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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Enantio- and Diastereoselective Synthesis of P-Stereogenic Phospholane Oxides via Cobalt-Catalyzed Hydroalkylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Chiral phospholane ligands and catalysts have been widely applied in asymmetric catalysis synthesis. However, the construction of chiral skeleton remains challenging primarily relies on use auxiliaries or resolution. In this work, a highly enantioselective diastereoselective synthesis P-stereogenic oxides has achieved through cobalt-catalyzed desymmetric hydroalkylation strategy. This method enables two discrete stereocenters with excellent yields enantiomeric excesses.

Language: Английский

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Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions

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

Published: Aug. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Language: Английский

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Cobalt-Catalyzed Regiodivergent and Asymmetric Reductive Coupling of 1,3-Dienes with Aldehydes

Synfacts, Journal Year: 2024, Volume and Issue: 20(07), P. 0710 - 0710

Published: June 14, 2024

Key words aldehydes - cobalt catalysis 1,3-dienes homoallylic alcohols regiodivergent

Language: Английский

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Cobalt-Catalyzed Three-Component Alkyl Arylation of Acrylates with Alkyl Iodides and Aryl Grignard Reagents

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9288 - 9293

Published: Oct. 21, 2024

A highly regioselective cobalt-catalyzed three-component alkyl arylation of acrylates with iodides and aryl Grignard reagents has been established. The reaction efficiently provides an alternative strategy for the construction α-aryl esters a broad substrate scope good yields under mild conditions. practical applicability this protocol is shown by scaled-up further transformations products. In addition, preliminary mechanistic explorations demonstrated that radicals generated efficient cobalt catalysis are instantaneously added to finally afford desired

Language: Английский

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Copper(I)-Catalyzed Asymmetric Nucleophilic Addition to Aldehydes with Skipped Enynes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(47), P. 10072 - 10077

Published: Nov. 18, 2024

The development of sustainable and novel strategies for constructing complex chiral molecules with versatile transformation potential is a long-term pursuit in the chemistry community. We report copper(I)-catalyzed enyne addition to aldehydes under proton-transfer conditions, unlike previous examples which were limited use preformed reactive nucleophiles containing allylic heteroatoms or electron-withdrawing groups. This protocol provides an efficient platform installing alcohol moieties broad substrate scope high regio-, stereo-, enantioselectivity.

Language: Английский

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