Organo/Transition-Metal Combined Catalysis Rejuvenates Both in Asymmetric Synthesis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2415 - 2437

Published: Jan. 20, 2022

Since its advent two decades ago, asymmetric organo/transition-metal combined catalysis (AOMC), including cooperative and relay catalysis, has leveraged redistribution of chemical bonds to build up molecular complexity enantio-differentiation form individual enantiomers with activations from versatile organocatalysts transition-metal complexes. The goal this perspective is provide readers the fundamental attributes AOMC─orthogonality, kinetics, mechanism, selectivity─to understand how an organocatalyst a complex would collaborate enable fruitful new reaction development what are intrinsic pathways unproductive events, such as catalyst self-quenching. In closing, future opportunities AOMC have been directed toward prediction effective combination, introducing enzyme focus on transient radical intermediate, animate area in years come.

Language: Английский

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Catalytic asymmetric reductive hydroalkylation of enamides and enecarbamates to chiral aliphatic amines

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Feb. 26, 2021

Abstract To increase the reliability and success rate of drug discovery, efforts have been made to C( sp 3 ) fraction avoid flat molecules. -Rich enantiopure amines are most frequently encountered as chiral auxiliaries, synthetic intermediates for pharmaceutical agents bioactive natural products. Streamlined construction aliphatic has long regarded a paramount challenge. Mainstream approaches, including hydrogenation enamines imines, C–H amination, alkylation were applied synthesis with circumscribed skeleton structures; typically, carbon centre was adjacent an auxiliary aryl or ester group. Herein, we report mild general nickel-catalysed asymmetric reductive hydroalkylation effectively convert enamides enecarbamates into drug-like α-branched derivatives. This reaction involves regio- stereoselective hydrometallation enamide enecarbamate generate catalytic amount enantioenriched alkylnickel intermediate, followed by C–C bond formation via alkyl electrophiles.

Language: Английский

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A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion

Nature Catalysis, Journal Year: 2021, Volume and Issue: 4(6), P. 523 - 531

Published: June 21, 2021

Language: Английский

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Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines

Nature, Journal Year: 2023, Volume and Issue: 618(7964), P. 294 - 300

Published: March 20, 2023

Language: Английский

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Visible light-mediated photolysis of organic molecules: the case study of diazo compounds

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(48), P. 7346 - 7360

Published: Jan. 1, 2023

This article discusses the photochemistry of several diazo compounds undergoing visible light-mediated photolysis to generate free carbenes (or other highly reactive intermediates), which can be sequentially trapped by different reacting partners.

Language: Английский

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Enantioselective propargylic amination and related tandem sequences to α-tertiary ethynylamines and azacycles

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 521 - 532

Published: March 19, 2024

Language: Английский

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Heterogeneous Rhodium Single-Atom-Site Catalyst Enables Chemoselective Carbene N–H Bond Insertion

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10847 - 10856

Published: April 7, 2024

Transition-metal-catalyzed carbene insertion reactions of a nitrogen–hydrogen bond have emerged as robust and versatile methods for the construction C–N bonds. While significant progress homogeneous catalytic metal N–H insertions has been achieved, control chemoselectivity in field remains challenging due to high electrophilicity intermediates. Herein, we present an efficient strategy synthesis rhodium single-atom-site catalyst (Rh-SA) that incorporates Rh atom surrounded by three nitrogen atoms one phosphorus doped carbon support. This Rh-SA catalyst, with loading only 0.15 mol %, exhibited exceptional performance heterogeneous various anilines heteroaryl amines combination diazo esters. Importantly, selectively transformed aniline derivatives bearing multiple nucleophilic moieties into single isomers, while popular Rh2(OAc)4 produced mixture overfunctionalized side products. Additionally, similar selectivities set stereoelectronically diverse esters were obtained, highlighting general applicability this catalysis approach. On basis density functional theory calculations, observed selectivity was attributed barriers accelerated proton transfer assisted Overall, investigation metal-catalyzed underscores potential powerful complementary tool organic synthesis.

Language: Английский

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Polymeric membranes with highly homogenized nanopores for ultrafast water purification

Nature Sustainability, Journal Year: 2024, Volume and Issue: 7(7), P. 901 - 909

Published: May 29, 2024

Language: Английский

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Photoinduced Regiodivergent and Enantioselective Cross-Coupling of Glycine Derivatives with Hydrocarbon Feedstocks

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from single set starting materials, significantly enriching their enantiomeric composition. However, design radical-mediated regiodivergent and enantioselective reactions that can accommodate wide range functional groups substrates has posed significant challenges. The obstacles primarily lie in switching regioselectivity achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed new catalytic system integrates photoinduced hydrogen atom transfer (HAT) copper catalysis, involving fine-tuning ligands, additives, other reaction parameters. facilitates cross-couplings between N-aryl glycine ester/amide derivatives abundant hydrocarbon feedstocks through strong C(sp3)–H bond activation. This approach allows controlled stereoselective formation C(sp3)–C(sp3) C(sp3)–N bonds, yielding rich variety C- or N-alkylated esters amides commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), enantioselectivities 96% ee). Our methodology not only provides promising avenue incorporation alkyl functionalities onto specific sites biologically molecules but also offers practical while simultaneously induction within photochemical reactions.

Language: Английский

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Highly Enantioselective O–H Bond Insertion Reaction of α-Alkyl- and α-Alkenyl-α-diazoacetates with Water

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(23), P. 10557 - 10566

Published: May 14, 2020

Catalytic asymmetric reactions in which water is a substrate are rare. Enantioselective transition-metal-catalyzed insertion of carbenes into the O-H bond can be used to incorporate stereogenic center, but reported chiral catalysts give good results only when α-aryl-α-diazoesters as carbene precursors. Herein we report first highly enantioselective between and α-alkyl- α-alkenyl-α-diazoesters precursors, with catalysis by combination achiral dirhodium complexes phosphoric acids or phosphoramides. Participation phosphoramides transfer reaction markedly suppressed competing side reactions, such β-H migration, dimerization, olefin isomerization, thus ensured yields desired products. Fine-tuning ester moiety facilitated enantiocontrol proton enol intermediates resulted excellent enantioselectivity. This protocol represents an efficient new method for preparation multifunctionalized α-alkyl α-alkenyl hydroxyl esters, readily undergo various transformations synthesis bioactive compounds. Mechanistic studies revealed that promoted [1,2]- [1,3]-proton intermediates. Maximization molecular orbital overlap transition states was original driving force involve shuttle this process.

Language: Английский

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