Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23910 - 23917

Опубликована: Окт. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

Язык: Английский

---

Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Год журнала: 2024, Номер 7(6), С. 655 - 665

Опубликована: Апрель 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Язык: Английский

---

Biomimetic 1,2-amino migration via photoredox catalysis

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Synthetic organic chemists continually draw inspiration from biocatalytic processes to innovate synthetic methodologies beyond existing catalytic platforms. Within this context, although 1,2-amino migration represents a viable biochemical process, it remains underutilized within the chemistry community. Here we present biomimetic accomplished through synergistic combination of mechanism and photoredox catalysis. This platform enables modular synthesis γ-substituted β-amino acids by utilizing abundant α-amino-acid derivatives readily available molecules as coupling partners. mild method features excellent substrate functionality compatibility, affording diverse range (more than 80 examples) without need for laborious multistep synthesis. Mechanistic studies, supported both experimental observations theoretical analysis, indicate that involves radical addition α-vinyl-aldimine ester, 3-exo-trig cyclization subsequent rearrangement process. We anticipate transformation will serve versatile highly efficient construction unnatural acids. Enzyme-catalysed process is currently Building upon mechanism, photoredox-catalysed has been developed. By integrating conditions, approach library

Язык: Английский

---

Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Язык: Английский

---

Dual Nickel/Photoredox-Catalyzed Arylsulfonylation of Allenes

Organic Letters, Год журнала: 2024, Номер 26(24), С. 5074 - 5081

Опубликована: Июнь 10, 2024

The nickel/photoredox dual catalysis system is an efficient conversion platform for the difunctionalization of unsaturated hydrocarbons. Herein, we disclose first nickel/photoredox-catalyzed intramolecular 1,2-arylsulfonylation allenes, which can accurately construct a C(sp2)–C(sp2) bond and C(sp3)–S bond. reaction exhibits excellent chemoselectivity regioselectivity, allowing modular conformations diverse series 3-sulfonylmethylbenzofuran derivatives. Control experiments showed that bipyridine ligand crucial formation stable σ-alkyl nickel intermediate, providing possibility sulfonyl radical insertion. Meanwhile, electrophilic facilitates further oxidative addition intermediate inhibits with allenes. In addition, control experiments, cyclic voltammetry tests, Stern–Volmer density functional theory calculations afford evidence Ni(0)/Ni(I)/Ni(II)/Ni(III) pathway in this 1,2-arylsulfonylation.

Язык: Английский

---

Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 13, 2024

ConspectusIn recent years, radical-mediated cross-coupling reactions have emerged as a compelling strategy for achieving rich diversity in molecular topologies under benign conditions. However, the inherent high reactivity of radicals presents considerable challenges controlling reaction pathways and selectivity, which often results limited range substrates constrained profile. Given capacity visible-light photoredox catalysis to generate wide variety reactive radical ions controlled manner propensity copper complexes toward species, we envisaged that synergy between chiral catalysts photoactive would pave way developing innovative strategies. This integration is poised unlock broad spectrum enantioselective multicomponent reactions.In this Account, describe our insights efforts realm reactions. These advancements been achieved through application dual photoredox/copper or bifunctional visible light irradiation. Our work systematically divided into two sections based on activation modes. The first section focuses photoinduced copper-catalyzed C-C C-O bond formation addition/nucleophilic trap sequence. discussion particularly concentrated asymmetric carbocyanation carboarylation vinylarenes, 1,3-enynes, 1,3-dienes. findings underscore irradiation with can adeptly modulate pace generation, thus orchestrating consecutive stages ensuring attainment both chemo- stereoselectivity. In domain formation, leveraging carboxylic acids nucleophilic oxygen source, introduce suite esterification benzylic, allylic, propargylic radicals. are derived from precursors, showcasing versatility approach. following highlights discovery field catalysis, enables three-component transformations via direct aromatic alkenes. methodology begins generation formal distonic anions photocatalytic single-electron reduction alkenes, thus, enabling orthogonal reactivity. Employing H

Язык: Английский

---

Photoredox/Nickel Dual Catalysis-Enabled Aryl Formylation with 2,2-Dimethoxy-N,N-dimethylethan-1-amine as CO Source

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1478 - 1482

Опубликована: Фев. 9, 2024

Herein, a dual photoredox/nickel catalyzed formylation of aryl bromide with commercially available 2,2-dimethoxy-N,N-dimethylethan-1-amine as an effective CO source has been successfully achieved, delivering series aromatic aldehydes in moderate to good yields. Compared the traditional reductive carbonylation process, this newly designed synthetic protocol provides straightforward toolbox access aldehydes, obviating use carbon monoxide and stoichiometric reductants. Finally, utility direct reaction was demonstrated pharmaceutical analogue synthesis.

Язык: Английский

---

Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines

Chemical Science, Год журнала: 2025, Номер 16(10), С. 4442 - 4449

Опубликована: Янв. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Язык: Английский

---

Enantioselective reductive cross-couplings to forge C(sp2)–C(sp3) bonds by merging electrochemistry with nickel catalysis

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 28, 2025

Abstract Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling benzyl chlorides aryl halides, yielding chiral 1,1-diaryl compounds good to excellent enantioselectivity. This catalytic reaction can not only be applied chlorides/bromides, which are challenging access other means, but also containing silicon groups. Additionally, absence sacrificial anode lays foundation for scalability. The combination cyclic voltammetry analysis electrode potential studies suggests that Ni I species activate halides via oxidative addition and alkyl single electron transfer.

Язык: Английский

---

Enantioselective Photoredox- and Cu-Catalyzed Cyanoalkylation of Styrenes via Deoxygenation of Alkoxyl Radicals with Organophosphorus Compounds(III)

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

The enantioselective cyanoalkylation of styrenes by a cooperative photoredox and copper catalysis system has been established, providing straightforward access to structurally diverse enantioenriched alkyl nitriles in good yields with excellent enantioselectivities under mild conditions via deoxygenation alkoxyl radicals organophosphorus compounds(III). In addition, the reaction features wide substrate scope functional group tolerance, resultant could be easily converted into series chiral carboxylic acids, amides, esters, etc.

Язык: Английский

---