Catalytic atroposelective synthesis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

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Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

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Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13301 - 13309

Published: Oct. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Language: Английский

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N,O-Auxiliary Enabled Cobaltaelectro-Catalyzed Atroposelective C–H Annulation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 1 - 9

Published: Dec. 7, 2023

Herein, we disclosed an efficient synthesis of C–N axially chiral pyridine-N-oxides through cobalt-catalyzed enantioselective C–H activation and annulation under electro-oxidative conditions. This protocol is accomplished by using a readily available cobalt(II) catalyst salicyloxazoline (Salox) ligand in undivided cell. The combination electrochemical simple Co/Salox system enabled effective control over the chemo- enantioselectivity process. A broad range benzamides alkynes bearing diverse functional groups are well compatible to deliver products with high yields enantioselectivities (up 97% yield 99% ee). scalability, asymmetric application, transformations demonstrated synthetic practicality. Moreover, photoluminescence properties further highlight potential applications this strategy material development performance enhancement.

Language: Английский

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Enantioselective C–H bond functionalization under Co(iii)-catalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3354 - 3369

Published: Jan. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Language: Английский

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Nickel-Catalyzed Atroposelective C–H Alkylation Enabled by Bimetallic Catalysis with Air-Stable Heteroatom-Substituted Secondary Phosphine Oxide Preligands

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9172 - 9180

Published: March 21, 2024

The catalytic asymmetric construction of axially chiral C–N atropisomers remains a formidable challenge due to their low rotational barriers and is largely reliant on toxic, cost-intensive, precious metal catalysts. In sharp contrast, we herein describe the first nickel-catalyzed atroposelective C–H alkylation for compounds with aid heteroatom-substituted secondary phosphine oxide (HASPO)-ligated Ni–Al bimetallic catalyst. A wide range alkenes, including terminal internal were well compatible reaction, providing variety benzimidazole derivatives in high yields enantioselectivities (up 97:3 e.r.). key success was identification novel HASPOs as highly effective preligands. Mechanistic studies revealed catalyst mode action, in-depth data science analysis elucidated features responsible preligands controlling enantioselectivity.

Language: Английский

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Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 17, 2024

In recent years, enantioselective electrocatalysis has surfaced as an increasingly-effective platform for sustainable molecular synthesis. Despite indisputable progress, strategies that allow the control of two distinct stereogenic elements with high selectivity remain elusive. contrast, we, herein, describe electrochemical cobalt-catalyzed C-H activations enable installation chiral centers along a axis levels enantio- and diastereoselectivities. The developed strategy allowed C-H/N-H activations/annulations cyclic non-cyclic alkenes providing expedient access to various central well atropo-chiral dihydroisoquinolinones paired valuable hydrogen evolution reaction. Studies on atropo-stability obtained compounds demonstrated exceedingly mild conditions ensured by electrocatalytic process were key achieved stereoselectivities.

Language: Английский

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Electrochemical enabled cobalt catalyzed enantioselective C-H acyloxylation of aryl phosphamide with carboxylic acid

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8323 - 8329

Published: Jan. 1, 2024

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Language: Английский

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Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 3, 2024

Language: Английский

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Enhancing electrochemical reactions in organic synthesis: the impact of flow chemistry

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Utilizing electrons directly offers significant potential for advancing organic synthesis by facilitating novel reactivity and enhancing selectivity under mild conditions. As a result, an increasing number of chemists are exploring electrosynthesis. However, the efficacy electrochemical transformations depends critically on design cell. Batch cells often suffer from limitations such as large inter-electrode distances poor mass transfer, making flow promising alternative. Implementing cells, however, requires foundational understanding microreactor technology. In this review, we briefly outline applications electrosynthesis before providing comprehensive examination existing reactor technologies. Our goal is to equip with insights needed tailor their meet specific requirements effectively. We also highlight application designs in scaling up processes integrating high-throughput experimentation automation. These advancements not only enhance synthetic community but hold promise both academia industry.

Language: Английский

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