Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

CCS Chemistry, Год журнала: 2021, Номер 4(1), С. 9 - 30

Опубликована: Окт. 15, 2021

Open AccessCCS ChemistryMINI REVIEW1 Jan 2022Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry Liang Yi†, Tengfei Ji†, Kun-Quan Chen, Xiang-Yu Chen Magnus Rueping Yi† Institute of Organic Chemistry, RWTH Aachen University, 52074 †L. Yi T. Ji contributed equally to this work.Google Scholar More articles by author , Ji† School Chemical Sciences, University the Chinese Academy Beijing 100049 Google *Corresponding authors: E-mail Address: [email protected] King Abdullah Science Technology (KAUST), Thuwal 23955 https://doi.org/10.31635/ccschem.021.202101196 SectionsAboutAbstractPDF ToolsAdd favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Metal-catalyzed cross-electrophile couplings have become a valuable tool carbon–carbon bond formation. This minireview provides comprehensive overview recent developments in topical field couplings, explanations current state-of-the-art, highlights new opportunities arising emerging fields photoredox catalysis electrochemistry. Download figure PowerPoint Introduction Carbon–carbon formations always been one most useful reactions both industry academia gained considerable attention from many synthetic chemists who developed novel strategies achieve improved sustainable transformations. Transition metal has continually provided activation modes C–C formations1–5 fascinated long time. Many named associated with transition powerful method cross-couplings electrophiles organometallic nucleophiles (Scheme 1a). Despite progress, use reagents can cause undesired side chemical wastes. Alternatively, cross-nucleophile coupling as an efficient synthesis synthetically biologically important compounds 1b).6–8 However, lower availability carbon represents limitation. Recently, metal-catalyzed cross-coupling between two bench stable under reductive conditions emerged construction bonds. In particular, nickel (Ni) catalysts, characterized low reduction potential electronegativity, undergo rapid oxidative addition.9 As such, it is not surprising that nickel-catalyzed flourishing area organic chemistry characteristic advantages over classical synthesis, such widely available avoiding unstable time-consuming costly prefunctional processes. Scheme 1 | (a–c) cross-coupling. Thus, there significant progress development constructing The first example was published about 100 years ago Wurtz10 Tollens Fittig11 using sodium reductant mediator aryl halides alkyl halides. Stoichiometric high temperatures are needed. Therefore, functional group tolerance application limited. Another strategy electrosynthesis. Early explorations electroreductive include cross/homo-coupling halides, acyl, carboxylation cross-couplings.12 be difficult specialized laboratory equipment required. These limitations restricted further formation bonds several years. electrosynthesis recently seen renaissance cross-couplings. popular combination metallic reducing agents number Mn or Zn reductants.13–20 its success, addition scalability efficiency problems, utility powders inevitably produces excess waste. photochemical alternatives developed. impressive achievements made merging photo- electrochemistry create avoid powders. Considering construction, provide conceptual understanding 1c). Against background, we attempt give state-of-the-art highlight pathways. Alkyl–Aryl Cross-Coupling Nickel/metallic agent system viability alkyl-aryl via initially demonstrated research groups Durandetti,21 Lipshutz,22 Wangelin23 2). Specifically, Durandetti co-workers21 described α-chloroesters, well Refortmatsky reaction presence manganese metal. Lipshutz co-workers22 investigated participation zinc palladium-catalyzed halide bromide, Wangelin co-workers23 reported cobalt-catalyzed early examples combined metal/reducing systems construct milder conditions. 2 reporting catalysis. recently, more recognized general concept actively researched exciting 2010, Weix co-workers24 Ni/Mn selective equimolar quantities halide. High cross-selectivities were achieved bipyridyl phosphine ligand 3a). 3 Overview alkyl–aryl protocol, stoichiometric required, broad range tolerated. drawback, secondary bromides resulted mixed isomer products. Nevertheless, direct without intermediate organomanganese species protocol. Regarding mechanism 3b), postulated key step valent Ni(0) generates Ar–Ni(II) I. Subsequent radical affords Ar–Ni(III)–R II. Finally, elimination II desired product Ni(I) III, which could produce single-electron transfer (SET) halogen-atom abstraction. Reduction III finishes catalytic cycle. Concurrently, similar results cobalt/phosphine disclosed Amatore Gosmini25 electron-deficient bromides. After these studies, great efforts focused on different 3c).26–38 Notably, Molander co-workers39,40 successfully expanded installation fragments onto pharmaceutically relevant heterocyclic motifs. A variety aliphatic tosylates underwent moderate good yields, furnishing substituted heteroaromatic compounds. achievements, alkylamines, abundant natural feedstocks, had realized until recently. 2017, Watson co-workers41 Suzuki–Miyaura boronic acids, employing Katritzky salts C-centered-radical precursors. Very Rueping,42 Watson,43 Martin,44 Han45 independently applied cases, employed optimal reductants elevated usually Han’s Ni/Zn enabled wider substrate scope including bromoalkynes Although primary developed, tertiary easy due dominant β-hydride reaction. 2015, Gong co-workers46 resolved issue pyridine (Py) 4-(N,N-dimethylamino)pyridine (DMAP) carbene salt additives suppress enhance 4). tolerated various better obtained electron-withdrawing substituents. 4 Until now, cases form at ipso-carbon where regioselectivity less explored 5a). An migratory Zhu co-workers47 2017 5b). proceeded smoothly Ni(ClO4)2(H2O)6/6,6′-dimethyl-2,2′-bipyridyl catalyst nonactivated affording 1,1-diarylalkane derivatives, widespread products active molecules, excellent yields regioselectivity. 5 Nickel-catalyzed proposed transformation 5c. Initially, inactivated bromide leads Ni(II) complex following insertion steps deliver thermodynamically benzylic-Ni(I) III. Then, Ni(III) IV. Ni(I)-X V. then reduced powder close class also Yin co-workers,48 NiI2/bathocuproine reductant. Interestingly, opposite proposed. step, rather than I′. chain process II′ generated SET Ni(I)−X ( IV′). Several control experiments trapping carried out support their mechanism. electrophiles, types cross-couplings, enable modes, still highly desirable. During last few years, metal/photoredox dual witnessed remarkable offered unconventional transformations.49–65 To date, strongly dominated redox neutral pathway, wherein nucleophile partner changes oxidation state nickel/photoredox offers alternative absence 6). 6 representation pathway Nickel-photoredox 2016, MacMillan co-workers66–68 catalyzed 7a). Ni/photoredox mechanism, Concomitantly, hydrogen-atom abstraction tris(trimethylsilyl)silane (TTMSS) bromine radicals forms stabilized silyl intermediate. mediated radical, binds I, leading photo Ir(II). case, photoexcited generate radical. 7 (a–d) Lei co-workers,69 studies MacMillan, Et3N terminal 7b. complex. At same time, low-valent resulting intercepted species. species, Ir(II) cycles. used Vannucci co-workers,70 triethanolamine Based previous developments, Jensen co-workers71 continuously stirred-tank reactor platform flow. gram-scale after 13 h, opened up applications system. related approach Brill co-workers72 assembly drug-like benzylic chlorides (hetero)aryl continuous flow highlighting industrial applicability. Furthermore, co-workers73 bathocuproine 7c). Compared iodides, simple abundant, inexpensive, readily methods. they electrophilic partners nucleophilic aromatic substitutions. chlorides. involving substrates, aminosilane reductant, NiCl2(bim) Ir-based photocatalyst, afforded C(sp2)−C(sp3) coupled generally 7d).74 context series salts, aziridines, epoxides. co-workers,75 identified C(sp3) 4CzIPN photocatalyst NiBr2(DME)/4,4′-di-tert-butylbipyridine (dtbbpy) catalyst, differently substrates 8a). 8 (a–f) Doyle co-workers32 nickel/Mn-catalyzed styrenyl aziridines iodides. drawback aziridine did work 8b). study co-workers76 constituted strategy. Their way newly showed scope. iodides NiBr2(DME)/dtbbpy catalyst. able cyclic classic methods, 8c). 8d. iodide β-iodoamine IV formed ring-opening aziridine. Subsequently, 4CzIPN−• Ni(I)−I III). I Then [4-CzIPN]−• nickel/Mn gave MnI2 instead β-iodoamine; thus, no obtained. Continued co-workers77 epoxides 8e). Ni/Ti/photoredox Various styrene oxides, epoxides, all reacted regioselectivities. Allylic carbonates proven suitable cross-couplings.78–80 nice Chu co-workers81 allylic vinyl triflates 8f). E- Z-configured 1,4-dienes choice photocatalysts. When Ir(ppy)2(dtbbpy)+ photoinduced contra-thermodynamic E→Z isomerization would occur (Z)-1,4-diene product.81 strategies, them rely potentials photocatalysts furnish addition, appealing when considering toxicity cost photoactive electron-donor-acceptor (EDA) allows generation mild based-photocatalysts dyes. strategy, co-workers82 EDA N-hydroxyphthalimide (NHPI) esters. proceeds NHPI ester Hantzsch (HE), upon radiation-induced (eq 1).82 Electrochemical may offer economical Recent ability bond-forming reactions. Within area, electrochemically induced integrating 9). seminal chloroesters electrochemical strategy.12 breakthrough very Hansen co-workers83 10a). sacrificial anode tuning found crucial cooperative circumvented need temperatures. exhibited generality. 9 10 aryl–alkyl Further Bio co-workers84 Hansen’s method, esters source amine divided cell 10b). Later, one-pot C(sp2)–C(sp3) Loren co-workers85 10c), redox-active situ carboxylates tetramethyluronium hexafluorophosphate. Sevov co-workers86 shuttles protect reduction, thus improving suppressing side-product 10d). across wide aryl, heteroaryl, Given importance concurrently, Rueping87 Mei88 11a). Both methods scope, giving rise corresponding derivatives yields. experimental density theory (DFT) co-workers87 plausible 11b). 11 (a b) cathode surface. gives Ar−Ni(I) occurs Ar−Ni(II)−Br cathodic will benzylic-Ni(II) release regenerate Ni(0). Aryl–Aryl Cross-Couplings comparison bonds, C(sp2)–C(sp2) challenging result subtle difference electrophiles. 2008, Gosmini89 unsymmetrical biaryl success reactivity profiles allowed extended 2-halopyridine group.90 co-workers91 selectivities controlled catalysts electronic properties reports 12a). Mechanistically, react exclusively Pd(0) Pd(II) transmetalation complex, Ar1–Pd(II)–Ar2 IV, asymmetrical biaryls. additive potassium fluoride (KF) achieving selectivity, presumably selectivity palladium triflate bromide. Olivares Weix92 other triflates, triflates,93 tosylates,94 ortho-fluoro-substituted amides,95 difluoromethyl 2-pyridyl sulfone,96 bromides, 2,2-difluorovinyl tosylate.97 12 aryl–aryl co-workers98 polyfluorinated arenes 12b). protocol opens entry multifluorinated starts generating [C5F5N]•− C5F5N, trapped II′. III′, Also, Ni(0)/Ni(I)/Ni(III)/Ni(I) cycle possible, involves Ni(I)–C5F4N IV′) Besides aryl-heteroarybond regard, Léonel co-workers99–102 heteroaryls, 3-chloro-6-methoxypyridazines, 3-amino-6-chloropyridazines, chloropyrimidines 12c). Alkyl–Alkyl discussed above,

Язык: Английский

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Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июнь 7, 2023

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal-catalyzed cross-coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Язык: Английский

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A guide to organic electroreduction using sacrificial anodes

Chemical Society Reviews, Год журнала: 2023, Номер 52(4), С. 1168 - 1188

Опубликована: Янв. 1, 2023

This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.

Язык: Английский

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Overview of Recent Scale-Ups in Organic Electrosynthesis (2000–2023)

Organic Process Research & Development, Год журнала: 2024, Номер 28(2), С. 338 - 366

Опубликована: Янв. 18, 2024

This review summarizes examples of organic electrosynthesis from the peer-reviewed literature 2000 to 2023 that have been conducted on scales 20 g or above. A significant portion these were a ≤100 scale, while detailed reports kilogram-scale remain scarce in pharmaceutical industry. In addition chemical transformation, this also highlights type reactor used and projected productivity metric as ways compare different reports. The selected scale-ups described herein illustrate remaining challenges currently preventing routine use large-scale

Язык: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

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Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3405 - 3415

Опубликована: Янв. 29, 2024

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Язык: Английский

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The applications of electrochemical synthesis in asymmetric catalysis

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 3019 - 3047

Опубликована: Окт. 27, 2022

Язык: Английский

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The Merger of Benzophenone HAT Photocatalysis and Silyl Radical-Induced XAT Enables Both Nickel-Catalyzed Cross-Electrophile Coupling and 1,2-Dicarbofunctionalization of Olefins

ACS Catalysis, Год журнала: 2022, Номер 12(18), С. 11216 - 11225

Опубликована: Сен. 1, 2022

A strategy for both cross-electrophile coupling and 1,2-dicarbofunctionalization of olefins has been developed. Carbon-centered radicals are generated from alkyl bromides by merging benzophenone hydrogen atom transfer (HAT) photocatalysis silyl radical-induced halogen (XAT) subsequently intercepted a nickel catalyst to forge the targeted C(sp3)-C(sp2) C(sp3)-C(sp3) bonds. The mild protocol is fast scalable using flow technology, displays broad functional group tolerance, amenable wide variety medicinally relevant moieties. Mechanistic investigations reveal that ketone catalyst, upon photoexcitation, responsible direct activation silicon-based XAT reagent (HAT-mediated XAT) furnishes radical ultimately involved in turnover catalytic cycle.

Язык: Английский

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Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis

Chemical Science, Год журнала: 2022, Номер 13(24), С. 7256 - 7263

Опубликована: Янв. 1, 2022

Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action nickel sodium decatungstate catalysis. A wealth ketones with high levels structural complexity was rapidly obtained via direct functionalization C(sp2)/C(sp3)-H in a modular manner. Furthermore, regioselective late-stage modification natural products showcased practical utility strategy, generally featuring resource economy ample substrate scope.

Язык: Английский

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Reactivity in Nickel‐Catalyzed Multi‐component Sequential Reductive Cross‐Coupling Reactions

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 21, 2022

The nickel-catalyzed three-component reductive carbonylation of alkyl halides, aryl and ethyl chloroformate is described. Ethyl utilized as a safe readily available source CO in this multi-component protocol, providing an efficient practical alternative for the synthesis aryl-alkyl ketones. reaction exhibits wide substrate scope good functional group compatibility. Experimental DFT mechanistic studies highlight complexity cross-electrophile coupling provide insight into sequence three consecutive oxidative additions halide, chloroformate, halide.

Язык: Английский

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