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Annulation Between Phenol and Indole Derivatives

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Annulation Between Phenol and Indole Derivatives ARTICLE DOI: 10.1038/s41467-017-00873-1 OPEN External oxidant-free electrooxidative [3 + 2] annulation between phenol and indole derivatives Kun Liu1, Shan Tang1, Pengfei Huang1 & Aiwen Lei1,2 Intermolecular [3 + 2] annulation is one of the most straightforward approaches to construct five membered heterocycles. However, it generally requires the use of functionalized substrates. An ideal reaction approach is to achieve dehydrogenative [3 + 2] annulation under oxidant-free conditions. Here we show an electrooxidative [3 + 2] annulation between phenols and N-acetylindoles under undivided electrolytic conditions. Neither external chemical oxidants nor metal catalysts are required to facilitate the dehydrogenation processes. This reaction protocol provides an environmentally friendly way for the selective synthesis of benzofuroindolines. Various N-acetylindoles bearing different C-3 and C-2 substituents are suitable in this electrochemical transformation, furnishing corresponding benzofuroindolines in up to 99% yield. 1 College of Chemistry and Molecular Sciences, the Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072 Hubei, China. 2 State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China. Kun Liu and Shan Tang contributed equally to this work. Correspondence and requests for materials should be addressed to A.L. (email: [email protected]) NATURE COMMUNICATIONS | 8: 775 | DOI: 10.1038/s41467-017-00873-1 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-00873-1 ive-membered heterocycles are highly important efficiency. Developing dehydrogenative [3 + 2] annulation structural motifs, which widely exist in natural products, under oxidant-free conditions may provide solutions to F 1–3 pharmaceuticals, and fundamental materials . these problems. Anodic oxidation represents an effective – Intermolecular [3 + 2] annulation are mostly employed approa- alternative to the oxidation by external chemical oxidants13 19. ches to construct five-membered heterocycles. One typical Over the past decade, increasing efforts have been made to method is 1,3-dipole cycloaddition, which generally requires the achieving dehydrogenative cross-coupling under electrochemical – use of functionalized substrates such as nitrones, azomethine conditions20 35. – ylides, azomethine imine, and azides4 7. To fulfill the demand Benzofuroindoline motifs exist in some important bioactive by green and sustainable chemistry, oxidative [3 + 2] annulation natural products such as diazonamides36, 37, azonazines38, and has been gradually developed to pursuit the synthesis of phalarine39. The direct oxidative [3 + 2] annulation between five-membered heterocycles from readily available starting phenols and indoles provides a straightforward and atom – materials8 12. However, external chemical oxidants are often economic way for the synthesis of benzofuroindolines, which required to facilitate the dehydrogenation processes, which lead could potentially lead to the formation of two regioisomers. In to the decreased atom economy of the overall transformation. analogous to the natural bias, the oxidative [3 + 2] annulation In addition, using strong chemical oxidants can also cause over- between phenols and indoles usually gives benzofuro[2,3-b] oxidation issues, which makes it difficult to achieve high reaction indolines. Over the past decade, different reaction protocols for a Oxidative cross-coupling to access benzofuro[3,2-b]indolines R3 R3 OH 1 O 4 FeCl (1.1 equiv.) R R R1 + 3 R4 DDQ (1.5 equiv.) N N H Ac Ac 27–62% yields b Electrochemical dehydrogenative cross-coupling to access benzofuro[3,2-b]indolines 3 R R3 OH 1 O R4 + Electricity R 1 R2 R4 R + H2 N 2 N Ac R Ac Up to 99% yield Fig. 1 Synthesis of benzofuro[3,2-b]indolines. a Synthesis of benzofuro[3,2-b]indolines by Vincent and co-workers. b Electrochemical synthesis of benzofuro[3,2-b]indolines under external oxidant-free conditions Table 1 Effects of reaction parametersa Me Me OH O C (+)⏐Pt (–): I = 10 mA + nBu NBF (0.02 M) MeO N 4 4 N H Ac Ac HFIP/CH2Cl2 (6:4), rt, 1.8 h MeO Undivided cell 1a 2a 3a Entry Variation from the standard conditions Yield 1 None 99% 2 5 mA instead of 10 mA, 3.6 h 85% 3 20 mA instead of 10 mA, 0.9 h 86% 4 Without CH2Cl2 78% 5 Without HFIP ND 6 MeOH instead of HFIP ND 7 nBu4NClO4 instead of nBu4NBF4 90% 8 nBu4NPF6 instead of nBu4NBF4 85% 9 Platinum plate anode instead of graphite rod anode 78% 10 Graphite rod cathode instead of platinum plate cathode 71% 11 Nickel plate cathode instead of platinum plate cathode 93% 12 Under air 94% 13 No electric current, under air NR ND not detected, NR no reaction. a Standard conditions: graphite rod anode (ϕ 6 mm), platinum plate cathode (15 mm × 15 mm × 0.3 mm), constant current = 10 mA, 1a (0.20 mmol), 2a (0.30 mmol), nBu4NBF4 (0.20 mmol), solvent (10 ml), room temperature, N2, 1.8 h (3.4 F). Yields are determined by GC analysis with biphenyl as the internal standard 2 NATURE COMMUNICATIONS | 8: 775 | DOI: 10.1038/s41467-017-00873-1 | www.nature.com/naturecommunications NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-00873-1 ARTICLE R3 R3 1 O 4 OH C(+)⏐Pt (–) R R R1 + R4 Undivided cell N N Ac H Ac 12 3 Br OAc Me Et O O O O N N H H Ac Ac MeO MeO N N H H Ac MeO Ac MeO 3a,99% 3b,83% 3c,73% 3d,78% Me Ph Me Me O O O O Me N N N N H H H Ac H MeO Ac MeO Ac MeO MeO Ac 3e,72% 3f,95% 3g,70% 3h,80% Me CF tBu O Me 3 Me Cl Me O O O Cl N H Ac N N N MeO H H Ac H Ac MeO Ac MeO MeO 3i,73% 3j,47% 3k,85% 3l,92% Br Me O MeO Me Me Me O O O N N N H Ac N H H MeO H Ac EtO Ac MeO Ac 3m,95% 3n,68% 3o,80% 3p,35% Fig. 2 Synthesis of benzofuro[3,2-b]indolines from 3-substituted N-acetylindoles. Reaction conditions: graphite rod anode (ϕ 6 mm), platinum plate 2 cathode (15 mm × 15 mm × 0.3 mm), constant current = 10 mA (J ≈ 16.7 mA/cm ), 1 (0.20 mmol), 2 (0.30 mmol), nBu4NBF4 (0.20 mmol), HFIP/CH2Cl2 (6.0 ml/4.0 ml), room temperature, N2, 1.8 h (3.4 F). Isolated yields are shown the synthesis of benzofuro[2,3-b]indoline moiety have been quantitative yield under 10 mA constant current for 1.8 h in developed by Harran37, 40, Danishefsky41, Vincent42, 43, and an undivided cell (Table 1, entry 1). Decreased reaction yields – others44 46. In contrast, attempts on phenol–indoles coupling were obtained when increasing or decreasing the operating for the synthesis of benzofuro[3,2-b]indolines have rarely current (Table 1, entries 2 and 3). In addition, solvent effect 47 succeeded . In 2014, Vincent and co-workers reported an was also investigated in this transformation. CH2Cl2 was oxidative [3 + 2] annulation between phenols and 3-substituted not indispensable for this electrochemical dehydrogenative N-acetylindoles for the synthesis of benzofuro[3,2]indolines using cross-coupling reaction. A good reaction efficiency could still be excess amount of FeCl3 and 2,3-dicyano-5,6-dichlor- achieved when HFIP was used as the sole solvent (Table 1, entry obenzoquinone, and the reaction yields ranged from 27 to 62% 4). However, HFIP was found to be crucial since no desired (Fig. 1a)48. It is highly desirable to develop more efficient product could be obtained when dichloromethane was used solely phenol–indole [3 + 2] annulation for the synthesis of benzofuro or HFIP was replaced by methanol (Table 1, entries 5 and 6). [3,2-b]indolines. As for the electrolyte used, the counter anion had slight effect on fi fi Here we present an ef cient electrooxidative [3 + 2] annulation the reaction ef ciency. nBu4NClO4 and nBu4NPF6 were also between phenols and N-acetylindoles in a simple undivided cell. suitable in this transformation (Table 1, entries 7 and 8). It enabled the selective synthesis of benzofuro[3,2]indolines The effect of the electrode material was also explored. Both under external oxidant- and catalyst-free conditions. Various replacing graphite rod anode by platinum plate anode and N-acetylindoles bearing different C-3 substituents are suitable in replacing platinum plate cathode by graphite rod cathode led this electrochemical transformation and can afford corresponding to lower reaction yields (Table 1, entries 9 and 10). However, benzofuro[3,2]indolines in up to 99% yield. platinum plate cathode was possible to be replaced by cheap nickel plate cathode for this dehydrogenative [3 + 2] Results annulation reaction (Table 1, entry 11). Importantly, the reaction could be conducted under atmospheric conditions with a high Investigation of reaction conditions. We anticipated that fi electrochemical anodic oxidation might provide a way to achieve reaction ef ciency (Table 1, entry 12). Obviously, no reaction external oxidant-free dehydrogenative [3 + 2] annulation took place without electric current under air atmosphere (Table 1, (Fig. 1b). p-Methoxylphenol (1a) and 3-methyl-N-acetylindole entry 13). (2a) were chosen as model substrates to test the reaction conditions. Utilizing nBu4NBF4 as the electrolyte and Substrate scope. To demonstrate the applicability of this fl fi 1,1,1,3,3,3-hexa uoroisopropyl alcohol (HFIP)/CH2Cl2 as transformation, we rst turned to explore the substrate scope for co-solvents, benzofuro[3,2-b]indoline 3a could be obtained in a the synthesis of benzofuro[3,2-b]indolines (Fig. 2). The reaction NATURE COMMUNICATIONS | 8: 775 | DOI: 10.1038/s41467-017-00873-1 | www.nature.com/naturecommunications 3 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-00873-1 MeO R3 OH R3 C(+)⏐Pt (–) + 2 R Undivided cell MeO N Ac O N R2 Ac 12 4 MeO MeO MeO MeO H H H H O N O N O N O N Ac Ac MeAc n EtOOC Ac C8H17 NC 4a,93% 4b,98% 4c,76% 4d,71% MeO MeO MeO H Me O N O N O N Ph Ac MeAc Ac 4e,81% 4f,82% 4g,84% Fig.
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