C(sp3)‐F Bond Activation by Lewis Base‐Boryl Radicals via Concerted Electron‐Fluoride Transfer DOI
Xiao‐Song Xue,

Xueying Guo,

Yu‐Chen Zhang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

Abstract Selective C−F bond activation through a radical pathway in the presence of multiple C−H bonds remains formidable challenge, owing to extraordinarily strong strength bond. By aid density functional theory calculations, we disclose an innovative concerted electron‐fluoride transfer mechanism, harnessing unique reactivity Lewis base‐boryl radicals selectively activate resilient fluoroalkanes. This enables direct abstraction fluorine atom and subsequent generation alkyl radical, thus expanding boundaries halogen reactions.

Language: Английский

Nickel-Catalyzed Asymmetric Homobenzylic Hydroamidation of Aryl Alkenes to Access Chiral β-Arylamides DOI
Xiang Lyu,

Eunmi Jeon,

Changhyeon Seo

et al.

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

Published: Feb. 25, 2025

Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in synthesis β-(hetero)arylethylamides. By employing transposed NiH catalysis approach, this method facilitates formation key chiral nickel-amido intermediates, enabling insertion into alkenes to produce desired β-arylamide products with excellent enantioselectivity. The exhibits high functional group tolerance utilizes readily available starting materials vinylarenes react dioxazolone as robust amidating source. Notably, approach was successfully applied pharmaceutical compounds natural products, such Clobenzorex, Direx, Selegiline, Sacubitril, Cipargamin.

Language: Английский

Citations

3
Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer DOI
Chengliang Deng, Hao Wu,

Sheng Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1294 - 1304

Published: Jan. 7, 2025

Given the widespread presence of spirocyclic scaffolds in natural products and pharmacologically relevant synthetic compounds, development efficient methodologies for their construction holds great importance medicinal chemistry pharmaceutical research. In this study, a general photochemical dearomative spirocyclization nonactivated arenes has been established. The key to method lies ability amine-borane radicals activate aryl bromides iodides via halogen-atom transfer, thereby allowing conversion halides into corresponding subsequent chemodivergent transformations. remarkable compatibility versatility 1,4-difunctionalization is showed by rapid assembly structurally diverse 1,4-cyclohexadiene-based spirocycles incorporating oxindole, indoline, or dihydrobenzofuran subunits. Moreover, potential utility protocol exemplified formal total synthesis vasopressin V2 receptor antagonist Satavaptan.

Language: Английский

Citations

1
Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical DOI Creative Commons

Yuto Yoshida,

Waka Okada,

Kazutake Takada

et al.

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

Published: Jan. 10, 2025

Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables strategic assembly a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated group transfer (CGT) strategy malononitriles under photocatalytic conditions. This allows for cleavage C(sp3)–CN and formation C(sp3)–D C(sp3) to realize decyanative deuteration cyclization via radical-polar crossover. Computational studies successfully demonstrated reactivity CGT promoters can be accurately assessed.

Language: Английский

Citations

1
Boryl Radical-Mediated Halogen-Atom Transfer (XAT) Enables the Sonogashira-Like Alkynylation of Alkyl Halides DOI Creative Commons
Javier Corpas, Maialen Alonso, Daniele Leonori

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The Sonogashira-like alkynylation of alkyl halides is achieved by a photocatalytic approach exploiting amine-ligated boryl radicals as halogen-atom transfer mediators in combination with alkynyl sulfones SOMOphilic reagents.

Language: Английский

Citations

5
Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation DOI Creative Commons

Chang-Zhen Fang,

Beibei Zhang,

Yongliang Tu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in transformations through halogen-atom transfer (XAT). However, unactivated chlorides still present an open challenge this strategy. We herein describe new activation mode of the LBR to construct C(sp

Language: Английский

Citations

4
Photocatalytic Borylation of Imines and Alkenes via Decarboxylation of Trimethylamine Carboxyborane: A New Approach for Generating Boryl Radicals DOI
Haowen Jiang,

Hao-Ni Qin,

Ai-Lian Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9282 - 9287

Published: Oct. 23, 2024

In this study, we investigated the photocatalytic decarboxylation of trimethylamine carboxyborane under mild conditions, successfully generating boryl radicals for subsequent borylation reactions with imines and various alkenes. This method exhibited broad substrate compatibility, including functionalization biologically relevant molecules. Our findings expand utility beyond its role as a carbon-monoxide- drug-releasing agent, highlighting potential in radical chemistry through decarboxylation. work establishes robust foundation further exploration synthetic application carboxyborane.

Language: Английский

Citations

3
Controllable Hydrodebromination of Tribromomethyl Groups via Lewis Base–Borane-Mediated Ionic and Radical Pathways DOI
Feng‐Lian Zhang, Yi‐Feng Wang, Yan Liu

et al.

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract Compounds bearing mono- and dibromomethyl groups are extensively utilized in synthetic medicinal chemistry. In this regard, selective debromination of readily or easily accessible tribromomethyl compounds offers a direct efficient method to access those two moieties. work, we introduced Lewis base–borane-mediated hydrodebromination via ionic radical pathway. Using 4-(dimethylamino)pyridine–borane (DMAP-BH3) as hydride donor, monohydrodebromination was achieved nucleophilic substitution by hydride, delivering groups. On the other hand, treatment with an N-heterocyclic carbene–borane (NHC-BH2CN) boryl precursor presence dilauroyl peroxide (DLP) initiator afforded monobromomethyl through consecutive bromine atom abstractions cleave C–Br bonds. Various group acetamides acetates were applied developed protocol, showcasing good functional tolerance broad substrate scope.

Language: Английский

Citations

0
A Radical Precursor Based on the Aromatization of p-Quinol Esters Enabled by Pyridine-Boryl Radical DOI
Xiaoli Huang,

Ruji Xiong,

Yi Cui

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

A class of prearomatic carboxylic acid p-quinol ester radical precursors has been developed successfully, which could undergo homolytic cleavage the para C-O bond esters via pyridine-boryl radical-induced aromatization in presence pyridines and diboron reagents, affording corresponding alkyl decarboxylation from carboxyl situ. In addition, were further applied substitution with phenylsulfonyl compounds self-coulpings. This method not only provides a new approach to generation intermediate but also expands application boron radicals.

Language: Английский

Citations

0
Cobalt-Catalyzed Remote Site-Selective Hydroboration of Unactivated Alkenes via Chain-Walking Strategy DOI
Zhiqiang Wang,

Mengjie Zhang,

Xue Li

et al.

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

Published: March 11, 2025

An expedient synthesis of α-aminoboronic acid derivatives via cobalt-catalyzed remote site-selective hydroboration unactivated alkenes is described herein. The strategy characterized by its simplicity, site-selectivity, and wide substrate scope, as both terminal internal could undergo the reaction smoothly, affording corresponding products in good yields. According to mechanism, Co-H generated from Co(acac)2 presence HBpin, which starts chain-walking a series alkene insertion β-H elimination process.

Language: Английский

Citations

0
MeOH-Triggered Halogen-Atom Transfer of Unactivated Alkyl Bromides Enabling the Photoredox Giese Addition DOI

Xian‐Chen He,

Yanling Liu, Jie Gao

et al.

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

Published: March 18, 2025

Herein, a nickel-catalyzed, photoredox Giese addition reaction with readily accessible alkyl bromides, driven by available feedstock MeOH as the halogen-atom transfer (XAT) reagent, was successfully achieved under mild conditions. The versatility of this protocol demonstrated through range structurally varied bromides and Giese-type acceptors moderate to good yields. Mechanistic investigation highlights that formation radicals XAT tentatively prompted •CH2OH, which derived from sequential photo-oxidation/1,2-hydrogen-atom MeOH.

Language: Английский

Citations

0