Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июнь 28, 2022

An unprecedented hydroalkylation of racemic allylic alcohols and ketimine esters enabled by Cu/Ru relay catalysis has been developed via merging the ruthenium-catalyzed asymmetric borrowing-hydrogen reaction with a copper-catalyzed Michael addition in one-pot procedure. The current method enables efficient preparation highly functionalized δ-hydroxyesters bearing 1,4-nonadjacent stereocenters good yields high levels diastereoselectivity excellent enantioselectivity under mild conditions. full complement four stereoisomers products could be readily accessed orthogonal permutations two chiral metal catalysts. work highlights power for stereodivergent construction that were otherwise inaccessible.

Язык: Английский

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Enantioconvergent transformations of secondary alcohols through borrowing hydrogen catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(16), С. 5541 - 5562

Опубликована: Янв. 1, 2023

Enantioconvergent transformations of racemic secondary alcohols to enantioenriched chiral amines, N-heterocycles, higher-order and ketones through borrowing hydrogen catalysis is covered in this review.

Язык: Английский

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Reductive Coupling of Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines by a Cobalt Single-Atom Catalyst

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 17329 - 17336

Опубликована: Июль 7, 2023

Despite the extensive applications, selective and diverse access to N,N'-diarylethane-1,2-diamines remains, date, a challenge. Here, by developing bifunctional cobalt single-atom catalyst (CoSA-N/NC), we present general method for direct synthesis of such compounds via reductive coupling cheap abundant nitroarenes formaldehyde, featuring good substrate functionality compatibility, an easily accessible base metal with excellent reusability, high step atom efficiency. Mechanistic studies reveal that N-anchored single atoms (CoN4) serve as catalytically active sites reduction processes, N-doped carbon support enriches HCHO timely trap in situ formed hydroxyamines affords requisite nitrones under weak alkaline conditions, subsequent inverse electron demand 1,3-dipolar cycloaddition imines followed hydrodeoxygenation cycloadducts furnishes products. In this work, concept catalyst-controlled nitroarene create specific building blocks is anticipated develop more useful chemical transformations.

Язык: Английский

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Chiral Adaptive Induction of an Achiral Cucurbit[8]uril‐Based Supramolecular Organic Framework by Dipeptides in Water

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(37)

Опубликована: Июль 20, 2023

Chiral induction by natural biomolecules can reveal the indispensable role of chiral structures in life and be used to develop chirality-sensing biomolecular recognition. Here, we present synthesis characterization an achiral supramolecular organic framework (SOF-1) constructed from cucurbit[8]uril (CB[8]) hexaphenylbenzene (HPB) derivative (1) water. Due propeller-like rotational conformation HPB units specific recognition properties CB[8], SOF-1 demonstrates adaptive water when interacting with N-terminal Trp-/Phe-containing dipeptides including L-TrpX L-PheX (X is amino acid residue), respectively, exhibiting contrasting circular dichroism (CD) circularly polarized luminescence (CPL) spectra. Consequently, has been developed as a host chiroptical sensor capable recognizing distinguishing sequence-opposite dipeptide pairs L-TrpX/L-XTrp L-PheX/L-XPhe based on sequence-selective CD responses.

Язык: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Язык: Английский

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Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Март 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Язык: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

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Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies

ACS Omega, Год журнала: 2022, Номер 7(42), С. 37008 - 37038

Опубликована: Окт. 11, 2022

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C–C bonds correspond to outstanding ways afford compounds with more versatile functional groups, which are commonly used building blocks production fine chemicals and feedstock for industrial field. Herein, we present an account Mn-catalyzed alkenes alkynes main objective finding mechanistic tendencies that could serve a platform works come.

Язык: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2023, Номер 27(3), С. 423 - 447

Опубликована: Фев. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Язык: Английский

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Iron- and Organo-Catalyzed Borrowing Hydrogen for the Stereoselective Construction of Tetrahydropyrans

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5788 - 5793

Опубликована: Июнь 27, 2024

Stereocontrolled oxa-Michael additions are challenging, given the high reversibility of process, which ultimately leads to racemization newly formed stereocenters. When iron-catalyzed borrowing hydrogen from allylic alcohols was combined with a stereocontrolled organocatalytic addition, wide array chiral tetrahydropyrans were efficiently prepared. The reaction could be performed in diastereoselective manner pre-existing stereocenters or enantioselectively achiral substrates. key success reactivity iron complex, selective for alcohol dehydrogenation and irreversibly led final product.

Язык: Английский

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