Rhodium-Catalyzed Decarbonylative Intramolecular Arylation of 2-(1H-Indole-1-carbonyl)benzoic Acids

Abstract

We developed a redox-neutral synthesis of isoindoloindolone via intramolecular arylation of 2-(1H-indole-1-carbonyl)benzoic acids. This protocol facilitates the formation of various substituted isoindoloindolones in yields ranging from 17% to 80%. Our mechanistic investigations indicate the pivotal role of NaI: the iodide anion promotes the formation of the desired isoindoloindolone, and the sodium cation suppresses the formation of acylated byproducts, thereby enabling the selective formation of isoindoloindolones in acceptable yields.

Key words

rhodium - intramolecular arylation - mixed anhydride - isoindoloindolones - C–H activation - indoles

Publikationsverlauf

Eingereicht: 15. Februar 2024

Angenommen nach Revision: 28. Februar 2024

Accepted Manuscript online:
28. Februar 2024

Artikel online veröffentlicht:
20. März 2024

• References and Notes

• 1a Xu W, Gavia DJ, Tang Y. Nat. Prod. Rep. 2014; 31: 1474
• 1b Zhang MZ, Chen Q, Yang GF. Eur. J. Med. Chem. 2015; 89: 421
• 1c Norwood VM, Huigens RW. ChemBioChem 2019; 20: 2273
• 2a Boussard MF, Truche S, Rojas AR, Briss S, Decscamps S, Droual M, Wierzbicki M, Ferry G, Aundint V, Delagrange P, Boutin JA. Biochem. Pharmacol. 2006; 41: 306
• 2b Guillaumel J, Pierre L, Renard P, Pfeiffer B, Peruchon L, Arimondo P, Monneret C. Oncol. Res. 2003; 13: 537
• 3a Crenshaw MD, Zimmer H. J. Heterocycl. Chem. 1984; 21: 623
• 3b Wang L, Sun M, Ding MW. Eur. J Org. Chem. 2017; 18: 2568
• 4 Kim G, Kim JH, Kim W, Kim YA. Tetrahedron Lett. 2003; 44: 8207
• 5a Guo S, Tao L, Wang F, Fan X. Chem. Asian J. 2016; 11: 3090
• 5b Yoo JM, Ho SL, Cho CS. Synlett 2016; 27: 1383
• 5c Huang Q, Han Q, Fu S, Yao Z, Su L, Zhang X, Lin S, Xiang S. J. Org. Chem. 2016; 81: 12135
• 6 Kandukuri SR, Oestreich M. J. Org. Chem. 2012; 77: 8750

For selected reviews on decarboxylative/decarbonylative arylations using carboxylic acids, see:
• 7a Rodríguez N, Goossen LJ. Chem. Soc. Rev. 2011; 40: 5030
• 7b Dzik WI, Lange PP, Gooβen LJ. Chem. Sci. 2012; 3: 2671
• 7c Wei Y, Hu P, Zhang M, Su W. Chem. Rev. 2017; 117: 8864
• 7d Perry GJ. P, Larrosa I. Eur. J. Org. Chem. 2017; 3517
• 7e Majumder S, Ghosh S, Pyne P, Ghosh A, Ghosh D, Hajra A. Chem. Rec. 2022; 22: e202100288

For selected examples on decarboxylative arylation using carboxylic acids, see:
• 8a Voutchkova A, Coplin A, Leadbeater NE, Crabtree RH. Chem. Commun. 2008; 6312
• 8b Wang C, Piel I, Glorius F. J. Am. Chem. Soc. 2009; 131: 4194
• 8c Cornella J, Lu P, Larrosa I. Org. Lett. 2009; 11: 5506
• 8d Zhang F, Greaney MF. Angew. Chem. Int. Ed. 2010; 49: 2768
• 8e Zhou J, Hu P, Zhang M, Huang S, Wang M, Su W. Chem. Eur. J. 2010; 16: 5876
• 8f Hu P, Zhang M, Jie X, Su W. Angew. Chem. Int. Ed. 2012; 51: 227
• 8g Zhao S, Liu Y.-J, Yan S.-Y, Chen F.-J, Zhang Z.-Z, Shi B.-F. Org. Lett. 2015; 17: 3338
• 8h Chen L, Ju L, Bustin KA, Hoover JM. Chem. Commun. 2015; 51: 15059
• 8i Patra T, Nandi S, Sahoo SK, Maiti D. Chem. Commun. 2016; 52: 1432
• 8j Honeycutt AP, Hoover JM. ACS Catal. 2017; 7: 4597
• 8k Li Y, Qian F, Wang M, Lu H, Li G. Org. Lett. 2017; 19: 5589
• 8l Yang K, Song M, Ma Z, Li Y, Li Z, Sun X. Org. Chem. Front. 2019; 6: 3996
• 8m Singh S, Shinde VN, Kumar S, Meena N, Bhuvanesh N, Rangan K, Kumar A, Joshi H. Chem. Asian J. 2023; 18: e2023006

For selected examples on decarbonylative arylations using carboxylic acids with acid anhydrides, see:
• 9a Pan F, Lei Z.-Q, Wang H, Li H, Sun J, Shi Z.-J. Angew. Chem. Int. Ed. 2013; 52: 2063
• 9b Maetani S, Fukuyama T, Ryu I. Org. Lett. 2013; 15: 2754
• 9c Lei Z.-Q, Ye J.-H, Sun J, Shi Z.-J. Org. Chem. Front. 2014; 1: 634
• 9d Zhang L, Xue X, Xu C, Pan Y, Zhang G, Xu L, Li H, Shi Z. ChemCatChem 2014; 6: 3069
• 9e Kwon S, Kang D, Hong S. Eur. J. Org. Chem. 2015; 3671
• 9f Qiu X, Wang P, Wang D, Wang M, Yuan Y, Shi Z. Angew. Chem. Int. Ed. 2019; 58: 1504
• 9g Zhao H, Xu J, Xu X, Pan Y, Yu Z, Xu L, Fan Q, Walsh PJ. Adv. Synth. Catal. 2021; 363: 3995

For our previous reports on Rh(I)-catalyzed C–H activation with carboxylic acids, see:
• 10a Suzuki H, Liao Y, Kawai Y, Matsuda T. Eur. J. Org. Chem. 2021; 4938
• 10b Suzuki H, Sasamori F, Mastuda T. Org. Lett. 2022; 24: 1141
• 10c Suzuki H, Kawai Y, Takemura Y, Matsuda T. Org. Biomol. Chem. 2022; 20: 2808
• 10d Suzuki H, Ito Y, Matsuda T. Chem. Lett. 2022; 51: 775
• 10e Suzuki H, Takemura Y, Matsuda T. Synlett 2023; 34: 1894
• 11 Fukuyama T, Sugimori T, Maetani S, Ryu I. Org. Biomol. Chem. 2018; 16: 7583

For selected reviews on transition-metal-mediated decarbonylation, see:
• 12a Dermenci A, Dong G. Sci. China Chem. 2013; 56: 685
• 12b Lu H, Yu T.-Y, Xu P.-F, Wei H. Chem. Rev. 2021; 121: 365
• 12c Saikia P, Gogoi S. Org. Biomol. Chem. 2021; 19: 8853
• 13 Dang Q, Chen J, Li T, Liu L, Huang T, Li C, Chen T. J. Org. Chem. 2023; 88: 12808
• 14 Typical Experimental Procedure for the Rhodium-Catalyzed Decarbonylative Intramolecular Arylation of Benzoic Acids 1 To an oven-dried test tube equipped with a stirring bar were added benzoic acid 1 (0.3 mmol), [RhCl(nbd)]₂ (6.9 mg, 0.015 mmol), and NaI (11.2 mg, 0.075 mmol), followed by the addition of 1,4-dioxane (0.6 mL). Subsequently, Piv₂O (83.8 mg, 91 μL, 0.45 mmol) was injected into the solution via a syringe, and the tube was sealed with a PTFE-lined cap. The reaction mixture was stirred at 170 °C for 18 h. After cooling to room temperature, the mixture was filtered through a pad of silica gel (EtOAc/hexane = 1:1). The filtrate was concentrated under reduced pressure, and the residue was purified by preparative thin-layer chromatography to yield product 2. 1-Methyl-6H-isoindolo[2,1-a]indol-6-one (2c) The title compound was obtained as a yellow solid (54.6 mg, 78%); purified by preparative TLC (dichloromethane/toluene/hexane = 1:1:2); mp 143.2–143.8 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.68–7.62 (m, 2 H), 7.45–7.37 (m, 2 H), 7.27–7.21 (m, 1 H), 7.11 (t, J = 7.7 Hz, 1 H), 6.88 (d, J = 7.4 Hz, 1 H), 6.53 (s, 1 H), 2.40 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.5, 138.0, 134.6, 133.9, 133.6, 133.5, 133.2, 131.8, 128.5, 126.2, 125.0, 124.4, 120.9, 110.7, 101.9, 18.3. IR (neat): 3424, 3115, 2100, 1733, 1621, 1494, 1468, 1448, 1386, 1282, 1218, 1183, 1145, 1080, 906, 827, 778, 759, 693, 545 cm^–1. HRMS (ESI-TOF): m/z calcd for C₁₆H₁₁NNaO⁺ [M + Na]⁺: 256.0733; found: 256.0736. 2-Bromo-6H-isoindolo[2,1-a]indol-6-one (2i) The title compound was obtained as a yellow solid (41.8 mg, 47%); purified by preparative TLC (dichloromethane/toluene/hexane = 1:1:1); mp 174.1–175.0 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.77–7.69 (m, 2 H), 7.58–7.46 (m, 3 H), 7.39–7.31 (m, 2 H), 6.50 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.3, 139.8, 136.1, 134.2, 133.9, 133.6, 132.1, 129.2, 128.9, 125.4, 124.9, 121.4, 116.9, 114.4, 102.3. IR (neat): 3116, 1728, 1621, 1437, 1380, 1355, 1318, 1174, 1140, 1047, 865, 798, 759, 695 cm^–1. HRMS (ESI-TOF): m/z calcd for C₁₅H₈ ⁷⁹BrNNaO⁺ [M + Na]⁺: 319.9681; found: 319.9669.