Lewis Acid Catalyzed Three-Component [3+2] Cycloaddition Reaction Using Pentafulvene as 2π Component: An Easy Way to Construct Pentaleno(1,2-b)indoles

Abstract

A facile route toward the synthesis of pentaleno(1,2-b)indoles via multicomponent reaction of indole, aldehyde, and pentafulvene is realized. The reaction proceeds through Lewis acid catalyzed [3+2] cycloaddition of in situ generated indolylmethanol and pentafulvene. This methodology provides an easy access to biologically relevant indole derivatives.

Keywords

fulvene - indole - cycloaddition - multicomponent reaction - cyclopentaleno indoles

• References and Notes

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• 16 Typical Experimental Procedure for 4aa A mixture of indole 1a (50 mg, 0.427 mmol), pentafulvene 3a (147 mg, 0.640 mmol), aldehyde 2a (70 mg, 0.640 mmol), and Sn(OTf)₂ (4 mg, 0.008 mmol) were weighed in to a reaction tube and dry MeCN (2 mL) was added and allowed to stir at r.t. for 2 h. The solvent was evaporated in vacuo and the residue on silica gel (100–200 mesh) column chromatography with mixture of hexane–EtOAc yielded the products.
• 17 Spectral Data of Compound 4aa Yield 115 mg, 62%; off-white solid, mp 155–160 °C; R_f = 0.43 (hexane–EtOAc = 9:1). IR (neat) ν _max = 3402, 3056, 3026, 2923, 1710, 1603, 1489, 1449, 1361, 1224, 1060, 1028, 750, 701 cm^–1. ¹H NMR (500 MHz, CDCl₃, TMS): δ = 7.84 (s, 1 H), 7.27–7.7.25 (m, 3 H), 7.23–7.21 (m, 1 H), 7.19–7.17 (m, 2 H), 7.14–7.13 (m, 5 H), 7.05–7.01 (m, 2 H), 7.00–6.97 (m, 3 H), 6.89 (t, J = 8 Hz, 1 H), 6.50–6.48 (m, 2 H), 6.44–6.43 (m, 1 H), 6.33 (d, J = 8.5 Hz, 1 H), 4.74–4.66 (m, 2 H), 4.20 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 148.0, 146.3, 143.6, 143.4, 142.9, 141.4, 136.8, 135.1, 134.8, 130.2, 129.7, 128.6, 127.9, 127.7, 126.9, 126.8, 126.7, 125.3, 124.3, 122.3, 121.1, 119.7, 118.9, 111.4, 61.5, 51.6, 50.8. ESI-HRMS: m/z calcd for C₂₃H₂₅N [M + H]⁺: 436.20652; found: 436.20610.