Nickel-catalyzed electrophiles-controlled enantioselective reductive arylative cyclization and enantiospecific reductive alkylative cyclization of 1,6-enynes DOI Creative Commons
Wenfeng Liu,

Yunxin Xing,

Denghong Yan

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 27, 2024

Transition metal-catalyzed asymmetric cyclization of 1,6-enynes is a powerful tool for the construction chiral nitrogen-containing heterocycles. Despite notable achievements, these transformations have been largely limited to use aryl or alkenyl metal reagents, and stereoselective stereospecific alkylative remains unexploited. Herein, we report Ni-catalyzed enantioselective reductive anti-arylative with iodides, providing enantioenriched six-membered carbo- heterocycles in good yields excellent enantioselectivities. Additionally, realized enantiospecific cis-alkylative alkyl bromides, furnishing five-membered high regioselectivity stereochemical fidelity. Mechanistic studies reveal that arylative initiated by oxidative addition Ni(0) halides triggered allylic acetates. The utility this strategy further demonstrated synthesis antiepileptic drug Brivaracetam.

Language: Английский

Enantioselective C(sp3)–C(sp3) Reductive Cross-Electrophile Coupling of Unactivated Alkyl Halides with α-Chloroboronates via Dual Nickel/Photoredox Catalysis DOI
Jun Zhou, Dong Wang,

Wenhao Xu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2081 - 2087

Published: Jan. 23, 2023

Substantial advances in enantioconvergent C(sp3)-C(sp3) bond formations have been made with nickel-catalyzed cross-coupling of racemic alkyl electrophiles organometallic reagents or nickel-hydride-catalyzed hydrocarbonation alkenes. Herein, we report an unprecedented enantioselective reductive by the direct utilization two different halides dual nickel/photoredox catalysis system. This highly selective coupling α-chloroboronates and unactivated iodides furnishes chiral secondary boronic esters, which serve as useful important intermediates realm organic synthesis enable a desirable protocol to fast construction enantioenriched complex molecules.

Language: Английский

Citations

65
Reductive Deoxygenative Functionalization of Alcohols by First‐Row Transition Metal Catalysis DOI

Xiaobo Pang,

Xing‐Zhong Shu

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(13), P. 1637 - 1652

Published: Jan. 23, 2023

Comprehensive Summary Alcohols are among the most accessible functionalities. Catalytic deoxygenative functionalization of alcohols is highly synthetically appealing. While significant progress has been made on reactions with nucleophiles, electrophilic coupling partners remain a real challenge. This manuscript highlights advance in this direction, which mainly achieved by first‐row transition metals. The low‐valent titanium catalyst shown unique reactivity to homolytically cleave C—OH bonds. formed carbon radicals could either undergo reduction give protonation products or couple fragments form C—C chemistry initially realized using stoichiometric amount reagents and later extended catalytic variants. Nickel features variety oxidation states ranging from Ni 0 IV , both two‐electron oxidative addition single‐electron process involved their activation an electrophile. These properties enable nickel catalyze reductive R–X electrophiles. reaction first reported allylic alcohols, then benzylic and, very recently non‐activated alcohols. Recent effort resulted many invaluable methodologies that improve efficiency for construction aliphatic use cobalt copper catalysts not only expands substrate scope these but also shows new selectivity issues.

Language: Английский

Citations

48
Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis DOI

Yun-Zhao Wang,

Bing Sun,

Xiaoyu Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 23910 - 23917

Published: Oct. 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.

Language: Английский

Citations

42
Insights into Recent Nickel-Catalyzed Reductive and Redox C–C Coupling of Electrophiles, C(sp3)–H Bonds and Alkenes DOI
Yuxin Gong, Jie Hu, Canbin Qiu

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(8), P. 1149 - 1162

Published: March 28, 2024

ConspectusTransition metal-catalyzed reductive cross-coupling of two carbon electrophiles, also known as cross-electrophile coupling (XEC), has transformed the landscape C–C chemistry. Nickel catalysts, in particular, have demonstrated exceptional performance facilitating XEC reactions, allowing for diverse elegant transformations by employing various electrophiles to forge bonds. Nevertheless, several crucial challenges remain be addressed. First, intrinsic chemoselectivity between structurally similar Ni-catalyzed C(sp3)–C(sp3) and C(sp2)–C(sp2) not been well understood; this necessitates an excess one partners achieve synthetically useful outcomes. Second, substitution economically environmentally benign nonmetal reductants Zn/Mn can help scale up reactions avoid trace metals pharmaceutical products, but research direction progressed slowly. Finally, it is highly warranted leverage mechanistic insights from develop innovative thermoredox protocols, specifically designed tackle associated with difficult substrates such C(sp3)–H bonds unactivated alkenes.In Account, we address aforementioned issues reviewing our recent work on C–X C–O strategy alkenes, use diboron esters coupling. We focus perspectives transformations, particularly how key C–NiIII–C intermediates are generated, order explain chemoselective regioselective results. The Account consists four sections. discuss Zn/Mn-mediated bond formations based selected alkyl/aryl, allyl/benzyl, other electrophiles. describe versatile C(sp3)–C(sp2) couplings, emphasis consideration construction Third, leveraging C(sp3)–O effective C(sp3)–C formation via situ halogenation alcohols preparation α-vinylated -arylated unusual amino esters. In final section, illustrate functionalization challenging aryl alkyl halides afford taking advantage compatibility Zn oxidant di-tert-butylperoxide (DTBP). Furthermore, a SiH/DTBP-mediated hydrodimerization terminal alkenes selectively head-to-head methyl branched This process, conducted presence or absence catalytic CuBr2, provides solution long-standing challenge: site-selective hydrocoupling produce

Language: Английский

Citations

18
Allylgermane synthesis via facile and general nickela-electrocatalyzed electrophile coupling DOI
Haifeng Chen,

Cai Zhai,

Chen Zhu

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101257 - 101257

Published: Feb. 1, 2025

Language: Английский

Citations

2
Regio- and Stereoselective Reductive Coupling of Alkynes and Crotononitrile DOI
Kun Cui, Yanlin Li, Gongqiang Li

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 23001 - 23009

Published: Dec. 8, 2022

A new regio- and stereoselective reductive coupling of alkynes crotononitrile has been developed via visible light organophotoredox cobalt dual catalysis. variety enantioenriched homoallylic nitriles bearing a stereodefined trisubstituted alkene have easily synthesized with good to excellent (up >20:1 rr), stereo- (>20:1 E/Z), enantioselectivity 98% ee) control under mild conditions. The corresponding nitrile products were smoothly converted into various chiral building blocks. Remarkably, simple organic base together water utilized as hydrogen sources in this photoinduced reaction.

Language: Английский

Citations

39
Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes DOI
Liangliang Qi,

Qiu‐Quan Pan,

Xiao‐Xue Wei

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13008 - 13014

Published: June 7, 2023

Transition-metal-catalyzed sila-cycloaddition has been a promising tool for accessing silacarbocycle derivatives, but the approach limited to selection of well-defined sila-synthons. Herein, we demonstrate potential chlorosilanes, which are industrial feedstock chemicals, this type reaction under reductive nickel catalysis. This work extends scope coupling from carbocycle synthesis and single C-Si bond formation reactions. The proceeds mild conditions shows good substrate functionality tolerance, it offers new access silacyclopent-3-enes spiro silacarbocycles. optical properties several dithienosiloles as well structural variations products demonstrated.

Language: Английский

Citations

34
An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer DOI Creative Commons
Krishnakumar Sachidanandan, Ben Niu, Sébastien Laulhé

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(21)

Published: Aug. 14, 2023

Abstract The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation carbon‐centered radicals in organic synthesis. XAT are unique that they generate without requiring use strong reductants necessary traditional single electron (SET) activation halides. Pathways achieve synthetic applications can categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based and iii) carbon‐based activators among which α‐aminoalkyl have taken center stage. Access these as reagents gained significant attention past few years due robustness reactions, simplicity required, broadness their applications. Generation is simply achieved through oxidation tertiary amines, after deprotonation at α‐position generates radicals. Due wide scope amines available tunable nucleophilicity radical formed, this strategy become an attractive alternative heteroatom/metal‐based XAT. In minireview, we focus our on recent (2020–2023) developments uses robust technology mediate processes.

Language: Английский

Citations

28
Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp3)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides DOI
Hiroki Miura,

Masafumi Doi,

Yuki Yasui

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4613 - 4625

Published: Feb. 20, 2023

Since C(sp3)–O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of will be key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO2, efficiently generated alkyl radicals via homolysis unactivated bonds, which consequently promoted C(sp3)–Si bond formation to give diverse organosilicon compounds. A wide array esters ethers, either commercially available or easily synthesized from alcohols participated heterogeneous gold-catalyzed silylation by disilanes alkyl-, allyl-, benzyl-, allenyl silanes high yields. In addition, this novel reaction could applied upcycling polyesters, i.e., degradation polyesters synthesis organosilanes were realized concurrently unique catalysis nanoparticles. Mechanistic studies corroborated notion generation is involved coupling cooperation an acid–base pair ZrO2 responsible stable bonds. The reusability air tolerance catalysts as well simple, scalable, green system enabled practical

Language: Английский

Citations

26
Enantioconvergent and regioselective reductive coupling of propargylic esters with chlorogermanes by nickel catalysis DOI
Guanyu Han,

Pei‐Feng Su,

Qiu‐Quan Pan

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 7(1), P. 12 - 20

Published: Oct. 30, 2023

Language: Английский

Citations

24