Catalytic Enantioselective Friedel–Crafts Alkylation of Indoles with Fumarate Derivatives in the Presence of Chiral Palladium Complexes

Abstract

The catalytic enantioselective Friedel–Crafts alkylation reaction promoted by chiral palladium complexes is described. The treatment of indoles with fumarate derivatives under the mild reaction conditions afforded the corresponding Friedel–Crafts alkylation adducts with high enantioselectivities (up to 91% ee).

Key words

Friedel–Crafts reaction - asymmetric catalysis - chiral palladium catalysts - indoles - fumamate derivatives

• References and Notes


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• 11 Typical Procedure To a stirred solution of N-(3-ethoxycarbonyl but-2-enoyl)oxazolidin-2-one (2e, 21.3 mg, 0.1 mmol), Pd catalyst 4a (4.8 mg, 0.005 mmol) in toluene (1 mL) was added indole (1a, 14.0 mg, 0.12 mmol) at r.t. The reaction mixture stirred for 60 h at r.t. The reaction was diluted with EtOAc (10 mL), then washed with sat. NH₄Cl. The organic layer was dried over anhyd MgSO₄, filtered, concentrated, and purified by flash column chromatography (EtOAc–hexane = 1:1) to afford (S)-N-[3-ethoxycarbonyl-3-(3′-indolyl)butanoyl]-oxazolidin-2-one (3e, 87%, 28.7 mg). [α]_D ²⁴ +95.5 (c 1.0, CHCl₃). ¹H NMR (200 MHz, CDCl₃): δ = 1.99 (t, J = 7.5 Hz, 3 H), 3.32 (dd, J = 3.9, 18.4 Hz, 1 H), 4.04–4.27 (m, 5 H), 4.35 (t, J = 8.0 Hz, 2 H), 4.46 (dd, J = 3.8, 10.8 Hz, 1 H), 7.10–7.16 (m, 3 H), 7.23–7.41 (m, 1 H), 7.73–7.77 (m, 1 H), 8.34 (br s, 1 H). ¹³C NMR (50 MHz; CDCl₃): δ = 14.0, 37.9, 38.3, 42.3, 61.1, 62.2, 111.3, 112.3, 119.2, 119.7, 122.3, 122.4, 126.2, 136.1, 153.5, 171.7, 173.7. ESI-HRMS: m/z calcd for C₁₇H₁₈N₂NaO₅ [M + Na]⁺: 353.1113; found: 353.1110. HPLC [n-hexane–i-PrOH (80:20), 254 nm, 1.0 mL/min] Chiralpak AS-H column, t _R (major) = 32.5 min; t _R (minor) = 38.1, 91% ee
• 12 The two-site binding interaction between substrate and palladium catalyst is crucial to guarantee reactivity as well as stereocontrol. In fact, when the monodentate ethyl fumarate was reacted with indole under the same reaction conditions, no reaction occurred