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Synlett 2017; 28(05): 572-576
DOI: 10.1055/s-0036-1588676
DOI: 10.1055/s-0036-1588676
letter
Ruthenium/Iridium-Catalyzed C-2 Activation of Indoles with Bicyclic Olefins: An Easy Access to Functionalized Heterocyclic Motifs
Further Information
Publication History
Received: 25 October 2016
Accepted after revision: 27 November 2016
Publication Date:
20 December 2016 (online)
‡ These authors contributed equally
Abstract
Selective C-2 functionalization of N-protected and free indoles is reported. The ruthenium-catalyzed C-2 activation of indoles provided an easy access to cyclopentenylated indoles. Hydroheteroarylated bicyclic motifs were synthesized via iridium-catalyzed C-2 activation of NH indoles. The methodology was extended to different bicyclic adducts such as diaza- or urea-derived bicyclic olefins.
Key words
indole - diazabicyclic olefins - urea derived - iridium catalyzed - ruthenium catalyzed - C–H activationSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588676.
- Supporting Information
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- 14 Typical Experimental Procedure for 3 A mixture of diazabicyclic olefin (60 mg, 0.2497 mmol, 1.5 equiv), indole (42 mg, 0.1665 mmol, 1.0 equiv), [RuCl2(p-cymene)]2 (3 mg, 0.0050 mmol, 3 mol%), and Cu(OAc)2·H2O (7 mg, 0.0333 mmol, 20 mol%) were weighed into a Schlenk tube and degassed for 10 min. Dry toluene (2 mL) was added, and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The crude reaction mixture was purified by silica gel (100–200 mesh) column chromatography using an EtOAc–hexane mixture to yield the cyclopentane-substituted indoles.
- 15 Spectroscopic Data for 3a Rf = 0.85 (hexane–EtOAc = 7:3 ). IR (neat): νmax = 3289, 2919, 1716, 1606, 1532, 1419, 1262, 1172, 1096, 1061, 758 cm–1. 1H NMR (500 MHz, CDCl3): δ = 9.99 (br s, 1 H), 7.49 (d, J = 8.0 Hz, 1 H), 7.34 (d, J = 8.0 Hz, 1 H), 7.08 (t, J = 7.0 Hz, 1 H), 7.01 (t, J = 7.5 Hz, 1 H), 6.57 (br s, 1 H), 6.19 (s, 1 H), 5.94 (s, 1 H), 5.88 (s, 1 H), 4.76 (br s, 1 H), 4.33–3.99 (m, 5 H), 2.57 (br s, 2 H), 1.37–1.25 (m, 4 H), 0.89–0.85 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 155.7, 138.8, 130.8, 128.1, 127.5, 120.9, 119.7, 118.8, 110.5, 99.7, 62.5, 34.7, 29.5, 14.4. ESI-HRMS: m/z calcd for C19H23N3O4Na: 380.15863; found: 380.15851.
- 16 Typical Experimental Procedure for 5 A mixture of bicyclic alkene (80 mg, 0.3329 mmol, 1.0 equiv), indole (35 mg, 0.2996 mmol, 0.9 equiv), [Ir(1,5-cod)Cl]2 (11 mg, 0.0166 mmol, 5 mol%) and dppe (13 mg, 0.0333 mmol, 10 mol%) were weighed into a Schlenk tube and degassed for 10 min. Dry toluene (2 mL) was added, and the reaction mixture was purged with argon and allowed to stir at 110 °C for 16 h. The crude reaction mixture was purified by alumina column chromatography using EtOAc–hexane mixture to yield the hydroheteroarylated bicyclic olefins.
- 17 Spectroscopic Data for Compound 5a Rf = 0.28 (hexane–EtOAc = 7:3). IR (neat): νmax = 3333, 3054, 2982, 2911, 1713, 1618, 1459, 1402, 1374, 1323, 1171 cm–1. 1H NMR (500 MHz, CDCl3): δ = 8.88–8.41 (m, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.33 (d, J = 8.0 Hz, 1 H), 7.15 (t, J = 7.0 Hz, 1 H), 7.07 (t, J = 7.0 Hz, 1 H), 6.21 (s, 1 H), 4.73–4.61 (m, 2 H), 4.27 (m, 4 H), 3.40 (br s, 1 H), 2.36–2.26 (m, 1 H), 2.11 (br s, 1 H), 1.92–1.90 (m, 1 H), 1.72 (br s, 1 H), 1.33–1.24 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 157.7, 139.3, 136.4, 128.1, 121.8, 120.0, 119.8, 110.8, 99.2, 64.4, 62.8, 60.2, 39.5, 35.6, 14.5. ESI-HRMS: m/z calcd for C19H23N3O4Na: 380.15863; found: 380.16012.
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Selected references:
Selected references: