of methylsulfinyl carbanions to N-tert-butylsulfinylimines. The new ligands, with C1, pseudo-meso, and pseudo-C2 symmetries, were successfully assayed in Rh-catalyzed additions of arylboronic acids to activated ketones. The sterically dissymmetric C1 ligand (RS,SC,RS)-N-[1-(phenylsulfinyl)-3-methylbut-2-yl] tert-butylsulfinamide turned out to be the optimal one, allowing the 1,4-additions of diverse arylboronic acids, on different α,β-unsaturated cyclic ketones with high chemical yields and enantioselectivities up to >99% ee.
- Borrego, Lorenzo G.,Recio, Rocío,álvarez, Eleuterio,Sánchez-Coronilla, Antonio,Khiar, Noureddine,Fernández, Inmaculada
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supporting information
p. 6513 - 6518
(2019/08/20)
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- Synthesis of Highly Enantioenriched Propelladienes and their Application as Ligands in Asymmetric Rh-Catalyzed 1,4-Additions
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The first synthesis of highly enantioenriched [4.3.3]propelladienes is reported. The novel bridged bicyclo[3.3.0] dienes were applied as steering ligands in the rhodium-catalyzed asymmetric arylation of cyclic enones. The catalytic system showed high catalytic activity, and the 1,4-adducts were obtained in good to excellent yields (46-99%) with enantioselectivities up to 96% ee.
- Pecchioli, Tommaso,Christmann, Mathias
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supporting information
p. 5256 - 5259
(2018/09/13)
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- A novel, C2-symmetric, chiral bis-cyclosulfinamide-olefin tridentate ligand in Rh-catalyzed asymmetric 1,4-additions
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A C2-symmetric, chiral bis-cyclosulfinamide-olefin ligand composed of two 1-oxo-2,3-dihydro-1,2-benzisothiazole moieties with rigid skeletons and a conformationally flexible butenylene chain is disclosed for the first time. HRMS and 1/sup
- Zhang, Li,Tan, Mingchao,Zhou, Lihong,Zeng, Qingle
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supporting information
p. 2778 - 2783
(2018/06/11)
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- Aqueous Asymmetric 1,4-Addition of Arylboronic Acids to Enones Catalyzed by an Amphiphilic Resin-Supported Chiral Diene Rhodium Complex under Batch and Continuous-Flow Conditions
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A rhodium-chiral diene complex immobilized on amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin (PS-PEG-diene?-Rh) has been developed. The immobilized rhodium-chiral diene complex (PS-PEG-diene?-Rh) efficiently catalyzed the asymmetric 1,4-addition of various arylboronic acids to cyclic or linear enones in water under batch conditions to give the corresponding β-arylated carbonyl compounds in excellent yields and with excellent enantioselectivity. The catalyst was readily recovered by simple filtration and reused 10 times without loss of its catalytic activity and enantioselectivity. Moreover, a continuous-flow asymmetric 1,4-addition in a flow reactor containing PS-PEG-diene?-Rh proceeded efficiently at 50 °C with retention of high enantioselectivity. Long-term continuous-flow asymmetric 1,4-addition during 12 h readily gave the desired product on a 10 g scale with high enantioselectivity.
- Shen, Guanshuo,Osako, Takao,Nagaosa, Makoto,Uozumi, Yasuhiro
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p. 7380 - 7387
(2018/07/29)
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- Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi-Miyaura Reaction
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A stereodivergent synthesis using inexpensive reagents, i.e., dibenzazepine and glucose-derived t-Bu-sulfinate diastereomers (RS)-6 or (SS)-6, affords respective S(O)-alkene hybrid ligands (S)-7 and (R)-7 on gram scales and in excellent optical purity (ee > 99%). Phenyl substitution of the dibenzoazepine backbone generates planar chirality to give epimerization-resistant (pS,RS)-10 diastereoisomer in high isomeric purity. Furthermore, the crystal structure of widely used sulfinate (RS)-6 is disclosed for the first time since its discovery a quarter of a century ago. Ligands 7 and 10 coordinate Rh(I) in a bidentate fashion through the S atoms and the alkene functions as evidenced by the crystal structures of complexes (R)-11 and (SN,SS)-12. (R)-11 catalyzes the conjugate addition of arylboronic acids to enones with enantioselectivities of up to 77% ee. The reaction proceeds smoothly also under base-free conditions at 40 °C. The planar chirality in ligand (pS,RS)-10 is shown to override and invert the sense of chiral induction predicted by the configuration of the sulfur donor atom.
- Chelouan, Ahmed,Bao, Siyuan,Frie?, Sibylle,Herrera, Alberto,Heinemann, Frank W.,Escalona, Ana,Grasruck, Alexander,Dorta, Romano
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p. 3983 - 3992
(2018/10/31)
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- Pd NPs-Loaded Homochiral Covalent Organic Framework for Heterogeneous Asymmetric Catalysis
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We herein report the fabrication of a palladium nanoparticles (Pd NPs) loaded homochiral covalent organic framework using S-(+)-2-methylpiperazine and cyanuric chloride (Pd@CCOF-MPC) (2) via a very facile chemical approach. The chiral COF support of 1 (CC
- Ma, Hui-Chao,Kan, Jing-Lan,Chen, Gong-Jun,Chen, Cheng-Xia,Dong, Yu-Bin
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p. 6518 - 6524
(2017/08/18)
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- Planar-chiral phosphine-olefin ligands exploiting a (Cyclopentadienyl)manganese(I) scaffold to achieve high robustness and high enantioselectivity
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A series of 2-methyl-1,3-propenylene-bridged (η5-diarylphosphinocyclopentadienyl)(phosphine)manganese(I) di-carbonyl complexes 2 have been developed as a new class of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold,
- Kamikawa, Ken,Tsen, Ya-Yi,Jian, Jia-Hong,Takahashi, Tamotsu,Ogasawara, Masamichi
-
supporting information
p. 1545 - 1553
(2017/02/10)
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- PHOSPHINE-OLEFIN LIGAND HAVING FACE ASYMMETRIC CYCLOPENTADIENYL-MANGANESE COMPLEX IN BASIC SKELETON
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PROBLEM TO BE SOLVED: To provide a face asymmetric ligand for a transition metal catalyst asymmetric reaction high in yield and optical purity to not only a cyclic enone compound, but also various enone compounds containing an aliphatic enone compound. SO
- -
-
Paragraph 0124
(2017/06/27)
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- A New Type of Chiral Cyclic Sulfinamide–Olefin Ligands for Rhodium-Catalyzed Asymmetric Addition
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A new type of chiral cyclic sulfinamide–olefin ligands, N-allylic 2,3-dihydro-1,2-benzoisothiazole 1-oxides, with 2,3-dihydro-1,2-benzoisothiazole 1-oxide as a unique chiral skeleton, is developed for the highly enantioselective rhodium-catalyzed asymmetr
- Wen, Quan,Zhang, Li,Xiong, Jing,Zeng, Qingle
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supporting information
p. 5360 - 5364
(2016/11/22)
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- Electronically deficient (Rax,S,S)-F12-C3-TunePhos and its applications in asymmetric 1,4-addition reactions
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A novel electronically deficient chiral diphosphine ligand (Rax,S,S)-F12-C3-TunePhos has been concisely synthesized. The electron-poor ligand features both chiral centers and chiral axis bearing fluoro-functional groups on
- Hu, Shu-Bo,Chen, Zhang-Pei,Zhou, Ji,Zhou, Yong-Gui
-
supporting information
p. 1925 - 1929
(2016/04/19)
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- Two phenyls are better than one or three: Synthesis and application of terminal olefin-oxazoline (TOlefOx) ligands
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A novel terminal olefin-oxazoline ligand was introduced into rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to enones and gave excellent enantioselectivities. The two phenyls proved better than one or three in ligand evaluations.
- Zhao, Yi-Shuang,Liu, Jian-Kang,He, Zhi-Tao,Tao, Jing-Chao,Tian, Ping,Lin, Guo-Qiang
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supporting information
p. 3686 - 3689
(2016/05/09)
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- Chiral Bicyclic Bridgehead Phosphoramidite (Briphos) Ligands for Asymmetric Rhodium-Catalyzed 1,2- and 1,4-Addition
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A complementary solution for Rh-catalyzed enantioselective 1,2- and 1,4-arylation with two structurally related chiral ligands is reported. A chiral bicyclic bridgehead phosphoramidite (briphos) ligand derived from 1-aminoindane was efficient for the 1,2-arylation of N-sulfonyl imines, while that derived from 1,2,3,4-tetrahydro-1-naphthylamine was efficient for 1,4-arylation of α,β-unsaturated cyclic ketones. For α,β-unsaturated N-tosyl ketimines, the briphos derived from 1-aminoindane was found to selectively provide γ, γ-diaryl N-tosyl enamines with high yields and stereoselectivities.
- Lee, Ansoo,Kim, Hyunwoo
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p. 3520 - 3527
(2016/05/24)
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- Chiral Phosphorus-Olefin Ligands for the RhI-Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins
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New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; t
- Chen, Qian,Li, Liang,Zhou, Guangli,Ma, Xiaoli,Zhang, Lu,Guo, Fang,Luo, Yi,Xia, Wujiong
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supporting information
p. 1518 - 1522
(2016/06/01)
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- The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions
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We have designed the first chiral diene-based metal-organic framework (MOF), E2-MOF, and postsynthetically metalated E2-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C-C bond fo
- Sawano, Takahiro,Ji, Pengfei,McIsaac, Alexandra R.,Lin, Zekai,Abney, Carter W.,Lin, Wenbin
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p. 7163 - 7168
(2015/11/23)
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- Chiral porous organic frameworks for asymmetric heterogeneous catalysis and gas chromatographic separation
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Three chiral robust diene-based porous organic frameworks (POFs) are prepared. POF-1 is shown to be an efficient heterogeneous catalyst after metallation for asymmetric conjugation addition with up to 93% ee, and it can also function as a new chiral stationary phase for gas chromatographic separation of racemates. This journal is
- Dong, Jinqiao,Liu, Yan,Cui, Yong
-
supporting information
p. 14949 - 14952
(2015/01/08)
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- CHIRAL DIENE LIGANDS, A FABRICATION METHOD THEREOF AND APPLICATIONS THEREOF
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The present invention proposes a chiral diene ligand, a fabrication method thereof and applications thereof. The chiral diene ligand is a bicyclo[2.2.1] diene ligand having structural specificity and high stability, which favors the bicyclo[2.2.1] diene l
- -
-
Paragraph 0030; 0031
(2013/04/24)
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- Asymmetric rhodium-catalyzed 1,4- and 1,2-additions of arylboronic acids to activated ketones in water at room temperature using a mixed sulfur-olefin ligand
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Performing catalytic enantioselective reactions, especially enantioselective carbon-carbon bond forming reactions, in water without using any organic solvents is one of the important goals in modern asymmetric synthesis. Herein, we report an efficient enantioselective micellar catalytic approach for the 1,4-addition of arylboronic acids to cyclic ketones. Noteworthy, applying the same catalytic system we have also developed the first addition of boronic acids to the more challenging α-keto carbonyl compounds in water, affording tertiary carbinols with high yields and high enantioselectivities. Beside the mild conditions used, the reported processes use as catalyst precursor the robust sulfinamido-olefin mixed ligand 1 obtained on a multigram scale and in one step from a sugar-derived sulfinate ester. Copyright
- Khiar, Noureddine,Valdivia, Victoria,Salvador, Alvaro,Chelouan, Ahmed,Alcudia, Ana,Fernandez, Inmaculada
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supporting information
p. 1303 - 1307
(2013/06/27)
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- Flexible C2-symmetric bis-sulfoxides as ligands in enantioselective 1,4-addition of boronic acids to electron-deficient alkenes
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The application of acyclic C2-symmetric chelating bis-sulfoxide ligands in the Rh(I)-catalyzed enantioselective 1,4-addition of boronic acids to electron-deficient alkenes is reported. Among the acyclic ethane-bridged bis-sulfoxides tested, the
- Khiar, Noureddine,Salvador, Alvaro,Valdivia, Victoria,Chelouan, Ahmed,Alcudia, Ana,Alvarez, Eleuterio,Fernandez, Inmaculada
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p. 6510 - 6521
(2013/07/26)
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- Cu-catalyzed enantioselective 1,4-additions of aryl-Grignard reagents to cyclohexenone in the presence of TADDOL-derived phosphane-phosphite ligands
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Asymmetric conjugate additions (1,4-additions) of aryl-Grignard reagents to cyclohex-2-enone, currently a more or less unsolved challenge, were investigated. For this purpose, a small library of phenol-derived chiral phosphane-phosphite ligands containing TADDOL- or BINOL-based phosphite moieties was evaluated. These ligands are easily prepared by a short modular scheme previously developed in this laboratory. Two particularly powerful ligands (4a and 4b, both TADDOL-derived and each possessing a bulky tert-butyl substituent ortho to the phosphite group) were identified. Conditions were optimized with use of the addition of (4-methoxyphenyl)magnesium bromide to cyclohexenone as a standard reaction system. Under optimized conditions [CuBr·SMe 2 (4 mol-%), ligand 4a (6 mol-%), 2-methyl-THF, -78 °C, slow addition of Grignard reagent] the 1,4-product was obtained with high enantioselectivity (up to 95 % ee) and good regioselectivity (r.r. = 90:10). The scope of the method was probed with different aryl-Grignard reagents. It was found that reagents with electron-donating substituents in meta- or para-positions performed particularly well, whereas the presence of F or CF 3 substituents led to decreased ee values. Only ortho-substituted aryl-Grignard reagents did not give rise to useful results. A series of phosphane-phosphite ligands were also tested in the Rh-catalyzed 1,4-addition of phenylboronic acid to cyclohexenone, but enantioselectivities did not exceed 70 % ee in this case. The difficult task of employing aryl-Grignard reagents in Cu-catalyzed enantioselective 1,4 addition reactions was achieved with the assistance of readily accessible chiral modular P,P ligands. High enantioselectivities were obtained in a number of synthetically relevant cases. Copyright
- Naeemi, Qaseem,Dindaroglu, Mehmet,Kranz, Darius P.,Velder, Janna,Schmalz, Hans-Guenther
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experimental part
p. 1179 - 1185
(2012/04/10)
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- Chiral sulfoxide-olefin ligands: Tunable stereoselectivity in Rh-catalyzed asymmetric 1,4-additions
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A class of chiral sulfoxide-olefins were designed and synthesized through concise routes. Their applications as ligands in Hayashi-Miyaura reaction were studied, which found that vinyl substituents of the ligands vary in stereocontrolling ability. Particularly, either isomer of adducts with excellent ees could be readily obtained through changing the position of the substituents of olefins as well as changing the configuration of the CC bond of the ligands. Meanwhile, the substrate scope of arylboronic acids and alkenes was clearly shown.
- Chen, Guihua,Gui, Jiangyang,Cao, Peng,Liao, Jian
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supporting information; experimental part
p. 3220 - 3224
(2012/06/01)
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- Easily accessible chiral dicyclopentadiene ligands for rhodium-catalyzed enantioselective 1,4-addition reactions
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A variety of novel C1-symmetric chiral diene ligands based on the dicyclopentadiene (DCP) skeleton were easily prepared from commercially available DCP. The application of these diene ligands in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds has been examined and excellent enantioselectivities (up to 97% ee) as well as good yields were achieved under mild reaction conditions.
- Shao, Cheng,Yu, Hong-Jie,Feng, Chen-Guo,Wang, Rui,Lin, Guo-Qiang
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supporting information; experimental part
p. 2733 - 2735
(2012/07/27)
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- The origins of enantioselectivity in Rh-diene complex catalysed arylation of cyclohex-2-enones
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Chiral diene ligands: Conjugate addition of aryl boronic acids to cyclohexenone is catalysed by Rh complexes of the simple chiral diene (S)-bicyclo[3.3.1]nona-2,6-diene in unexpectedly high ee. Insight into the reasons, and more generally the TS structure
- Gosiewska, Silvia,Raskatov, Jevgenij A.,Shintani, Ryo,Hayashi, Tamio,Brown, John M.
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supporting information; experimental part
p. 80 - 84
(2012/03/09)
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- Expanding the C1-symmetric bicyclo[2.2.1]heptadiene ligand family: Highly enantioselective synthesis of cyclic β-aryl-substituted carbonyl compounds
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The efficient preparation of highly enantioenriched cyclic β-aryl-substituted carbonyl compounds has been achieved through the Rh I-catalyzed asymmetric 1,4-addition of an array of arylboronic acids to cyclic α,β-unsaturated carbonyl compounds. In the presence of 0.1 or 0.5 mol-% of the RhI/1g complex, the products of conjugate addition were isolated in 89 to 98%ee and in good to excellent yield.
- Liu, Chia-Chen,Janmanchi, Damodar,Chen, Chun-Chih,Wu, Hsyueh-Liang
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supporting information; experimental part
p. 2503 - 2507
(2012/06/04)
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- Design of chiral sulfoxide-olefins as a new class of sulfur-based olefin ligands for asymmetric catalysis
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The design and development of a novel class of chiral sulfur-olefin hybrid ligands with high synthetic feasibility are described. These new sulfoxide-olefin ligands showed excellent catalytic activities and enantioselectivities (up to 98% ee) in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids to α,β-unsaturated carbonyl compounds.
- Qi, Wei-Yi,Zhu, Ting-Shun,Xu, Ming-Hua
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supporting information; experimental part
p. 3410 - 3413
(2011/08/22)
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- Chiral sulfoxide-olefin ligands: Completely switchable stereoselectivity in rhodium-catalyzed asymmetric conjugate additions
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Have it both ways: A novel class of chiral sulfoxide-olefin ligands was synthesized from a single chiral source. These ligands were evaluated in rhodium-catalyzed 1,4-additions of arylboronic acids to electron-deficient olefins, and remarkable olefin-directed reversal of stereoselectivity (up to >99 ee, R isomer; 98 ee, S isomer) was observed when the reversal ligand pair L1 (branched olefin) and L2 (linear olefin) were utilized (see scheme). Copyright
- Chen, Guihua,Gui, Jiangyang,Li, Liangchun,Liao, Jian
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supporting information; experimental part
p. 7681 - 7685
(2011/10/17)
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- (R)-3,5-diCF3-SYNPHOS and (R)- p -CF3-SYNPHOS, electron-poor diphosphines for efficient room temperature Rh-catalyzed asymmetric conjugate addition of arylboronic acids
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Two new atropisomeric electron-poor chiral diphosphine ligand analogues of SYNPHOS were prepared, and their electronic properties are described. These two ligands afforded high performance for the Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds at room temperature.
- Berhal, Farouk,Esseiva, Olivier,Martin, Charles-Henri,Tone, Hitoshi,Genet, Jean-Pierre,Ayad, Tahar,Ratovelomanana-Vidal, Virginie
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supporting information; experimental part
p. 2806 - 2809
(2011/07/09)
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- Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones with DIFLUORPHOS and SYNPHOS analogues
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Applications of electron-deficient DIFLUORPHOS and SYNPHOS analogues in the rhodium-catalyzed asymmetric conjugate addition of boronic acids to α,β-unsaturated ketones afford the 1,4-addition adducts in yields up to 92% and with 99% ee. Particularly, a Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to nonsubstituted maleimide substrates using the (R)-3,5-diCF3-SYNPHOS ligand is also reported. This protocol provides access to various enantioenriched 3-substituted succinimide units of biological interest, in high yields and good to excellent ee up to 93%, which could be upgraded up to 99% ee, after a single crystallization.
- Berhal, Farouk,Wu, Zi,Genet, Jean-Pierre,Ayad, Tahar,Ratovelomanana-Vidal, Virginie
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scheme or table
p. 6320 - 6326
(2011/10/05)
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- α,β-Divinyl tetrahydropyrroles as chiral chain diene ligands in rhodium(I)-catalyzed enantioselective conjugated additions
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A series of α,β-divinyl tetrahydropyrroles, synthesized by asymmetric allylic C-H bond activation/conjugated diene addition reaction of ene-2-dienes, were found to be very efficient chiral chain diene ligands in the rhodium-catalyzed conjugated addition of organoboronic acids to various α,β-unsaturated compounds, achieving the desired chiral adducts with good to excellent yields and ee values.(Figure Presented)
- Li, Qian,Dong, Zhe,Yu, Zhi-Xiang
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supporting information; experimental part
p. 1122 - 1125
(2011/04/23)
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- Sulfoxide-alkene hybrids: A new class of chiral ligands for the Hayashi-Miyaura reaction
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Sulfoxide-alkene hybrids are introduced as a new class of chiral heterodentate ligands for the Hayashi-Miyaura reaction. The synthesis of these ligands was achieved without the use of protecting groups. A chiral resolution was performed via simple column-chromatographic separation of the diastereomeric ligands. Both diastereomers proved to be excellent ligands in Rh-catalyzed 1,4-addition reactions, furnishing chiral products with high enantioselectivities and, remarkably, opposite stereoconfigurations.
- Thaler, Tobias,Guo, Li-Na,Steib, Andreas K.,Raducan, Mihai,Karaghiosoff, Konstantin,Mayer, Peter,Knochel, Paul
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supporting information; experimental part
p. 3182 - 3185
(2011/08/06)
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- One step synthesis of chiral olefins via asymmetric diamination and their applications as ligands for rhodium (I)-catalyzed 1, 4-additions
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A variety of acyclic chiral dienes were synthesized in a single step via palladiums-cata-lyzed asymmetric allylic and homoallylic C-H di-amination of terminal olefins. The applications of such simple dienes as steering ligands for rhodi-um(I)-catalyzed as
- Hu, Xichao,Cao, Ziping,Liu, Zhaoqun,Wang, Yazhou,Du, Haifeng
-
supporting information; experimental part
p. 651 - 655
(2010/06/20)
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- Hemilabile P-alkene ligands in chiral rhodium and copper complexes: Catalytic asymmetric 1,4 additions to enones. 2
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Two equivalents of the chiral dibenz[b,f]azepine-derived P-alkene ligands 2-6 per metal afforded mononuclear Rh(I) and Cu(I) complexes that were used as catalysts for asymmetric conjugate addition reactions. Rh formed square-planar neutral (8-10) and cati
- Dorta, Romano,Drinkel, Emma,Briceno, Alexander,Dorta, Reto
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experimental part
p. 2503 - 2514
(2010/08/04)
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- Tert-butanesulfinylphosphines: Simple chiral ligands in rhodium-catalyzed asymmetric addition of arylboronic acids to electron-deficient olefins
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An efficient rhodium complex catalyst system was developed by using a class of simple tert-butanesulfinylphosphines as bidentate ligands, which solely bear sulfur chirality and combine the advantages of both sulfoxide and phosphine ligands. Excellent activities (in 0.5 hour, up to 99% yield) and enantioselectivities (up to 98% ee) were displayed in Rh-catalyzed asymmetric 1,4-additions under mild conditions.
- Lang, Feng,Li, Dong,Chen, Junmin,Chen, Jun,Li, Liangchun,Cun, Linfeng,Zhu, Jin,Deng, Jingen,Liao, Jian
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supporting information; experimental part
p. 843 - 846
(2010/06/15)
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- Highly active and enantioselective rhodium-catalyzed asymmetric 1,4-addition of arylboronic acid to α,β-unsaturated ketone by using electron-poor MeO-F12-BIPHEP
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The asymmetric 1,4-addition of phenylboronic acid to cyclohexenone were performed by using a low amount of rhodium/(R)-(6,6′-dimethoxybiphenyl-2, 2′-diyl)bis[bis(3,4,5-trifluorophenyl)phosphine] (MeO-F 12-BIPHEP) catalyst. Because the catalyst
- Korenaga, Toshinobu,Maenishi, Ryota,Hayashi, Keigo,Sakai, Takashi
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experimental part
p. 3247 - 3254
(2011/02/23)
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- A class of readily available optically pure 7,7′-disubstituted BINAPs for asymmetric catalysis
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A class of optically pure 7,7′-disubstituted BINAPs have been prepared starting with a catalytic asymmetric oxidative coupling reaction. A general, concise, and straightforward synthetic procedure has been established, and is suitable for all optically pure 7,7′-disubstituted BINAPs 1a-h, regardless of the substituents' structure in the 7,7′-positions. The catalytic potential of this class of ligands has been investigated in the highly enantioselective Rh-catalyzed 1,4-addition of aryl boronic acids to enones (up to 99.8% ee), and Ru-catalyzed asymmetric hydrogenation of simple aromatic ketones (up to S/C=100,000, up to 98% ee) and β-ketoesters (up to S/C=10,000, up to 99.8% ee), respectively.
- Yuan, Wei-Cheng,Cun, Lin-Feng,Mi, Ai-Qiao,Jiang, Yao-Zhong,Gong, Liu-Zhu
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experimental part
p. 4130 - 4141
(2009/09/30)
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- Electron-poor chiral diphosphine ligands: High performance for rh-catalyzed asymmetric 1,4-addition of arylboronic acids at room temperature
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Electron-poor chiral diphosphine ligands, MeO-F28-BIPHEP (1a) and MeO-F12-BIPHEP (1b), were synthesized for controlling a transition-metal catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetri
- Korenaga, Toshinobu,Osaki, Kazutaka,Maenishi, Ryota,Sakai, Takashi
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supporting information; experimental part
p. 2325 - 2328
(2009/09/30)
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- Simple chiral chain dienes as ligands for Rh(I)-catalyzed conjugated additions
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This paper describes that a simple and readily available chain diene (3R,4R)-hexa-1,5-diene-3,4-dlol (L1) was successfully utilized as a novel steering ligand for Rh(I)-catalyzed asymmetric conjugated additions. Encouraging yields and ee's have been achieved, which may provide a new and practical direction for designing chiral diene ligands In the future.
- Hu, Xichao,Zhuang, Minyang,Cao, Ziping,Du, Haifeng
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supporting information; experimental part
p. 4744 - 4747
(2009/12/24)
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- Asymmetric 1,4-addition of organoboronic acids to α,β-unsaturated ketones and 1,2-addition to aldehydes catalyzed by a palladium complex with a ferrocene-based phosphine ligand
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A combination of palladium with ferrocene-based phosphine ligand with a carbon-bromine bond was found to be a good catalyst for the 1,4-addition of arylboronic acids to α,β-unsaturated ketones and the 1,2-addition to aldehydes. Using Pd(dba)2 and (S,Rp)-[1-(2-bromoferrocenyl)ethyl]diphenylphosphine (S,Rp)-1, 3-phenylcyclohexanone was obtained from the reaction of 2-cyclohexen-1-one with phenylboronic acid in the presence of K2CO3 in toluene at room temperature after 3 h in 92% yield with 76% ee. In the 1,2-addition of 4-methylphenylboronic acid to benzaldehyde, 96% of (4-methylphenyl)phenylmethanol was afforded after 24 h, while the enantiomeric excess was only 6%.
- Suzuma, Yoshinori,Hayashi, Shoko,Yamamoto, Tetsuya,Oe, Yohei,Ohta, Tetsuo,Ito, Yoshihiko
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experimental part
p. 2751 - 2758
(2010/04/26)
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- Enantioselective hydrogenation of enones with a hydroformylation catalyst
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Use of a typical rhodium precatalyst for hydroformylation results in the enantioselective hydrogenation of cyclic enones with up to 90% ee. Extensive screening of chiral ligands reveals the simple ligand Chiraphos as the best ligand, so far. The hydrogenation shows high chemoselectivity. Exclusive formation of saturated, chiral b-branched ketones is observed. It is proposed that the catalyst follows a frustrated hydroformylation pathway ("monohydride-based mechanism") and differs by that from the classical cationic Schrock-Osborn type rhodium precatalysts ("dihydride-based mechanism") for enantioselective hydrogenation. The catalyst operates under neat conditions and is easily recyclable by simply distilling off the reaction mixture and treatment with syn gas prior to hydrogenation.
- Scheuermann Nee Taylor, Caroline J.,Jaekel, Christoph
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supporting information; experimental part
p. 2708 - 2714
(2009/10/06)
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- Chiral tetrafluorobenzobarrelenes as highly efficient ligands for the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids
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New C2-symmetric chiral diene ligands bearing a tetrafluorobenzobarrelene framework and (-)-menthyl groups as chiral auxiliaries were prepared through [4 + 2] cycloaddition of 1,4-bis((-)-menthoxymethyl) benzene with tetrafluorobenzyne. The die
- Nishimura, Takahiro,Nagaosa, Makoto,Hayashi, Tamio
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p. 860 - 861
(2008/12/22)
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- Rh-catalyzed enantioselective conjugate addition of arylboronic acids with a dynamic library of chiral tropos phosphorus ligands
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A library of 19 chiral tropos phosphorus ligands, based on a free-to-rotate (tropos) biphenol unit and a chiral P-bonded alcohol (11 phosphites, 1-P(O)2O to 11-P(O)2O) or secondary amine (8 phosphoramidites, 12-P(O)2N to 19-P(O)2N). were screened, individually and in combinations of two, in the rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to enones and enoates. High enantioselectivities (up to 99% ee) and excellent yields were obtained in the addition to either cyclic or acyclic substrates. The flexible biphenolic P ligands outperformed the analogous rigid binaphtholic P ligands. Variable-temperature 31P NMR studies revealed that the biphenolic ligands are tropos even at low temperature. Only below 190 K was a coalescence observed: upon further cooling, two atropisomers were detected. The Rh homocomplexes ([Rh(La)2]+) were also studied: in general, a single doublet (P-Rh coupling) was observed in the case of the biphenolic phosphite ligands, over the temperature range 380-230 K, demonstrating their tropos nature in the rhodium complexes even at low temperatures. On the other hand, the phosphoramidites showed different behaviors depending on the structure of the ligand and on the nature of the rhodium source. The spectrum at 230 K of the mixture of [Rh(acac)(eth)2] (eth = C2H4) with phosphite 6-P(O)2O and phosphoramidite 19-P(O)2N (the most enantioselective ligand combination in the conjugate addition reaction) revealed the presence of four homocomplexes (total approximately 40%: [Rh(6-P(O)2}2], [Rh{(aR)-19-P(O)2N}2], [Rh((aS)-19-P(O)2N) 2], [Rh((aR)-19-P(O)2N}((aS)-19-P(O)2N}]) and one heterocomplex, [Rh{6-P(O)2O){(aR)-19-P(O)2NJ] (approximately 60%) In the heterocomplex, the biphenol-derived phosphite is free to rotate (tropos) while the biphenol-derived phosphoramidite shows a temperature-dependent tropos/atropos behavior (coalescence temperature = 310 K).
- Monti, Chiara,Gennari, Cesare,Piarulli, Umberto
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p. 1547 - 1558
(2008/02/03)
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- Enantioselective palladium-catalysed conjugate addition of arylsiloxanes
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The complex formed from Pd(CH3CN)4(BF 4)2 and (R,R)-MeDUPHOS is a highly enantioselective catalyst for the asymmetric conjugate addition of aryltriethylsiloxanes to a variety of unsaturated ketones, lactones and
- Gini, Francesca,Hessen, Bart,Feringa, Ben L.,Minnaard, Adriaan J.
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p. 710 - 712
(2007/10/03)
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- Asymmetric 1,4-addition reaction of arylboronic acid to eneone catalyzed by palladium with ferrocene-based phosphine ligand
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Asymmetric 1,4-addition reaction of arylboronic acid to cyclic enone was carried out in the presence of a chiral ferrocene-based phosphine ligand-palladium catalyst. The reaction of 2-cyclohexen-1-one by palladium complex with (S,Rp)-[1-(2-bromoferrocenyl)ethyl]diphenylphosphine afford a optically active β-arylcyclohexanone in good yield up to 71% ee. Copyright
- Suzuma, Yoshinori,Yamamoto, Tetsuya,Ohta, Tetsuo,Ito, Yoshihiko
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p. 470 - 471
(2008/02/02)
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- Chiral bicyclo[3.3.0]octa-2,5-dienes as steering ligands in substrate-dependent rhodium-catalyzed 1,4-addition of arylboronic acids to enones
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The synthesis of disubstituted chiral diene ligands (3aR,6aR)- and (3aS,6aS)-10 with a pentalene backbone from the corresponding bicyclo[3.3.0]octa1,4-diones 7 is described. The latter were accessible by enzymatic resolution of the racemic diol rac-5 and
- Heibig, Sarah,Sauer, Sven,Cramer, Nicolai,Laschat, Sabine,Baro, Angelika,Frey, Wolfgang
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p. 2331 - 2337
(2008/09/19)
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