Dynamic Kinetic Resolution of 3-Aryl-4-pentenoic Acids

Koszelewski, Dominik; Brodzka, Anna; Żądło, Anna; Paprocki, Daniel; Trzepizur, Damian; Zysk, Małgorzata; Ostaszewski, Ryszard

doi:10.1021/acscatal.6b00271

Cited by 22 publications

(9 citation statements)

References 105 publications

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“…In our primary studies, we found that the Novozym 435-catalyzed polycondensation between racemic Asp diesters and achiral diols was not successful, because Novozym 435 showed a high preference for l -Asp diesters and the chain growth reaction was stopped when slow-reacting d -Asp diesters locating at the chain terminal. This problem was similar to that one observed in Novozym 435-catalyzed ROP of 6-MeCL and polycondensation of racemic diols and dicarboxylic acid derivatives. , However, the strategy proposed by Meijer and Heise was not efficient in this case because of the difficult racemization of general racemic acid derivatives without the α-electron-withdrawing group . Herein, this paper reports Novozym 435-catalyzed preparation of various chiral polyesters with high optical purity and high molecular weight starting from diols and l - or d -Asp diesters with different N -substituents.…”

Section: Introductionsupporting

confidence: 57%

Substrate Engineering in Lipase-Catalyzed Selective Polymerization of d-/l-Aspartates and Diols to Prepare Helical Chiral Polyester

Xia

Lin

et al. 2021

Biomacromolecules

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The synthesis of optically pure polymers is one of the most challenging tasks in polymer chemistry. Herein, Novozym 435 (Lipase B from Candida antarctica, immobilized on Lewatit VP OC 1600)-catalyzed polycondensation between d-/l-aspartic acid (Asp) diester and diols for the preparation of helical chiral polyesters was reported. Compared with d-Asp diesters, the fast-reacting l-Asp diesters easily reacted with diols to provide a series of chiral polyesters containing N-substitutional l-Asp repeating units. Besides amino acid configuration, N-substituent side chains and the chain length of diols were also investigated and optimized. It was found that bulky acyl N-substitutional groups like N-Boc and N-Cbz were more favorable for this polymerization than small ones probably due to competitively binding of these small acyl groups into the active site of Novozym 435. The highest molecular weight can reach up to 39.5 × 103 g/mol (M w, Đ = 1.64). Moreover, the slow-reacting d-Asp diesters were also successfully polymerized by modifying the substrate structure to create a “nonchiral” condensation environment artificially. These enantiocomplementary chiral polyesters are thermally stable and have specific helical structures, which was confirmed by circular dichroism (CD) spectra, scanning electron microscope (SEM), and molecular calculation.

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Section: Introductionsupporting

confidence: 57%

Substrate Engineering in Lipase-Catalyzed Selective Polymerization of d-/l-Aspartates and Diols to Prepare Helical Chiral Polyester

Xia

Lin

et al. 2021

Biomacromolecules

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“…Heteroleptic dirhodium complexes for highly enantioselective processes start to appear [105] . Dirhodium compounds can be used as catalysts for hydrogenation of alkenes [106] (such reactions were proposed to proceed via heterolytic splitting of hydrogen by the dirhodium complex) or can be used as catalysts for transfer hydrogenations [107] , dynamic kinetic resolution of alcohols, DKR of homoallyl‐carboxylic acids [108] or as catalysts in other processes as hydroformylation of alkenes [109,274] or reduction of CO 2 with silanes [110] . Photochemical and thermal evolution of molecular hydrogen from water [111] can be catalyzed with dirhodium paddlewheel complexes with electron withdrawing carboxylate ligands [112] .…”

Section: Applications Of Dirhodium(iiii) Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh2A4. These complexes have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, they act as Lewis acids to activate unsaturated bonds, serve as hydrogenation catalysts and participate in oxidation/reduction processes. Dirhodium paddlewheel complexes are composed of the Rh‐Rh backbone and four bridging anions, which surround the core. According to the application, the electrochemical potential of the Rh atom can be modulated, as can the geometry and physical and chemical properties of the metal complex. Dirhodium complexes can be prepared in one step from basic inorganic precursors or by post‐functionalization of the paddlewheel structures.

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“…Other metals that have been recently used in chemoenzymatic transformations are Rh, [73] Pt, [74] and Co [75] . However, these reactions were performed in a telescopic or in a non‐stereoselective fashion, out of the scope of this minireview, although it is expected that in the close future examples of asymmetric cascades using these metals will be described [76] …”

Section: Metal‐enzyme Cascade Processesmentioning

confidence: 99%

Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

et al. 2023

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The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse organic molecules in a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due to the possibility to assemble metal catalysis in C−C coupling, olefin metathesis, hydration and other reactions with the exquisite stereospecificity displayed by enzymes. Thus, this minireview is organized based on the action of the metal species (Pd, Ru, Au, Ir, Fe…) in combination with different enzymes. Special attention will be paid to the design of sequential processes and concurrent cascades, presenting solutions such as the use of surfactants or compartmentalization strategies for those cases where incompatibilities could hamper the overall process.

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Dynamic Kinetic Resolution of 3-Aryl-4-pentenoic Acids

Cited by 22 publications

References 105 publications

Substrate Engineering in Lipase-Catalyzed Selective Polymerization of d-/l-Aspartates and Diols to Prepare Helical Chiral Polyester

Substrate Engineering in Lipase-Catalyzed Selective Polymerization of d-/l-Aspartates and Diols to Prepare Helical Chiral Polyester

Dirhodium(II,II) Paddlewheel Complexes

Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

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