Biomimetic asymmetric catalysis

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1553 - 1633

Опубликована: Апрель 25, 2023

Язык: Английский

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Cyclolignan synthesis streamlined by enantioselective hydrogenation of tetrasubstituted olefins

Nature Synthesis, Год журнала: 2024, Номер 3(8), С. 986 - 997

Опубликована: Июнь 20, 2024

Язык: Английский

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Regenerable Dihydrophenanthridine via Borane-Catalyzed Hydrogenation for the Asymmetric Transfer Hydrogenation of Benzoxazinones

Organic Letters, Год журнала: 2022, Номер 24(22), С. 3955 - 3959

Опубликована: Май 27, 2022

The highly enantioselective transfer hydrogenation of benzoxazinones with chiral phosphoric acids under H2 was successfully achieved, where boranes promoted the phenanthridine for regeneration dihydrophenanthridine as hydrogen donor. A variety dihydrobenzoxazinones were obtained in high yields up to 99% ee. current work provides a promising solution unreactive substrates frustrated Lewis pair-catalyzed asymmetric hydrogenation.

Язык: Английский

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Enantioselective Synthesis of 2-Aryl-3,3-Disubstituted Indolines from 3H-Indoles via Deracemization

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 8, 2025

An enantioselective synthesis of 2-aryl 3,3-disubstituted 3H-indoles has been successfully developed via a deracemization process involving borane-catalyzed hydrogenation and chiral phosphoric-acid-catalyzed asymmetric transfer hydrogenation. A variety were effective substrates to afford the desired indolines in 86-95% yields with 45-92% ee's.

Язык: Английский

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Biomimetic Asymmetric Reduction Based on the Regenerable Coenzyme NAD(P)H Models

Accounts of Chemical Research, Год журнала: 2023, Номер 56(15), С. 2096 - 2109

Опубликована: Июль 13, 2023

ConspectusIn nature, the coenzyme NAD(P)H is utilized for transfer of hydrogen and electrons in biocatalytic reduction, which involves process recycling, usage, reduction. Inspired by biological system, a series nonregenerable achiral chiral models were synthesized employed. However, this approach faced intractable limitations, such as need an equivalent amount mimics, accompanied production byproducts, resulted poor atom economy difficult separation products. Therefore, development new efficient methodologies synthesis, regeneration, application organic synthesis greatly desired.To tackle these challenges, regenerable designed based on principles reduction applied them biomimetic asymmetric (BMAR) reactions. This Account summarizes our endeavors rational design, models. First, we will introduce design (dihydrophenanthridine dihydropyrroloquinoxaline), successfully to BMAR imines heteroaromatics using homogeneous ruthenium complex regeneration catalyst, phosphoric acid terminal reductant. Regenerable require addition catalysts or ligands stereoselective control during process. screening tedious. Narrow substrate scope further limited their synthesis. (CYNAM FENAM) with planar chirality, commercially available Brønsted acids, Lewis organocatalysts catalyst. Notably, original factor enantioselective from In addition, strategy could also realize myriad electron-deficient tetrasubstituted alkenes, are challenging substrates transition metal catalyzed hydrogenation. methodology provides building blocks bioactive molecules. Finally, detailed mechanism BMAR, models, was elaborated through combination experiments density functional theory calculations. summary, believe that results presented hold significant implications beyond work have potential applications field catalysis synthetic methodology.

Язык: Английский

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Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions

Advanced Functional Materials, Год журнала: 2024, Номер 34(47)

Опубликована: Апрель 15, 2024

Abstract Many of the functions and features practically useful materials are province molecular‐level chemistry their modulation at different length‐scale. This report illustrates behind [2.2]paracyclophane‐based with a particular focus on most recent explorations through‐space conjugated small‐molecule organic emitters, π‐stacked macrocyclic molecules polymers, poly(p‐phenylenevinylene)s featuring well‐defined donor‐acceptors sequence control, surface engineering technologically‐relevant parylenes that finds broad applications across field chemical science technology. largely deals potential opportunities associated molecular planar chirality, conformational behaviors, strain‐induced non‐planarity aromatics, profound impacts conjugation π‐electron interactions/delocalization optoelectronic properties π‐conjugated polymers extended structures consisting cyclophanes. A special is put concept supramolecular using chemically‐programmed chiral cyclophanes via non‐covalent stacking controlled arrangements. Illustrating cyclophane as precursors/monomers fabrication strategies for incorporation in structurally‐controlled (poly( p ‐xylylene)s formed vapor deposition polymerization post‐deposition interface described. Demonstrating rather approach electronically‐dictated ring‐opening metathesis employing strained cyclophane‐diene precursors generate poly( ‐phenylenevinylene)s (i.e., low dispersity) donor‐acceptor control also discussed. will serve an indispensable one‐stop reference organic, polymer chemists, well material scientists working research innovations.

Язык: Английский

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Enantioselective Synthesis of 2-Functionalized Tetrahydroquinolines through Biomimetic Reduction

Organic Letters, Год журнала: 2021, Номер 23(23), С. 9112 - 9117

Опубликована: Ноя. 12, 2021

Biomimetic asymmetric reduction of 2-functionalized quinolines has been successfully developed with the chiral and regenerable NAD(P)H model CYNAM in presence transfer catalyst simple achiral phosphoric acids, providing tetrahydroquinolines up to 99% ee. Using this methodology as a key step, potent opioid analgesic containing 1,2,3,4-tetrahydroquinoline motif was synthesized high overall yield.

Язык: Английский

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Metallated dihydropyridinates: prospects in hydride transfer and (electro)catalysis

Chemical Science, Год журнала: 2023, Номер 14(31), С. 8234 - 8248

Опубликована: Янв. 1, 2023

Hydride transfer (HT) is a fundamental step in wide range of reaction pathways, including those mediated by dihydropyridinates (DHP − s).

Язык: Английский

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Catalytic Asymmetric Hydrogenation of Tetrasubstituted Unsaturated Lactams: An Efficient Approach to Enantioenriched 3,4-Disubstituted Piperidines

Organic Letters, Год журнала: 2022, Номер 24(2), С. 675 - 680

Опубликована: Янв. 10, 2022

Asymmetric hydrogenation of tetrasubstituted alkenes remains a formidable challenge in asymmetric catalysis. We report herein an unprecedented Rh-catalyzed enantioselective and diastereoselective easily accessed α,β-disubstituted unsaturated lactams to afford synthetically valuable chiral with 1,2-consecutive stereocenters. The reaction could be performed on the gram scale, products concisely transformed enantiomerically pure trans-3,4-disubstituted piperidines, which are prevalent structural units medicinal agents.

Язык: Английский

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Transfer-catalyst-free biomimetic asymmetric reduction of 3-sulfonyl coumarins with a regenerable NAD(P)H model

Chemical Communications, Год журнала: 2022, Номер 58(24), С. 3973 - 3976

Опубликована: Янв. 1, 2022

A novel transfer-catalyst-free biomimetic reduction of the tetrasubstituted olefins 3-sulfonyl coumarins with chiral and regenerable [2.2]paracyclophane-based NAD(P)H model CYNAM has been developed, affording dihydrocoumarins excellent enantioselectivities.

Язык: Английский

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