Nickel(ii)-hydrazineylpyridine catalyzed regioselective synthesis of α-benzyl substituted β-hydroxy ketones via a Fenton free radical reaction

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Ni-PyH-catalyzed regioselective synthesis of α-benzyl substituted β-hydroxy ketones is reported via a Fenton free-radical reaction. Protocol enables facile access to products in good excellent yields toluene at room temperature 100 °C.

Язык: Английский

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Cobalt-Catalyzed Enantioselective Reductive Arylation, Heteroarylation, and Alkenylation of Michael Acceptors via an Elementary Mechanism of 1,4-Addition

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20477 - 20493

Опубликована: Июль 10, 2024

Cobalt complexes with chiral quinox ligands effectively promote the enantioselective conjugate addition of enones using aryl, heteroaryl, and alkenyl halides sulfonates. Additionally, a cobalt complex strongly donating diphosphine, BenzP*, successfully catalyzes asymmetric reductive arylation alkenylation α,β-unsaturated amides. Both catalytic systems show broad scopes tolerance sensitive functional groups. reactions can be scaled up low loadings catalysts. Experimental results density theory (DFT) calculations suggest new mechanism elementary 1,4-addition aryl cobalt(I) complexes.

Язык: Английский

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Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones

Advanced Science, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Abstract Herein, the study reports first electrochemical nickel‐catalyzed enantioselective hydro‐arylation/alkenylation of enones in an undivided cell with low‐cost electrodes absence external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for efficient preparation more than 56 valuable β‐arylated/alkenylated ketones a simple manner (up to 97% yield, ee). With advantages electrochemistry, excellent functional group tolerance late‐stage modification complex natural products pharmaceuticals made established protocol greener economic. Mechanism investigation suggests that Ni I /Ni III cycle may be involved this electro‐reductive reaction rather metal reductant driven 0 II cycle. Overall, activation turnover nickel catalyst avoid drawbacks posed by employment stoichiometric amount sensitive powder reductants.

Язык: Английский

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Nickel-Catalyzed Reductive Alkenylation of Enol Derivatives: A Versatile Tool for Alkene Construction

Accounts of Chemical Research, Год журнала: 2024, Номер 57(22), С. 3356 - 3374

Опубликована: Ноя. 1, 2024

ConspectusKetone-to-alkene transformations are essential in organic synthesis, and transition-metal-catalyzed cross-coupling reactions involving enol derivatives have become powerful tools to achieve this goal. While substantial progress has been made nucleophile-electrophile reactions, recent developments nickel-catalyzed reductive alkenylation garnered increasing attention. These methods accommodate a broad range of functional groups such as aldehyde, ketone, amide, alcohol, alkyne, heterocycles, organotin compounds, providing an efficient strategy access structurally diverse alkenes. This Account primarily highlights the contributions from our laboratory growing field while also acknowledging key other researchers.Our early efforts area focused on coupling radical-active substrates, α-chloroboronates. method follows conventional radical chain mechanism, resulting facile valuable allylboronates. Encouraged by these promising results, we subsequently expanded substrate scope encompass radical-inactive compounds. By developing new strategies for controlling cross-selectivity, enabled Csp

Язык: Английский

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Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 72 - 80

Опубликована: Дек. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Язык: Английский

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Cobalt-Catalyzed Enantioselective Reductive Addition of Ketimine with Cyclopropyl Chloride to Construct the Chiral Amino Esters Bearing Cyclopropyl Fragments

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(22), С. 6311 - 6318

Опубликована: Янв. 1, 2024

Co-catalyzed asymmetric reductive addition of ketimine with cyclopropyl chloride has been realized to access diverse chiral amino esters bearing fragments broad functional group tolerance and excellent enantioselectivities.

Язык: Английский

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Oxazaborolidine Catalyzed Asymmetric 1,4-Addition of Diarylphosphine Oxides to α,β-Unsaturated N-Acylindoles and N-Acylpyrroles

Tetrahedron, Год журнала: 2024, Номер unknown, С. 134331 - 134331

Опубликована: Окт. 1, 2024

Язык: Английский

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Enantioselective Nickel-Catalyzed Electrochemical Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

We present an asymmetric electrochemical nickel-catalysed reductive conjugate addition of alkenyl bromides/aryl iodides to α,β-unsaturated ketones in undivided cell, which afforded β-alkenylate/arylate high yields with excellent enantioselectivities.

Язык: Английский

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