Skeletal Editing of (Hetero)Arenes Using Carbenes

Chemistry - A European Journal, Год журнала: 2023, Номер 29(42)

Опубликована: Май 26, 2023

Abstract (Hetero)arenes continue to prove their indispensability in pharmaceuticals, materials science, and synthetic chemistry. As such, the controllable modification of biologically significant (hetero)arenes towards diverse more‐potent complex molecular scaffolds through peripheral skeletal editing has been considered a challenging goal organic Despite many excellent reviews on ( i. e ., C−H functionalization) (hetero)arenes, editings via single atom insertion, deletion, or transmutations have received less attention review literature. In this review, we systematically summarize state‐of‐the‐art reactions using carbenes, with focus general mechanistic considerations applications natural product syntheses. The potential opportunities inherent challenges encountered while developing these strategies are also highlighted.

Язык: Английский

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Organocatalytic Asymmetric Dearomatizing Hetero-Diels–Alder Reaction of Nonactivated Arenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7374 - 7381

Опубликована: Апрель 13, 2022

Nonactivated arenes, such as benzene derivatives, are chemically inert due to their intrinsic aromaticity and low polarity. The catalytic asymmetric dearomatization (CADA, coined by You co-workers) of the nonactivated arenes represents a formidable challenge. We herein demonstrated an organocatalytic dearomatizing hetero-Diels–Alder reaction derivatives. tunable regioselectivity this strategy allowed delivery diversity stereochemically complex polycyclic compounds oxahelicenes with excellent stereoselectivity. high complexity three-dimensionality products crucial for potential applications in materials science drug discovery. Mechanistic studies suggested that proceeds through chiral tetra-substituted vinylidene ortho-quinone methide (VQM) intermediate, which is extremely active overcome loss derivatives concomitant chirality transfer.

Язык: Английский

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Oxidative Dearomatization of Pyridines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2358 - 2363

Опубликована: Янв. 17, 2024

Dearomatization of pyridines is a well-established synthetic approach to access piperidines. Although remarkably powerful, existing dearomatization processes have been limited the hydrogenation or addition carbon-based nucleophiles activated pyridiniums. Here, we show that arenophile-mediated dearomatizations can be applied directly introduce heteroatom functionalities without prior substrate activation. The arenophile platform in combination with olefin oxidation chemistry provides dihydropyridine cis-diols and epoxides. These previously elusive compounds are now readily accessible used for downstream preparation diversely functionalized

Язык: Английский

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Gd(III)-Catalyzed Regio-, Diastereo-, and Enantioselective [4 + 2] Photocycloaddition of Naphthalene Derivatives

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 16982 - 16989

Опубликована: Июнь 13, 2024

Catalytic asymmetric dearomatization (CADA) reactions have evolved into an efficient strategy for accessing chiral polycyclic and spirocyclic scaffolds from readily available planar aromatics. Despite the significant developments, CADA reaction of naphthalenes remains underdeveloped. Herein, we report a Gd(III)-catalyzed naphthalene with PyBox ligand via visible-light-enabled [4 + 2] cycloaddition. This features application Gd/PyBox complex, which regulates reactivity selectivity simultaneously, in excited-state catalysis. A wide range functional groups is compatible this protocol, giving highly enantioenriched bridged polycycles excellent yields (up to 96%) >20:1 chemoselectivity, dr, >99% ee). The synthetic utility demonstrated by 2 mmol scale reaction, removal directing group, diversifications products. Preliminary mechanistic experiments are performed elucidate mechanism.

Язык: Английский

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Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19261 - 19270

Опубликована: Июль 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Язык: Английский

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Photoinduced Pd-Catalyzed Dearomative 2,5-Difunctionalizition of Furans via Cascade C–C/C–O Bond Formation

Organic Letters, Год журнала: 2024, Номер 26(5), С. 1083 - 1087

Опубликована: Янв. 26, 2024

We report an efficient and mild approach for radical dearomatization via photoinduced palladium-catalyzed reaction of three components (i.e., furans, alcohols, bromoalkanes). In this strategy, various functionalized spiro-heterocycles were prepared from furans in one step cascade C–C/C–O bond formation under redox neutral conditions.

Язык: Английский

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Gold‐Catalyzed Transformation of Ynamides

The Chemical Record, Год журнала: 2021, Номер 21(12), С. 4123 - 4149

Опубликована: Авг. 25, 2021

Ynamide, a unique species with inherited polarization of nitrogen lone pair electron to triple bond, has been largely used for the developement novel synthetic methods and construction unusual N-bearing heterocycles. The reaction versatility ynamide on umpolung reactivity, radical reactions asymmetric synthesis have recently reviewed. This review provides an overall scenic view into gold catalyzed transformation ynamides. ynamides reactivity towards nitrogen-transfer reagents, such as azides, ylides, isoxazoles, anthranils; oxygen atom-transfer like nitrones, sulfoxides, pyridine N-oxides; carbon nucleophiles under catalysis are herein uncovered. scope well mechanistic insights each is also briefed.

Язык: Английский

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Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO ₂ via Visible-Light-Induced Reductive Dearomatization

CCS Chemistry, Год журнала: 2021, Номер 4(5), С. 1565 - 1576

Опубликована: Май 28, 2021

Open AccessCCS ChemistryCOMMUNICATION1 May 2022Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO2 via Visible-Light-Induced Reductive Dearomatization Yuzhen Gao, Hao Wang, Zhuomin Chi, Lei Yang, Chunlin Zhou and Gang Li Gao Key Laboratory Coal to Ethylene Glycol Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute Research on the Structure Matter, University Chinese Academy Sciences, Fuzhou, 350002 , Wang Chi College Chemistry Materials Science, Normal University, 350117 Yang *Corresponding author: E-mail Address: [email protected] Frontiers Science Transformative Molecules, Shanghai Jiao Tong 200240 https://doi.org/10.31635/ccschem.021.202100995 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Visible-light-induced reductive dearomatization nonactivated arenes is a very challenging transformation remains its infancy. Herein, we report novel strategy achieve visible-light-induced spirocyclizative remote arylcarboxylation including naphthalenyl- phenyl-bearing aromatics under mild conditions through radical-polar crossover cascade (RPCC). This protocol rapidly delivers broad range spirocyclic valuable carboxylic acid derivatives from readily accessible aromatic precursors generally good regioselectivity chemoselectivity. Download figure PowerPoint Introduction represents unique synthetic that converts available planar into three-dimensional alicyclic molecules.1–6 Notable methods include Birch reduction,7 transition-metal-catalyzed dearomative functionalization,8,9 oxidative electron-rich (hetero)aromatics,10 UV-light-promoted photochemical cycloadditions.11 However, progress has mainly been made studies heteroaromatics indoles, such as phenols naphthols.1–24 In contrast, only limited important advances have electronically unbiased naphthalene benzene possess high resonance stabilization energy.6,25–35 Of particular note, You group25 Hong Jia's group26 simultaneously reported two types elegant, highly diastereoselective 1,4-difunctionalization reactions 1-naphthamides palladium-catalyzed at slightly elevated temperature. Therefore, challenging, development complementary desirable. recent years, visible-light photoredox catalysis36–45 emerged promising developing protocols dearomatization,46–59 several significant arenes,60–74 cycloadditions were groups Sarlah Bach,60–63 dearomatization.64–66 A distinct redox-neutral hydroalkylative was also by group Zhang, Mei, You.67 there are handful reports arenes.68–74 König68 Miyake69 independently catalyst (PC)-induced Birch-type reduction arenes. Meanwhile, monofunctionalizations hydroalkylation70–72 hydroboration73 photoreduction disclosed Stephenson,70 Murakami,71 Curran,73 respectively (Scheme 1a). Notably, Jui group74 achieved hydroarylation using an amine reductant 1a), avoiding use toxic reagents SmI2/hexamethylphosphoramide (HMPA)75 similar traditional transformations. Despite this progress, difunctionalization possibly due competing protonation rearomatization. Scheme 1 | (a–c) More recently, our group76 styrenes (RPCC), which initiated reactive aryl radicals generated halides. We wondered whether RPCC process76–91 could be applied CO2. during investigation, Yu group92 2,3-arylcarboxylation class well-studied heteroarene reactions, 5-exo-trig cyclization 1b). Surprisingly, chemoselective phenyl ring 6-exo-trig occurred 2-phenyl indoles substates reaction conditions, leading products those Yu's work 1c). line continuous interest catalytic utilization CO2,93,94 abundant, low-cost, sustainable, nontoxic C1 building block, herein bearing naphthalenyl, phenyl, quinolinyl provides rapid access valuable, complex, frameworks type Hantzsch ester reaductant, is, 4-potassium carboxylate HE (4-CO2K-HE), discovered study. Results Discussion To start derivative 1a (Table 1) utilized model substrate, irradiated 30 W blue light-emitting diodes (LEDs) presence commercially PC Ru(bpy)3Cl2 atmospheric pressure ambient After extensive screening 1,4-arylcarboxylation product 2, methylated original ease isolation, obtained 83% isolated yield employing 4-CO2K-HE reductant95–97 K2CO3 base dimethylformamide (DMF; entry 1). The structure 2 confirmed X-ray analysis, representing formal C–H carboxylation CO2.98–100 Control revealed no observed without either or light, indicating promoted light (entries 3). decrease when carrying out nitrogen atmosphere (entry 4), suggesting some produced oxidation 4-CO2K-HE. detected addition 5), much better than other reductants (HEH), N,N-diisopropylethylamine (DIPEA), Et3N, revealing critical role 6–8). desired HCO2K, contrast previous 9).76 decreased dramatically carried Cs2CO3 absence 10 11). PCs 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) iridium complexes, proved most suitable one 12–14). Slight loading reduced mol % 15). Moreover, solvents examined, DMF found best comparing dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), CH3CN 16–18). Finally, bromide chloride analog employed starting material recovered 19 20). Table Optimization Reaction Conditionsa Entry Deviation Standard Conditions Yield (%)b None 87 (83)c Without N.D. 3 dark 4 Under 37 5 6 HEH (2.0 equiv) 61 7 DIPEA 18 8 Et3N(2.0 9 HCO2K instead 11 41 12 4CzIPN 45 13 [Ir(ppy)2(dtbbpy)]PF6 14 fac-Ir(ppy)3 15 (2 %) 73 16 DMSO 60 17 DMA 74 Br I 20 Cl Note: N.D., not detected; 4-CO2K-HE, potassium 3,5-bis(ethoxycarbonyl)-2,6-dimethyl-1,4-dihydropyridine-4-carboxylate HE; HEH, ester; bpy, 2,2′-bipyridine; ppy, 2-phenylpyridine; dtbbpy, 4,4-di-tert-butyl-2,2′-bipyridine. aReaction conditions: (0.1 mmol), (3 %), (0.12 mmol, 1.2 equiv), (0.2 2.0 (1 mL), atm CO2, rt, 24 h, LEDs; then MeI (0.5 °C, h. bYield determined 1H NMR CH2Br2 internal standard. cYield parentheses 0.2 mmol scale. optimized tested series quinoline investigate generality arylcarboxylation. As shown phenol ether linker various functional groups, halide (F, Cl, Br) CO2Me, afforded corresponding dearomatized yields ( 2– 7). Substrates possessing or/and pyridyl compatible produce structurally diverse heterocycles 8– addition, N-protected aniline linkers different protecting (such Boc, Ac, Cbz, CO2Ph) tolerated 12– substitution patterns allowed give satisfied 16– 21). spiroindolines delivered substrates 22 23). trace amounts side competitive substrates, except less 5% 23. Scope naphthalenes quinolines (0.24 (0.4 (1.0 Isolated yields. aMethylation SOCl2 MeOH (4 100 Subsequently, versatility spiro-dearomative process studied 3).25 Pleasingly, N-alkyl methyl, benzyl, isopropyl) reaction, delivering 25– 27 (73–76%). electron-donating (Me OMe), electron-withdrawing (halides, CF3, CN) meta para position all affording (28–38, 60–75%). Substrate methyl C6 gave 39 64% yield. substrate viable transformation, providing target 40 acceptable C4 naphthalenyl tolerated, producing 4-carboxylated 41– 43) reasonable yields, though about 10% these examples. aYield major diastereomer, minor diastereomer isolated. Furthermore, explored 2-tethered 4). after being subjected led 1,2-arylcarboxylation 45– 48) whose structures above-mentioned 1-tethered naphthalenes, albeit moderate 1,2-hydroarylation (10–20%) substrates. Importantly, approach dearomatize benzamide rings 49– 53), scope phenanthridin-6-one 49 50, unknown 51– 53. 44 48 aStructure displayed; 10–20% observed. b24 During study, surprisingly unexpected reactivity 5). Interestingly, predominantly rather activated indole ring's C2–C3 double bond study same substrate.92 55 carboxylation.98–100 rationale chemoselectivity clear present. Initially, iodide employed, but it effective 55). It should mentioned lower 55. suspected might labile, resulting relatively Gratifyingly, substituents converted (56–65). indole's bond, debromination (about 5%) well (generally <5%) noted unreacted transformed unidentifiable decomposed. amide since substate 2-bromobenzyl 2-bromobenzamide group. 54 LEDs, h; yields; a2 moved conduct preliminary mechanistic obtain insight mechanism. First, Stern–Volmer luminescence experiments showed light-activated Ru (PC*) quenched effectively 54a (see Supporting Information details). determine carboxyl source product, 13CO2 (99% 13C) gas 88% 13C incorporation 6a). isotope-labeling diene d- 66 suggested possible anion intermediate 6b). radical trapping performed, 1,1-diphenyl ethylene 2,2,6,6-tetramethylpiperidinooxy (TEMPO), identifiable trapped, TEMPO probably suppressed oxidizing Information). scaled up 6c). derivation briefly generate 67 allylic alcohol 68 6d). (a–d) Mechanistic studies, scale-up derivation. mechanism proposed based above Upon irradiation, excited PC* A) subsequently reductively (E = −0.90 V vs. saturated calomel electrode (SCE) DMF, see Information) B) (E1/2 [RuII*/RuI] +0.77 vs SCE MeCN)101 dihydropyridine C) release Reduction B [RuI/RuII] −1.33 D underwent afford E. Single-electron transfer C E anionic G, nucleophilic H. base-promoted rearrangement followed methylation Proposed cycle. Conclusion developed novel, N-benzylanilines RPCC. An interesting unusual presented. dearomatization/arylcarboxylation efficiently precursors, method complex molecule construction. available, general experimental procedures characterization spectra. Conflict Interest authors declare financial interest. Preprint Statement presented article posted preprint server ChemRxiv prior publication CCS Chemistry. can here: [DOI: http://dx.doi.org/10.26434/chemrxiv.14449728]. Acknowledgments gratefully acknowledge support NSFC (grant nos. 21871257, 22022111, 21801240), Natural Foundation Province no. 2020J02008), Strategic Priority Program Sciences XDB20000000). thank Weiping Cai FJIRSM help cyclic voltammetry experiment Tao Shaoxing crystallographic structural data analysis. References 1. Roche S. P.; Porco J. A.Dearomatization Strategies Synthesis Complex Products.Angew. Chem. Int. Ed.2011, 4068–4093. Google Scholar 2. Zhuo C.-X.; Zhang W.; S.-L.Catalytic Asymmetric Reactions.Angew. Ed.2012, 51, 12662–12686. 3. Zheng C.; S.-L.Transition-Metal-Catalyzed Allylic Reactions.Acc. Res.2014, 47, 2558–2573. 4. James M. J.; O'Brien Taylor R. K.; Unsworth W. P.Synthesis Spirocyclic Indolenines.Chem. Eur. J.2016, 22, 2856–2881. 5. Bariwal Voskressensky L. G.; Van der Eycken V.Recent Advances Spirocyclization Indole Derivatives.Chem. Soc. Rev.2018, 3831–3848. 6. Wertjes Southgate H.; D.Recent Chemical Arenes.Chem. 7996–8017. 7. A. J.Reduction Dissolving Metals. 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Язык: Английский

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Rh₂(ii)-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor–donor carbenes

Chemical Science, Год журнала: 2022, Номер 13(7), С. 1992 - 2000

Опубликована: Янв. 1, 2022

The chiral dirhodium(ii) tetracarboxylate-catalyzed enantioselective intramolecular Büchner reaction of donor/donor-carbenes was reported and a series valuable polycyclic products were synthesized. Both aryloxy enynones diazo compounds efficient carbene precursors for this reaction. Excellent yields (up to 99%) outstanding enantioselectivities >99% ee) achieved under standard conditions. For furyl substituted cyclohepta[b]benzofurans bearing substituent at the C4 position on cycloheptatrienes, control reactions showed that could slowly racemize either dark or natural light A diradical-involved mechanism rather than zwitterionic intermediate proposed explain racemization. Furthermore, fluorene derivatives obtained via asymmetric aromatic substitution when biaryl employed as precursors.

Язык: Английский

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Photoinduced ynamide structural reshuffling and functionalization

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Апрель 29, 2022

The radical chemistry of ynamides has recently drawn the attention synthetic organic chemists to construction various N-heterocyclic compounds. Nevertheless, ynamide-radical remains a long-standing challenge for due its high reactivity, undesirable byproducts, severe inherent regio- and chemoselective problems. Importantly, ynamide C(sp)-N bond fission an unsolved challenge. In this paper, we observe Photoinduced trigger fission, structural reshuffling functionalization 2-alkynyl-ynamides prepare synthetically inaccessible/challenging chalcogen-substituted indole derivatives with excellent step/atom economy. key breakthroughs work includes, cleavage, divergent precursors, broad scope, easy handle, larger-scale reactions, generation multiple bonds (N-C(sp2), C(sp2)-C(sp2), C(sp2)-SO2R/C-SR, C-I/C-Se/C-H) in few minutes without photocatalysts, metals, oxidants, additives. Control experiments 13C-labeling supporting conclusion that sulfone radicals contribute processes via pathway.

Язык: Английский

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