Ligand–Metal Cooperation Enables Net Ring-Opening C–C Activation/Difunctionalization of Cyclopropyl Ketones DOI
Michael M. Gilbert, Michael J. Trenerry,

Victoria Longley

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11277 - 11290

Published: Aug. 11, 2023

Reactions that cleave C–C bonds and enable functionalization at both carbon sites are powerful strategic tools in synthetic chemistry. Stereodefined cyclopropyl ketones have become readily available would be an ideal source of 3-carbon fragments, but general approaches to net activation/difunctionalization unknown. Herein, we demonstrate the cross-coupling with organozinc reagents chlorotrimethylsilane form 1,3-difunctionalized, ring-opened products. A combination experimental theoretical studies rules out more established mechanisms sheds light on how cooperation between redox-active terpyridine (tpy) ligand nickel atom enables bond activation step. The reduced (tpy·–)NiI species activates via a concerted asynchronous ring-opening transition state. resulting alkylnickel(II) intermediate can then engaged by aryl, alkenyl, alkylzinc furnish cross-coupled This allows quick access products difficult make conjugate addition methods, such as β-allylated β -benzylated enol ethers. utility this approach is demonstrated synthesis key (±)-taiwaniaquinol B total prostaglandin D1.

Language: Английский

Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides DOI
Xuan‐Feng Jiang, Hao Jiang, Qian Yang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8347 - 8354

Published: April 28, 2022

Grignard addition is one of the most important methods used for syntheses alcohol compounds and has been known over a hundred years. However, research on asymmetric catalysis relies use organometallic nucleophiles. Here, we report first visible-light-induced cobalt-catalyzed reductive Grignard-type synthesizing chiral benzyl alcohols (>50 examples, up to 99% yield, ee). This methodology advantages mild reaction conditions, good functionality tolerance, excellent enantiocontrol, avoidance mass metal wastes, precious catalysts. Kinetic realization studies suggested that migratory insertion an aryl cobalt species into aldehyde was rate-determining step reaction.

Language: Английский

Citations

92
Catalytic multicomponent reaction involving a ketyl-type radical DOI
Huan‐Ming Huang, Peter Bellotti, Suhyeon Kim

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(6), P. 464 - 474

Published: June 13, 2022

Language: Английский

Citations

43
Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji–Trost Homologative Amination Reaction toward Allylic Amines DOI

Nikita Kvasovs,

Jian Fang, Fedor Kliuev

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18497 - 18505

Published: Aug. 9, 2023

A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds

Language: Английский

Citations

36
Phenanthroline-Initiated Anti-selective Hydrosulfonylation of Unactivated Alkynes with Sulfonyl Chlorides DOI

Ci-Shuang Dong,

Wen‐Yan Tong,

Peng Ye

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6983 - 6993

Published: May 8, 2023

A simple and general method for anti-selective hydrosulfonylation of unactivated alkynes with sulfonyl chlorides in the presence a catalytic amount phenanthroline-based Lewis base (Me3Si)3SiH as hydrogen atom donor has been developed. The protocol proceeds efficiently under mild metal-free conditions, delivering diverse set (Z)-vinyl sulfones high stereoselectivity. Additionally, displays excellent functional-group compatibility can be applied to late-stage modifications complex drugs their derivatives. Experimental density functional theory studies unveiled that key transformation's success is employment base, which interacts form halogen-bond accelerates cleavage S–Cl bonds irradiation visible light.

Language: Английский

Citations

26
Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence DOI

Zhan Dong,

Changyu Xu,

Jianchao Chang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4395 - 4406

Published: March 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Language: Английский

Citations

14
Unlocking carbene reactivity by metallaphotoredox α-elimination DOI
Benjamin T. Boyle, Nathan W. Dow, Christopher B. Kelly

et al.

Nature, Journal Year: 2024, Volume and Issue: 631(8022), P. 789 - 795

Published: June 6, 2024

Language: Английский

Citations

13
Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

Citations

12
Ni/Photoredox-Catalyzed Enantioselective Acylation of α-Bromobenzoates with Aldehydes: A Formal Approach to Aldehyde-Aldehyde Cross-Coupling DOI
Chengyang Li,

Junliang Cheng,

Xiang Wan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19909 - 19918

Published: June 12, 2024

The catalytic cross-coupling of identical or similar functional groups is a cornerstone strategy for carbon-carbon bond formation, as exemplified by renowned methods, such olefin cross-metathesis, Kolbe electrolysis, and various cross-electrophile couplings. However, methodologies coupling aldehydes─fundamental building blocks in organic synthesis─remain underdeveloped. While the benzoin-type condensation, first reported 1832, offers reliable route aldehyde dimerization, chemo- enantioselective nonidentical yet aldehydes remains an unsolved challenge. Herein, we report unified platform enabling highly aldehydes. By leveraging nickel photoredox catalysis tandem with discrete activation strategies each aldehyde, this mechanistically distinct approach facilitates union aldehyde-derived α-oxy radical acyl radical, photocatalytically generated from aldehyde. This novel enables modular access to enantioenriched α-oxygenated ketones two minimally differentiated aliphatic substituents, feat not achievable existing chemocatalytic biocatalytic techniques. synthetic utility method demonstrated its application streamlined asymmetric synthesis medicinally relevant molecules. Additionally, mechanistic investigations rationalize versatility exploit new pathways addressing long-standing challenges.

Language: Английский

Citations

9
Synthesis of Acylbenzo[b]thiophenes, Benzofurans and Indoles via Intramolecular Oxidative Cyclization Enabled by Photocatalytic Hydrogen Atom Transfer (HAT) DOI Creative Commons

Fen-Dou Wang,

Jin Jiang,

Tiantian Xu

et al.

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100119 - 100119

Published: Jan. 1, 2025

An efficient strategy for intramolecular oxidative cyclization of 2-alkynylthioanisoles toward 3-acylbenzo[b]thiophenes by photochemical hydrogen atom transfer catalysis has been developed. 3-Acylbenzo[b]selenophenes, benzofurans and indoles can also be prepared this protocol. This reaction is convenient to perform at room temperature under simple conditions using air as the oxidant. Mechanistic studies revealed that formation α-thioalkyl radicals intermediate crucial.Graphical abstract

Language: Английский

Citations

1
Nickel-Catalyzed Defluorinative Coupling of Aliphatic Aldehydes with Trifluoromethyl Alkenes DOI
Jichao Xiao, John Montgomery

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2463 - 2471

Published: Feb. 3, 2022

A simple procedure is reported for the nickel-catalyzed defluorinative alkylation of unactivated aliphatic aldehydes. The process involves catalytic reductive union trifluoromethyl alkenes with aldehydes using a nickel complex 6,6'-disubstituted bipyridine ligand zinc metal as terminal reductant. protocol distinguished by its broad substrate scope, mild conditions, and setup. Reaction outcomes are consistent intermediacy an α-silyloxy(alkyl)nickel intermediate generated low-valent catalyst, silyl electrophile, aldehyde substrate. Mechanistic findings cyclopropanecarboxaldehyde provide insights into nature reactive intermediates illustrate fundamental reactivity differences that governed subtle changes in structure.

Language: Английский

Citations

38