γ-Selective C(sp3)–H amination via controlled migratory hydroamination DOI Creative Commons
Changseok Lee, Huiyeong Seo, Jinwon Jeon

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Sept. 27, 2021

Abstract Remote functionalization of alkenes via chain walking has generally been limited to C(sp 3 )–H bonds α and β polar-functional units, while γ -C(sp through controlled alkene transposition is a longstanding challenge. Herein, we describe NiH-catalyzed migratory formal hydroamination alkenyl amides achieved chelation-assisted control, whereby various amino groups are installed at the -position aliphatic chains. By tuning olefin isomerization ligand directing group optimization, -selective amination can be stabilization 6-membered nickellacycle by an 8-aminoquinoline subsequent interception aminating reagent. A range amines bond unactivated with varying alkyl lengths, enabling late-stage access value-added -aminated products. Moreover, employing picolinamide-coupled substrates, this approach further extended δ amination. The chain-walking mechanism pathway selectivity investigated experimental computational methods.

Language: Английский

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes DOI
Shubhankar Kumar Bose, Lujia Mao,

Laura Kuehn

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

Citations

246
Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes DOI
Jun Guo, Zhaoyang Cheng, Jianhui Chen

et al.

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(11), P. 2701 - 2716

Published: May 20, 2021

ConspectusTransition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition catalysts have laid cornerstone in this field, on account their superior reactivity selectivity. In recent years, from an economical sustainable standpoint, first-row, earth-abundant metals received considerable attention, due high natural reserves, affordable costs, low toxicity. Meanwhile, reactions also gained much interest been investigated gradually. However, since chiral ligand libraries for transition-metal catalysis are limited date, development highly enantioselective versions remains a significant challenge.This Account summarizes our efforts developing suitable ligands iron cobalt applications (hydroboration hydrosilylation) alkenes alkynes. design, we envisioned that unsymmetric NNN-tridentate (UNT) scaffolds could promote these transformations with metals. Therefore, several types UNT were designed prepared laboratory, utilizing amino acids as sources. very beginning, oxazoline iminopyridine (OIP) proposed through rational combination nitrogen-containing scaffolds. After systematic survey effects, imine moiety rigid OIP was replaced by conformationally more flexible amine unit, leading construction reactive aminoisopropylpyridine (OAP) ligands. Subsequently, imidazoline (IIP) thiazoline (TIP) altering oxygen atom nitrogen sulfur linkers, respectively. To further expand library, other tridentate containing twisted pincer, anionic, nonrigid backbone synthesized, including iminophenyl oxazolinyl phenylamine (IPOPA) phenyl picolinamide (ImPPA). The efficacy induction has demonstrated sequential alkynes, which exhibit excellent well chemo-, regio-, stereoselectivity broad functional group tolerance. Notably, regio- challenging substrates, such 1,1-disubstituted aryl terminal aliphatic alkenes, achieved. Furthermore, isomerization/hydroboration internal alkynes demonstrates synthetic power catalytic systems. enantioenriched products obtained methodologies be potentially utilized organic synthesis, medicinal chemistry, materials science. We believe continuous field would beneficial catalysis.

Language: Английский

Citations

222
Enantioselective benzylic C–H arylation via photoredox and nickel dual catalysis DOI Creative Commons
Xiaokai Cheng,

Huangzhe Lu,

Zhan Lu

et al.

Nature Communications, Journal Year: 2019, Volume and Issue: 10(1)

Published: Aug. 7, 2019

Abstract The asymmetric cross-coupling reaction is developed as a straightforward strategy toward 1,1-diaryl alkanes, which are key skeleton in series of natural products and bioactive molecules recent years. Here we report an enantioselective benzylic C(sp 3 )−H bond arylation via photoredox/nickel dual catalysis. Sterically hindered chiral biimidazoline ligands designed for this reaction. Readily available alkyl benzenes aryl bromides with various functional groups tolerance can be easily directly transferred to useful alkanes including pharmaceutical intermediates molecules. This proceeds smoothly under mild conditions without the use external redox reagents.

Language: Английский

Citations

188
Recent advances in asymmetric borylation by transition metal catalysis DOI
Jiefeng Hu, Matthias Ferger, Zhuangzhi Shi

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 13129 - 13188

Published: Jan. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Language: Английский

Citations

179
Transition metal-catalyzed alkene isomerization as an enabling technology in tandem, sequential and domino processes DOI Creative Commons
Daniele Fiorito,

Simone Scaringi,

Clément Mazet

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 1391 - 1406

Published: Dec. 10, 2020

One-pot reactions based on catalytic isomerization of alkenes not only offer the inherent advantages atom-, step- and redox-economy but also enable preparation value-added products that would be difficult to access by conventional methods.

Language: Английский

Citations

175
Recent advances in tridentate iron and cobalt complexes for alkene and alkyne hydrofunctionalizations DOI

Huanan Wen,

Guixia Liu, Zheng Huang

et al.

Coordination Chemistry Reviews, Journal Year: 2019, Volume and Issue: 386, P. 138 - 153

Published: Feb. 18, 2019

Language: Английский

Citations

163
Copper-catalysed asymmetric hydroboration of alkenes with 1,2-benzazaborines to access chiral naphthalene isosteres DOI
Wanlan Su,

Jide Zhu,

Yu Chen

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1312 - 1319

Published: April 8, 2024

Language: Английский

Citations

21
NiH‐Catalyzed Migratory Defluorinative Olefin Cross‐Coupling: Trifluoromethyl‐Substituted Alkenes as Acceptor Olefins to Form gem‐Difluoroalkenes DOI
Fenglin Chen,

Xianfeng Xu,

Yuli He

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(13), P. 5398 - 5402

Published: Jan. 17, 2020

We report a NiH-catalyzed migratory defluorinative coupling between two electronically differentiated olefins. A broad range of unactivated donor olefins can be joined directly to acceptor containing an electron-deficient trifluoromethyl substituent in both intra- and intermolecular fashion form gem-difluoroalkenes. This shows site- chemoselectivity under mild conditions, with the formation tertiary or quaternary carbon center.

Language: Английский

Citations

128
Visible‐Light Photoredox‐Catalyzed Remote Difunctionalizing Carboxylation of Unactivated Alkenes with CO2 DOI
Lei Song,

Dongmin Fu,

Liang Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(47), P. 21121 - 21128

Published: Aug. 4, 2020

Remote difunctionalization of unactivated alkenes is challenging but a highly attractive tactic to install two functional groups across long distances. Reported herein the first remote with CO2 . This visible-light photoredox catalysis strategy provides facile method synthesize series carboxylic acids bearing valuable fluorine- or phosphorus-containing groups. Moreover, this versatile protocol shows mild reaction conditions, broad substrate scope, and good functional-group tolerance. Based on DFT calculations, radical adds an alkene smoothly form new carbon radical, followed by 1,5-hydrogen atom-transfer process, rate-limiting step, generating more stable benzylic radical. The reduction radicals IrII species generates corresponding carbanions as key intermediates, which further undergo nucleophilic attack generate carboxylates.

Language: Английский

Citations

126
Rapid Access to Highly Functionalized Alkyl Boronates by NiH‐Catalyzed Remote Hydroarylation of Boron‐Containing Alkenes DOI
Yao Zhang, Bo Han, Shaolin Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(39), P. 13860 - 13864

Published: July 9, 2019

The direct and selective functionalization of relatively simple readily accessible precursors to produce highly functionalized alkyl boronates is a synthetically useful process. Herein we report NiH-catalyzed remote hydroarylation process that can, through synergistic combination chain walking subsequent cross-coupling, introduce an aryl group at the adjacent carbon atom under mild conditions. By means preliminary experiment with moderate enantioselectivity, it was shown asymmetric version could also be realized.

Language: Английский

Citations

116