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Relevant academic research and scientific papers

Efficient, rhodium-catalyzed hydrogenation of α-dehydroamino acid esters with chiral monodentate aminophosphanes bearing two binaphthyl groups

All four stereoisomers of 4-{4,5-dihydro-3H-dinaphtho-[2,1-c:1′, 2′-e]azepin-4-yl)dinaphtho[2,1-d:1′,2′-f[1,3,2] dioxaphosphepine have been prepared from (R or S)-1,1′-binaphthyl-2, 2′-diyl chlorophosphite and the appropriate dinaphtho-azepine. When react

Phosphane-phosphite chelators built on a α-cyclodextrin scaffold: Application in rh-catalysed asymmetric hydrogenation and hydroformylation

Four hybrid phosphane-phosphite ligands were synthesised by regioselective A,B-functionalisation of a methylated α-cyclodextrin (α-CD) scaffold. In all these ligands the phosphite part comprises a 2,2′-bisaryloxyphosphanyloxy group. The ligands, which dis

Asymmetric Reduction of Aromatic α-Dehydroamino Acid Esters with Water as Hydrogen Source

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.

Topology-Based Functionalization of Robust Chiral Zr-Based Metal-Organic Frameworks for Catalytic Enantioselective Hydrogenation

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.

Diaza-Crown Ether-Bridged Chiral Diphosphoramidite Ligands: Synthesis and Applications in Asymmetric Catalysis

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.

Chiral bisphosphine ligands based on quinoline oligoamide foldamers: application in asymmetric hydrogenation

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.

An Atropos Chiral Biphenyl Bisphosphine Ligand Bearing Only 2,2′-Substituents and Its Application in Rh-Catalyzed Asymmetric Hydrogenation

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

Synthesis of a new bulky phosphite ligand and its application in the enantioselective hydrogenation

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

Synthesis of new chiral amidophosphite ligands and their application in hydrogenation of benzodiazepinones and enamides

New chiral amidophosphites were synthesized and tested in the Ir-catalyzed hydrogenation of 4-substituted 1,3-dihydro-2H-1,5-benzodiazepin-2-ones and Rh-catalyzed hydrogenation of dehydro amino acid derivatives. The triphenylphosphine additive can considerably increase the enantioselectivity of both processes.

Site- and Stereoselective Chemical Editing of Thiostrepton by Rh-Catalyzed Conjugate Arylation: New Analogues and Collateral Enantioselective Synthesis of Amino Acids

The synthesis of complex, biologically active molecules by catalyst-controlled, selective functionalization of complex molecules is an emerging capability. We describe the application of Rh-catalyzed conjugate arylation to the modification of thiostrepton, a complex molecule with potent antibacterial properties for which few analogues are known. By this approach, we achieve the site- and stereoselective functionalization of one subterminal dehydroalanine residue (Dha16) present in thiostrepton. The broad scope of this method enabled the preparation and isolation of 24 new analogues of thiostrepton, the biological testing of which revealed that the antimicrobial activity of thiostrepton tolerates the alteration of Dha16 to a range of amino acids. Further analysis of this Rh-catalyzed process revealed that use of sodium or potassium salts was crucial for achieving high stereoselectivity. The catalyst system was studied further by application to the synthesis of amino esters and amides from dehydroalanine monomers, a process which was found to occur with up to 93:7 er under conditions milder than those previously reported for analogous reactions. Furthermore, the addition of the same sodium and potassium salts as applied in the case of thiostrepton leads to a nearly full reversal of the enantioselectivity of the reaction. As such, this study of site-selective catalysis in a complex molecular setting also delivered synergistic insights in the arena of enantioselective catalysis. In addition, these studies greatly expand the number of known thiostrepton analogues obtained by any method and reveal a high level of functional group tolerance for metal-catalyzed, site-selective modifications of highly complex natural products.