Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(3), P. 1855 - 1969

Published: Dec. 24, 2018

In this review, we summarize the origin and advancements of iridium-catalyzed asymmetric allylic substitution reactions during past two decades. Since first report in 1997, Ir-catalyzed have attracted intense attention due to their exceptionally high regio- enantioselectivities. been significantly developed recent years many respects, including ligand development, mechanistic understanding, substrate scope, application synthesis complex functional molecules. an explicit outline ligands, mechanism, scope nucleophiles, applications is presented.

Language: Английский

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Progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(23), P. 3967 - 3998

Published: Jan. 1, 2020

This review summarizes the progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives and their applications total synthesis natural products, gives some insights into challenging issues this research field.

Language: Английский

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Pd‐Catalyzed Dearomatization of Anthranils with Vinylcyclopropanes by [4+3] Cyclization Reaction

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(17), P. 5739 - 5743

Published: Feb. 27, 2019

Abstract Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd‐catalyzed [4+3] cyclization reaction has been realized. In the presence a catalytic amount borane as an activator, bridged cyclic products were obtained in good to excellent yields stereoselectivities. By introducing chiral PHOX ligand ( L5 ), asymmetric dearomatization reactions proceeded enantioselectivity. Borane plays key role for reactivity, likely owing formation borane–anthranil complex which confirmed NMR experiments.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7374 - 7381

Published: April 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.

Language: Английский

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Tandem Dearomatization/Enantioselective Allylic Alkylation of Pyridines

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 11907 - 11913

Published: May 22, 2023

Herein, we report a multistep one-pot reaction of substituted pyridines leading to N-protected tetrahydropyridines with outstanding enantioselectivity (up 97% ee). An iridium(I)-catalyzed dearomative 1,2-hydrosilylation enables the use N-silyl enamines as new type nucleophile in subsequent palladium-catalyzed asymmetric allylic alkylation. This telescoped process overcomes intrinsic nucleophilic selectivity synthesize enantioenriched, C-3-substituted tetrahydropyridine products that have been otherwise challenging access.

Language: Английский

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Electrochemical cascade migratory versus ortho-cyclization of 2-alkynylbenzenesulfonamides

Chemical Science, Journal Year: 2024, Volume and Issue: 15(8), P. 2827 - 2832

Published: Jan. 1, 2024

Efficient control over several possible reaction pathways of free radicals is the chemical basis their highly selective transformations. Among various competing pathways, sulfonimidyl generated from electrolysis 2-alkynylbenzenesulfonamides undergo cascade migratory or

Language: Английский

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Enantioselective dearomative [3+2] cycloaddition of 2-nitrobenzofurans with aldehyde-derived Morita–Baylis–Hillman carbonates

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(62), P. 9144 - 9147

Published: Jan. 1, 2019

The phosphine-catalyzed asymmetric dearomative [3+2] cycloaddition of 2-nitrobenzofurans with aldehyde-derived Morita-Baylis-Hillman (MBH) carbonates or allenoate was developed. reaction MBH resulted in a series cyclopentabenzofurans containing three contiguous stereocenters good to high yields, diastereoselectivities and enantioselectivities. use also gave the target product moderate enantioselectivity.

Language: Английский

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

CCS Chemistry, Journal Year: 2021, Volume and Issue: 4(5), P. 1565 - 1576

Published: May 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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Language: Английский

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Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(10), P. 8991 - 8995

Published: Sept. 3, 2019

A catalytic dearomative three-component reaction of bromoarenes with TMS-diazomethane and allyl borate was developed. The key this assembling is the use a diazo compound to generate Pd-π-benzyl intermediate through Pd-carbene species. This method allowed for functionalization, using arenes as limiting reagents. Heteroaryl bromides were also applicable give dearomatized structures under conditions.

Language: Английский

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Advances in research of spirodienone and its derivatives: Biological activities and synthesis methods

European Journal of Medicinal Chemistry, Journal Year: 2020, Volume and Issue: 203, P. 112577 - 112577

Published: July 15, 2020

Language: Английский

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