3618-96-0Relevant articles and documents
Synthesis of new monodentate spiro phosphoramidite ligand and its application in Rh-catalyzed asymmetric hydrogenation reactions
Wu, Shulin,Zhang, Weicheng,Zhang, Zhaoguo,Zhang, Xumu
, p. 3565 - 3567 (2004)
(Chemical Equation Presented) A new spirocyclic diol, 9,9′- spirobixanthene-1,1′-diol, was synthesized in two steps from readily available starting material m-phenoxyanisole. Resolution of the racemic diol was achieved by cocrystallization with N-benzylcinchondimium chloride and N-benzylquininium chloride in acetonitrile. The corresponding spiro monodentate phosphoramidite ligand has been prepared for Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives and itaconic acid with excellent enantioselectivities (up to >99% ee).
Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds
Zhong, Hongyu,Friedfeld, Max R.,Chirik, Paul J.
, p. 9194 - 9198 (2019)
Chloride abstraction from [(R,R)-(iPrDuPhos)Co(μ-Cl)]2 with NaBArF4 (BArF4=B[(3,5-(CF3)2)C6H3]4) in the presence of dienes, such as 1,
Versatile synthesis of P-chiral (ephedrine) AMPP ligands via their borane complexes. Structural consequences in Rh-catalyzed hydrogenation of methyl α-acetamidocinnamate
Moulin, Dominique,Darcel, Christophe,Juge, Sylvain
, p. 4729 - 4743 (1999)
An efficient and versatile synthesis of aminophosphine phosphinite (AMPP) ligands derived from ephedrine, with possible stereogenic P(III)- center(s) is described, using the borane complex methodology. The reaction of oxazaphospholidine borane with an org
Chiral diphosphites derived from D-glucose: new highly modular ligands for the asymmetric catalytic hydrogenation.
Dieguez, Montserrat,Ruiz, Aurora,Claver, Carmen
, p. 3796 - 3801 (2002)
A series of novel diphosphite ligands derived from readily available D-(+)-glucose have been synthesized. These ligands were screened in the Rh-catalyzed hydrogenation of a series of alpha,beta-unsaturated carboxylic acid derivatives. Both excellent enantioselectivities (ee up to >99%) and activities were achieved. The advantage of these ligands is that their modular nature allows an easy systematic variation in the configuration of the stereocenters (C-3, C-5) at the ligand backbone and in the biaryl substituents, so the optimum configuration for maximum enantioselectivity in asymmetric hydrogenation can be determined. Results show that enantiomeric excesses depend strongly on the absolute configuration of C-3 and slightly on the stereocenter carbon C-5, while the sense of the enantiodiscrimination is predominantly controlled by the configuration of the biaryls at the phosphite moieties. Moreover, the presence of bulky substituents at the ortho-positions of the biaryl diphosphite moieties has a positive effect on enantioselectivity.
Instant ligand libraries. Parallel synthesis of monodentate phosphoramidites and in situ screening in asymmetric hydrogenation
Lefort, Laurent,Boogers, Jeroen A. F.,De Vries, Andre H. M.,De Vries, Johannes G.
, p. 1733 - 1735 (2004)
Matrix presented. Chiral phosphoramidites have been identified as excellent ligands for various metal-catalyzed enantioselective transformations. Taking advantage of their easy preparation and modular nature, we designed a fully automated protocol for the
A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands
Chen, Weiping,Mbafor, William,Roberts, Stanley M.,Whittall, John
, p. 3922 - 3923 (2006)
A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands has been developed. On the basis of this new methodology, several new families of ferrocene-based phosphine ligands have been prepared coupling chirality at phosphorus with other, more standard stereogenic features. The introduction of P-chirality into ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding Rh catalyst when a matching among the planar chirality, carbon chirality, and the chirality of phosphorus is achieved. Copyright
Mechanistically Guided One Pot Synthesis of Phosphine-Phosphite and Its Implication in Asymmetric Hydrogenation
Sen, Anirban,Kumar, Rohit,Pandey, Swechchha,Vipin Raj,Kumar, Pawan,Vanka, Kumar,Chikkali, Samir H.
supporting information, (2022/01/11)
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.
Asymmetric Reduction of Aromatic α-Dehydroamino Acid Esters with Water as Hydrogen Source
Dai, Yuze,Chen, Jingchao,Wang, Zheting,Wang, Ting,Wang, Lin,Yang, Yong,Qiao, Xingfang,Fan, Baomin
supporting information, p. 7141 - 7147 (2021/05/29)
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.
Ferrocene boron-containing chiral diphosphine ligand as well as preparation method and application thereof
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Paragraph 0099-0101, (2021/07/17)
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
Asymmetric Full Saturation of Vinylarenes with Cooperative Homogeneous and Heterogeneous Rhodium Catalysis
Andersson, Pher G.,Massaro, Luca,Peters, Bram B. C.,Wu, Haibo,Yang, Jianping,Zheng, Jia
supporting information, p. 20377 - 20383 (2021/12/03)
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.
