Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO 2 via Visible-Light-Induced Reductive Dearomatization
2021; Chinese Chemical Society; Volume: 4; Issue: 5 Linguagem: Inglês
10.31635/ccschem.021.202100995
ISSN2096-5745
AutoresYuzhen Gao, Hao Wang, Zhuomin Chi, Lei Yang, Chunlin Zhou, Gang Li,
Tópico(s)Catalytic C–H Functionalization Methods
ResumoOpen 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 Yuzhen Gao Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 , Hao Wang Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 , Zhuomin Chi Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350117 , Lei Yang Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 , Chunlin Zhou Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 and Gang Li *Corresponding author: E-mail Address: [email protected] Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fuzhou, Fujian 350002 Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 https://doi.org/10.31635/ccschem.021.202100995 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Visible-light-induced reductive dearomatization of nonactivated arenes is a very challenging transformation and remains in its infancy. Herein, we report a novel strategy to achieve a visible-light-induced spirocyclizative remote arylcarboxylation of nonactivated arenes including naphthalenyl- and phenyl-bearing aromatics with CO2 under mild conditions through a radical-polar crossover cascade (RPCC). This reductive dearomatization protocol rapidly delivers a broad range of spirocyclic and valuable carboxylic acid derivatives from readily accessible aromatic precursors with generally good regioselectivity and chemoselectivity. Download figure Download PowerPoint Introduction Dearomatization represents a unique synthetic strategy that converts readily available planar arenes into valuable three-dimensional alicyclic molecules.1–6 Notable methods include the Birch reduction,7 transition-metal-catalyzed dearomative functionalization,8,9 oxidative dearomatization of electron-rich (hetero)aromatics,10 and UV-light-promoted photochemical cycloadditions.11 However, progress has mainly been made in the studies of heteroaromatics including indoles, and electron-rich arenes such as phenols and naphthols.1–24 In contrast, only limited important advances have been made in the dearomatization of electronically unbiased aromatics such as naphthalene and benzene derivatives that possess high resonance stabilization energy.6,25–35 Of particular note, the You group25 and the Hong and Jia's group26 have simultaneously reported two types of elegant, highly diastereoselective 1,4-difunctionalization reactions of 1-naphthamides via palladium-catalyzed dearomatization at slightly elevated temperature. Therefore, the dearomatization of nonactivated arenes remains challenging, and the development of a mild and complementary protocol for dearomatization of nonactivated arenes is highly desirable. In recent years, visible-light photoredox catalysis36–45 has emerged as a promising strategy for developing mild protocols for dearomatization,46–59 including several significant protocols for the dearomatization of nonactivated arenes,60–74 such as dearomative cycloadditions that were mainly from the groups of Sarlah and Bach,60–63 and oxidative dearomatization.64–66 A distinct redox-neutral hydroalkylative dearomatization of naphthalene derivatives was also reported by the group of Zhang, Mei, You.67 However, there are only a handful of reports on visible-light-induced reductive dearomatization of nonactivated arenes.68–74 Of particular note, the groups of König68 and Miyake69 independently reported the challenging photoredox catalyst (PC)-induced Birch-type reduction of arenes. Meanwhile, dearomative monofunctionalizations of arenes including hydroalkylation70–72 and hydroboration73 through photoreduction have been disclosed by the groups of Stephenson,70 Murakami,71 and Curran,73 respectively (Scheme 1a). Notably, the Jui group74 achieved the only visible-light-induced reductive spirocyclizative hydroarylation of arenes via radical-polar crossover using an amine reductant (Scheme 1a), avoiding the use of toxic reagents such as SmI2/hexamethylphosphoramide (HMPA)75 in similar traditional transformations. Despite this significant progress, difunctionalization of nonactivated arenes through visible-light-induced reductive dearomatization remains challenging, possibly due to competing protonation and rearomatization. Scheme 1 | (a–c) Visible-light-induced reductive dearomatization of nonactivated arenes. Download figure Download PowerPoint More recently, our group76 reported the reductive arylcarboxylation of styrenes with CO2 via a radical-polar crossover cascade (RPCC), which was initiated by highly reactive aryl radicals that were generated from the reduction of readily available aryl halides. We wondered whether this RPCC process76–91 could be applied to dearomative difunctionalization of nonactivated arenes with CO2. Notably, during our investigation, the Yu group92 reported the 2,3-arylcarboxylation of indoles, a class of well-studied electron-rich heteroarene in dearomatization reactions, via 5-exo-trig cyclization (Scheme 1b). Surprisingly, a chemoselective dearomatization of nonactivated phenyl ring via 6-exo-trig cyclization occurred with 2-phenyl indoles substates under our reaction conditions, leading to products that were distinct from those of Yu's work (Scheme 1c). In line with our continuous interest in catalytic utilization of CO2,93,94 which is an abundant, low-cost, sustainable, and nontoxic C1 building block, herein we report a spirocyclizative remote arylcarboxylation of arenes with CO2 by visible-light-induced reductive dearomatization of aromatics bearing naphthalenyl, phenyl, and quinolinyl groups via RPCC that provides rapid access to valuable, complex, three-dimensional frameworks (Scheme 1c). Notably, a novel type of Hantzsch ester reaductant, that is, 4-potassium carboxylate HE (4-CO2K-HE), was discovered during our study. Results and Discussion To start our investigation, naphthalene derivative 1a (Table 1) was utilized as the model substrate, which was irradiated under 30 W blue light-emitting diodes (LEDs) in the presence of a commercially available PC Ru(bpy)3Cl2 and under an atmospheric pressure of CO2 at ambient temperature. After extensive screening of the reaction conditions, the spirocyclic 1,4-arylcarboxylation product 2, which was the methylated product from original carboxylic acid due to its ease of isolation, was obtained in an 83% isolated yield by employing a novel 4-CO2K-HE reductant95–97 and K2CO3 as the base in dimethylformamide (DMF; entry 1). The structure of 2 was confirmed by X-ray analysis, representing a formal remote C–H carboxylation with CO2.98–100 Control reactions revealed that no product was observed without either a PC or light, indicating the reaction was promoted by light (entries 2 and 3). A significant decrease in the yield was obtained when carrying out the reaction under the nitrogen atmosphere (entry 4), suggesting that some CO2 could be produced from the oxidation of 4-CO2K-HE. Of note, no product was detected without addition of the reductant 4-CO2K-HE (entry 5), which was much better than other reductants such as Hantzsch ester (HEH), N,N-diisopropylethylamine (DIPEA), or Et3N, revealing the critical role of 4-CO2K-HE for the reaction (entries 6–8). Of note, no desired product could be obtained using HCO2K, which was in contrast to our previous reductive arylcarboxylation of styrenes with CO2 (entry 9).76 The yield decreased dramatically when the reaction was carried out using Cs2CO3 as the base or in the absence of K2CO3 (entries 10 and 11). After screening other PCs such as 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) and iridium complexes, Ru(bpy)3Cl2 proved to be the most suitable one (entries 12–14). Slight decrease in the yield was observed when the loading of PC was reduced to 2 mol % (entry 15). Moreover, solvents were also examined, and DMF was found to be the best comparing with solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), and CH3CN (entries 16–18). Finally, no desired product was obtained when the bromide or chloride analog of 1a was employed and most of the starting material was recovered (entries 19 and 20). Table 1 | Optimization of the Reaction Conditionsa Entry Deviation from Standard Conditions Yield (%)b 1 None 87 (83)c 2 Without Ru(bpy)3Cl2 N.D. 3 In the dark N.D. 4 Under a nitrogen atmosphere 37 5 Without 4-CO2K-HE N.D. 6 HEH (2.0 equiv) as reductant 61 7 DIPEA (2.0 equiv) as reductant 18 8 Et3N(2.0 equiv) as reductant N.D. 9 HCO2K (2.0 equiv) as reductant N.D. 10 Cs2CO3 instead of K2CO3 10 11 Without K2CO3 41 12 4CzIPN as PC 45 13 [Ir(ppy)2(dtbbpy)]PF6 as PC N.D. 14 fac-Ir(ppy)3 as PC N.D. 15 Ru(bpy)3Cl2 (2 mol %) 73 16 DMSO instead of DMF 60 17 DMA instead of DMF 74 18 CH3CN instead of DMF N.D. 19 Br instead of I in 1a N.D. 20 Cl instead of I in 1a N.D. Note: N.D., desired product not detected; 4-CO2K-HE, potassium 3,5-bis(ethoxycarbonyl)-2,6-dimethyl-1,4-dihydropyridine-4-carboxylate HE; HEH, Hantzsch ester; bpy, 2,2′-bipyridine; ppy, 2-phenylpyridine; dtbbpy, 4,4-di-tert-butyl-2,2′-bipyridine. aReaction conditions: 1a (0.1 mmol), Ru(bpy)3Cl2 (3 mol %), 4-CO2K-HE (0.12 mmol, 1.2 equiv), K2CO3 (0.2 mmol, 2.0 equiv), DMF (1 mL), 1 atm CO2, rt, 24 h, 30 W blue LEDs; then MeI (0.5 mmol), 60 °C, 2 h. bYield was determined by 1H NMR using CH2Br2 as internal standard. cYield of isolated product in parentheses on 0.2 mmol scale. The optimized reaction conditions for 1a were then tested with a series of naphthalene and quinoline derivatives to investigate the generality of this spirocyclizative arylcarboxylation. As shown in Scheme 2, naphthalene derivatives with a phenol ether linker bearing various functional groups, such as halide (F, Cl, and Br) and CO2Me, afforded the corresponding dearomatized products in good yields ( 2– 7). Substrates possessing a quinolinyl or/and pyridyl group were also compatible with the protocol to produce structurally diverse heterocycles ( 8– 11). In addition, N-protected aniline linkers with different protecting groups (such as Boc, Ac, Cbz, and CO2Ph) were also tolerated ( 12– 15). Moreover, several substitution patterns on the aniline ring were allowed with the reaction to give desired products in satisfied yields ( 16– 21). Finally, spiroindolines could be delivered with quinolinyl substrates with the aniline linkers ( 22 and 23). Of note, only trace amounts of side product from the competitive hydroarylation reaction could be observed for most of the substrates, except less than 5% of hydroarylation side products were detected with products 9 and 23. Scheme 2 | Scope of spirocyclizative arylcarboxylation of naphthalenes and quinolines with CO2. Reaction conditions: 1 (0.2 mmol), Ru(bpy)3Cl2 (3 mol %), 4-CO2K-HE (0.24 mmol, 1.2 equiv), K2CO3 (0.4 mmol, 2.0 equiv), DMF (2 mL), 1 atm CO2, rt, 24 h, 30 W blue LEDs; then MeI (1.0 mmol), 60 °C, 2 h. Isolated yields. aMethylation conditions: SOCl2 (0.4 mL), MeOH (4 mL), 100 °C, 6 h. Download figure Download PowerPoint Subsequently, the versatility of the spiro-dearomative arylcarboxylation process was studied with 1-naphthamides (Scheme 3).25 Pleasingly, using our protocol several N-alkyl groups (such as methyl, benzyl, and isopropyl) were compatible with the reaction, delivering desired products 25– 27 in good yields (73–76%). Notably, substrates bearing electron-donating groups (Me and OMe), or electron-withdrawing groups (halides, CO2Me, CF3, and CN) at the meta or para position of the phenyl ring were all tolerated with this reaction, affording the desired products in generally good yields (28–38, 60–75%). Substrate bearing a methyl at the C6 position gave the desired product 39 in 64% yield. In addition, substrate with a pyridyl group was also viable in this transformation, providing the target product 40 in an acceptable yield. Of note, substrates bearing a methyl at the C4 position of the naphthalenyl were tolerated, producing the 4-carboxylated products ( 41– 43) in reasonable yields, though about 10% of hydroarylation side product was also observed for these examples. Scheme 3 | Scope of spirocyclizative arylcarboxylation of 1-naphthamides with CO2. Reaction conditions: 24 (0.2 mmol), Ru(bpy)3Cl2 (3 mol %), 4-CO2K-HE (0.24 mmol, 1.2 equiv), K2CO3 (0.4 mmol, 2.0 equiv), DMF (2 mL), 1 atm CO2, rt, 24 h, 30 W blue LEDs; then MeI (1.0 mmol), 60 °C, 2 h. Isolated yields. aYield of major diastereomer, minor diastereomer not isolated. Download figure Download PowerPoint Furthermore, the reaction was explored with 2-tethered naphthalenes and phenyl aromatics (Scheme 4). Pleasingly, after being subjected to our reaction conditions, 2-tethered naphthalenes led to 1,2-arylcarboxylation dearomatized products ( 45– 48) whose structures were different from the above-mentioned remote 1,4-arylcarboxylation of 1-tethered naphthalenes, albeit in moderate yields. Of note, some 1,2-hydroarylation side product (10–20%) was also generated with these substrates. Importantly, this approach could be applied to dearomatize challenging benzamide and nonactivated phenyl rings ( 49– 53), though the scope is limited for this type of substrate and a phenanthridin-6-one side product (10–20%) was observed with products 49 and 50, and some minor unknown side products were also produced with products 51– 53. Scheme 4 | Scope of spirocyclizative arylcarboxylation of 2-tethered naphthalenes and phenyl aromatics with CO2. Reaction conditions: 44 (0.2 mmol), Ru(bpy)3Cl2 (3 mol %), 4-CO2K-HE (0.24 mmol, 1.2 equiv), K2CO3 (0.4 mmol, 2.0 equiv), DMF (2 mL), 1 atm CO2, rt, 48 h, 30 W blue LEDs; then MeI (1.0 mmol), 60 °C, 2 h. Isolated yields. aStructure of major diastereomer displayed; 10–20% of hydroarylation side product observed. b24 h. Download figure Download PowerPoint During our study, we also obtained surprisingly unexpected reactivity with 2-phenyl indoles (Scheme 5). Interestingly, dearomatization occurred predominantly at the nonactivated phenyl ring via 6-exo-trig cyclization rather than at the activated indole ring's C2–C3 double bond via 5-exo-trig as in the previous study with the same substrate.92 This led to spirocyclic product 55 with a formal remote C–H carboxylation.98–100 The rationale for this chemoselectivity is not clear at present. Initially, the iodide substrate was also employed, but it was less effective than its bromide analog ( 55). It should be mentioned that the original carboxylic acid product was isolated in a lower yield than its methyl ester product 55. We suspected the product might be labile, resulting in a relatively lower yield. Gratifyingly, substrates bearing a series of substituents on the indole ring or the aryl bromide ring could be converted into the corresponding products in moderate yields (56–65). It should be mentioned that generally about 5% product of arylcarboxylation of indole's C2–C3 double bond, and side products from debromination (about 5%) as well as hydroarylation of the 2-phenyl group (generally <5%) were also observed. We noted that the unreacted substrate could not be recovered and was either transformed to other unidentifiable product or decomposed. Moreover, the amide group was important since no desired product was obtained with substate bearing a 2-bromobenzyl group instead of the 2-bromobenzamide group. Scheme 5 | Scope of spirocyclizative arylcarboxylation of 2-phenyl indoles with CO2. Reaction conditions: 54 (0.2 mmol), Ru(bpy)3Cl2 (3 mol %), 4-CO2K-HE (0.24 mmol, 1.2 equiv), K2CO3 (0.4 mmol, 2.0 equiv), DMF (2 mL), 1 atm CO2, 30 W blue LEDs, rt, 24 h; then MeI (1.0 mmol), 60 °C, 2 h. Isolated yields; about 5% of arylcarboxylation of indole's C2–C3 double bond, and debromination (about 5%) and hydroarylation of the phenyl group (generally <5%) side products were observed. a2 mmol scale. Download figure Download PowerPoint We moved on to conduct preliminary mechanistic studies to obtain insight into the reaction mechanism. First, the Stern–Volmer luminescence experiments showed the light-activated Ru catalyst (PC*) was quenched effectively by 4-CO2K-HE rather than substrate 54a (see Supporting Information for details). To determine the carboxyl source for the product, 13CO2 (99% 13C) gas was employed, and 88% 13C incorporation was found in the carboxyl of the product (Scheme 6a). Moreover, the isotope-labeling study that produced the diene product d- 66 suggested the possible presence of an anion intermediate (Scheme 6b). Furthermore, radical trapping reactions were also performed, such as using 1,1-diphenyl ethylene and 2,2,6,6-tetramethylpiperidinooxy (TEMPO), but no identifiable radical intermediate was trapped, and TEMPO probably suppressed the reaction by oxidizing 4-CO2K-HE (see Supporting Information). The reaction could be scaled up to 5 mmol without much decrease in the yield of 2 (Scheme 6c). Finally, product derivation was briefly carried out to generate ester 67 and valuable allylic alcohol 68 in high yields (Scheme 6d). Scheme 6 | (a–d) Mechanistic studies, scale-up reaction, and product derivation. Download figure Download PowerPoint A possible mechanism was proposed based on the above mechanistic studies (Scheme 7). Upon blue light irradiation, the excited PC* ( A) was produced and subsequently quenched reductively by 4-CO2K-HE (E = −0.90 V vs. saturated calomel electrode (SCE) in DMF, see Supporting Information) to give reduced PC ( B) (E1/2 [RuII*/RuI] = +0.77 V vs SCE in MeCN)101 and corresponding dihydropyridine radical ( C) with the release of CO2. Reduction of aryl bromide 54a by B (E1/2 [RuI/RuII] = −1.33 V vs SCE in MeCN)101 produced aryl radical D which underwent dearomatization via the 6-exo-trig cyclization to afford the spirocyclic radical E. Single-electron transfer from the dihydropyridine radical C to E generated anionic intermediate G, which underwent nucleophilic addition to CO2 to produce the carboxylate H. Finally, base-promoted double bond rearrangement followed by methylation afforded methyl ester 55. Scheme 7 | Proposed catalytic cycle. Download figure Download PowerPoint Conclusion We have developed a novel, strategy of visible-light-induced spirocyclizative remote arylcarboxylation of a series of nonactivated arenes including naphthalenes, 2-phenyl indoles, and N-benzylanilines with CO2 under mild conditions through RPCC. An interesting unusual chemoselective dearomatization of 2-phenyl indoles via 6-exo-trig cyclization was presented. This reductive dearomatization/arylcarboxylation protocol efficiently delivers valuable three-dimensional carboxylic acid derivatives from readily accessible aromatic precursors, providing a distinct method for complex molecule construction. Supporting Information Supporting Information is available, including general experimental procedures and characterization spectra. Conflict of Interest The authors declare no competing financial interest. Preprint Statement Research presented in this article was posted on the preprint server ChemRxiv prior to publication in CCS Chemistry. 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