Cross-Electrophile Couplings of Activated and Sterically Hindered Halides and Alcohol Derivatives

Accounts of Chemical Research, Год журнала: 2020, Номер 53(9), С. 1833 - 1845

Опубликована: Авг. 25, 2020

ConspectusTransition metal catalyzed cross-electrophile coupling of alkyl electrophiles has evolved into a privileged strategy that permits the facile construction valuable C(sp3)–C bonds. Numerous elegant Ni-catalyzed methods, for example, arylation, allylation, acylation, and vinylation primary secondary halides have been developed. This prior work provided important mechanistic insights selectivity reactivity partners, which are largely dictated by both catalysts reactants. In spite advances made to date, number challenging issues remain, including (1) achieving stereoselective syntheses C–C bonds rely primarily on functionalized or activated precursors, (2) diversifying electrophiles, (3) gaining underlying reaction mechanisms.In this Account, we summarize Ni- Fe-catalyzed reductive bond forming methods developed in our laboratory, allowed us couple activated, sterically hindered tertiary C(sp3)–O access methylated trifluoromethylated products, esters, C-glycosides, quaternary carbon centers. We will begin with brief discussion chemoselective unactivated alkyl–alkyl bonds, focus effects ligands reductants, along leaving group-directed reactivities halides, role they play promoting methyl, trifluoromethyl, glycosyl chloroformates. Matching these suitable partners is considered essential success; something can be tuned means appropriate Ni catalysts. Second, detail how tuning steric electronic nickel labile pyridine-type additives (primarily MgCl2) effective creation arylated all-carbon centers through aryl encumbered halides. contrast, use bulkier bipyridine terpyridine incorporation relative small-sized acyl allyl groups acylated allylated Finally, show knowledge gained halide enabled develop permit oxalates allyl, aryl, vinyl wherein Barton C–O radical fragmentation mediated Zn MgCl2 promoted The same protocol applicable arylation derived from α-hydroxyl carbonyl substrates, involves formation relatively stable α-carbonyl centered radicals. Thus, Account not only summarizes synthetic allow using but also provides insight relationship between structure substrates catalysts, as well additives.

Язык: Английский

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Metallaphotoredox-enabled deoxygenative arylation of alcohols

Nature, Год журнала: 2021, Номер 598(7881), С. 451 - 456

Опубликована: Авг. 31, 2021

Язык: Английский

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Alkoxy Radicals See the Light: New Paradigms of Photochemical Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2429 - 2486

Опубликована: Окт. 6, 2021

Alkoxy radicals are highly reactive species that have long been recognized as versatile intermediates in organic synthesis. However, their development has impeded due to a lack of convenient methods for generation. Thanks advances photoredox catalysis, enabling facile access alkoxy from bench-stable precursors and free alcohols under mild conditions, research interest this field renewed. This review comprehensively summarizes the recent progress radical-mediated transformations visible light irradiation. Elementary steps radical generation either or central reaction development; thus, each section is categorized discussed accordingly. Throughout review, we focused on different mechanisms well impact synthetic utilizations. Notably, catalytic abundant still early stage, providing intriguing opportunities exploit diverse paradigms.

Язык: Английский

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Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(9), С. 3536 - 3543

Опубликована: Фев. 23, 2021

As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C–C bonds. Here, we demonstrate that the combination of anodic preparation alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)–C(sp3) bonds, in which free aryl bromides—both readily available chemicals—can be directly used as coupling partners. This paired electrolysis reaction features broad substrate scope bearing wide gamut functionalities, was illustrated by late-stage arylation several structurally complex natural products pharmaceuticals.

Язык: Английский

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Deaminative Reductive Arylation Enabled by Nickel/Photoredox Dual Catalysis

Organic Letters, Год журнала: 2019, Номер 21(9), С. 3346 - 3351

Опубликована: Апрель 17, 2019

Described is a cross-electrophilic, deaminative coupling strategy harnessing Katritzky salts as new species of electrophile in Ni/photoredox dual catalytic reductive cross-coupling reactions. Distinguishing features this arylation protocol include its mild reaction conditions, high chemoselectivity, and adaptability to variety complex substrates [i.e., pyridinium derived from amines partners (hetero)aryl bromides].

Язык: Английский

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Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 4162 - 4184

Опубликована: Янв. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Язык: Английский

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Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Chlorides with Primary Alkyl Chlorides

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(22), С. 9902 - 9907

Опубликована: Май 15, 2020

Alkyl chlorides and aryl are among the most abundant stable carbon electrophiles. Although their coupling with nucleophiles is well developed, cross-electrophile of alkyl has remained a challenge. We report here first general approach to this transformation. The key productive, selective cross-coupling use small amount iodide or bromide along recently reported ligand, pyridine-2,6-bis(N-cyanocarboxamidine) (PyBCamCN). scope reaction demonstrated 35 examples (63 ± 16% average yield), we show that Br– I– additives act as cocatalysts, generating low, steady-state concentration more-reactive bromide/iodide.

Язык: Английский

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Deoxygenative Borylation of Secondary and Tertiary Alcohols

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(28), С. 9561 - 9564

Опубликована: Май 3, 2019

Abstract Two different approaches for the deoxygenative radical borylation of secondary and tertiary alcohols are presented. These transformations either proceed through a metal‐free silyl‐radical‐mediated pathway or utilize visible‐light photoredox catalysis. Readily available xanthates methyl oxalates used as precursors. The reactions show broad substrate scope high functional‐group tolerance, conducted under mild practical conditions.

Язык: Английский

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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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Reductive Cross-Coupling of Unreactive Electrophiles

Accounts of Chemical Research, Год журнала: 2022, Номер 55(17), С. 2491 - 2509

Опубликована: Авг. 11, 2022

ConspectusTransition-metal-catalyzed reductive coupling of electrophiles has emerged as a powerful tool for the construction molecules. While major achievements have been made in field cross-couplings between organic halides and pseudohalides, an increasing number reports demonstrates reactions involving more readily available, low-cost, stable, but unreactive electrophiles. This account summarizes recent results our laboratory focusing on this topic. These findings typically include deoxygenative C–C alcohols, alkylation alkenyl acetates, C–Si chlorosilanes, C–Ge chlorogermanes.The alcohols with is synthetically appealing, potential chemistry remains to be disclosed. Our initial study focused reaction allylic aryl bromides by combination nickel Lewis acid catalysis. method offers selectivity that opposite classic Tsuji–Trost reactions. Further investigation benzylic led foundation dynamic kinetic cross-coupling strategy applications nickel-catalyzed arylation cobalt-catalyzed enantiospecific alkenylation alcohols. The titanium catalysis was later established produce carbon radicals directly from unactivated tertiary via C–OH cleavage. development their fragments delivers new methods all-carbon quaternary centers. shown high functionalization leaving primary secondary intact. Alkenyl acetates are inexpensive, environmentally friendly considered most attractive reagents. benzyl ammoniums alkyl mild approaches conversion ketones into aliphatic alkenes.Extensive studies enabled us extend cross-electrophile silicon germanium chemistry. harness ready availability chlorosilanes chlorogermanes suffer challenge low reactivity toward transition metals. Under catalysis, broad range couple well vinyl- hydrochlorosilanes. use partners formation functionalized alkylsilanes. seems less substrate-dependent, various common aryl, alkenyl, In general, functionalities such Grignard-sensitive groups (e.g., acid, amide, alcohol, ketone, ester), acid-sensitive ketal THP protection), fluoride chloride, bromide, tosylate mesylate, silyl ether, amine tolerated. provide access organosilicon organogermanium compounds, some which challenging obtain otherwise.

Язык: Английский

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