Enantioselective Halocyclization of Indole Derivatives: Using 1,3-Dihalohydantoins with Anionic Chiral Co(III) Complexes

Abstract

Highly enantioselective halocyclization reactions of indole derivatives, including tryptophols and tryptamines, have been accomplished by means of anionic chiral Co(III) complexes and 1,3-dihalohydantoins (as little as 0.50 equiv). 3-Halo-fused indolines were obtained in excellent yields (up to 98%) and enantioselectivities (up to 98% ee), employing the chiral anion phase-transfer-catalysis strategy.

Key words

anion phase-transfer catalysis - chiral Co(III) complex - Brønsted acid - indole derivatives - halocyclization

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• 12 General Experimental Procedures for a Representative Iodocyclization to 3a A 10 mL oven-dried vial was charged with DIDMH (0.10 mmol or 0.05 mmol), catalyst Λ-1a (7.2 mg, 0.01 mmol), activated 4 Å MS (100.0 mg) and CCl₄ (4.0 mL) at room temperature in the absence of light. The mixture was cooled to –20 °C and stirred for 30 min. A precooled solution of tryptophol 2a (0.10 mmol) in CCl₄ (1.0 mL) was added dropwise to the mixture over 20 min, and the reaction was stirred vigorously until the reaction was complete (monitored by TLC). The reaction was then quenched with pre-cooled NEt₃ (–20 °C, 1.0 mmol) and saturated aqueous Na₂S₂O₃ (0.50 mL). After workup, the mixture was purified by flash column chromatography (silica gel, PE/EtOAc = 10:1) to give the enantioenriched product 3a. Yield for 1.0 equiv DIDMH, 37.9 mg (98%); yield for 0.5 equiv DIDMH, 32.5 mg (84%); (flash column chromatography eluent, PE/EtOAc = 10:1); colorless oil; [α]_D ²⁰ –82.6 (c 0.38 CH₃OH). ¹H NMR (600 MHz, CDCl₃): δ = 7.79 (s, 1 H), 7.39 (d, J = 7.2 Hz, 1 H), 7.23 (t, J = 7.0 Hz, 1 H), 7.05 (t, J = 7.4 Hz, 1 H), 6.45–6.17 (m, 1 H), 3.85–3.76 (m, 1 H), 3.45–3.32 (m, 1 H), 2.99–2.86 (m, 2 H), 1.61 (s, 9 H). ¹³C NMR (151 MHz, CDCl₃): δ = 151.92, 129.93, 125.17, 123.84, 115.02, 110.12, 103.32, 82.23, 67.81, 67.32, 47.91, 28.46. HRMS (ESI). m/z calcd for C₁₅H₁₈INNaO₃ [M + Na]⁺: 410.0229; found: 410.0223; ee for 1.0 equiv DIDMH, 95%; ee for 0.5 equiv DIDMH, 92%; determined by HPLC (Daicel Chirapak IE, hexane/isopropanol = 90:10, flow rate 1.0 mL/min, T = 30 °C, 254 nm): t _maj = 9.20 min, t _min = 8.43 min.
• 13 See the Supporting Information for details.
• 14 CCDC 1938720 (3b) and 1938617 (4b) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via . www.ccdc.cam.ac.uk/getstructures
• 15 General Experimental Procedures for a Representative Bromocyclization to 4a A 10 mL oven-dried vial was charged with DBDMH (0.10 mmol or 0.05 mmol), catalyst Λ-1a (7.2 mg, 0.01 mmol), activated 4 Å MS (100.0 mg) and PhMe/CCl₄ (1:20, 4.0 mL) at room temperature in the absence of light. The mixture was cooled to –30 °C and stirred for 30 min. A precooled solution of tryptophol 2a (0.10 mmol) in PhMe/CCl₄ (1:20, 1.0 mL) was added dropwise to the mixture over 20 min, and the reaction was stirred vigorously until the reaction was complete (monitored by TLC). The reaction was then quenched with pre-cooled NEt₃ (–30 °C, 1.0 mmol) and saturated aqueous Na₂S₂O₃ (0.50 mL). After workup. the mixture was purified by flash column chromatography (silica gel, PE/EtOAc = 10:1) to give the enantioenriched product 4a. Yield for 1.0 equiv DBDMH, 32.3 mg (95%); yield for 0.5 equiv DBDMH, 28.6 mg (84%); (flash column chromatography eluent, PE/EtOAc = 10:1); colorless oil; [α]_D ²⁰ –137.1 (c 0.32 CH₃OH). ¹H NMR (600 MHz, CDCl₃): δ = 7.84 (s, 1 H), 7.41 (d, J = 7.5 Hz, 1 H), 7.28 (t, J = 7.8 Hz, 1 H), 7.08 (t, J = 7.5 Hz, 1 H), 6.34–6.12 (m, 1 H), 4.00 (t, J = 8.0 Hz, 1 H), 3.53–3.45 (m, 1 H), 2.94–2.86 (m, 1 H), 2.80 (dd, J = 12.3, 3.8 Hz, 1 H), 1.60 (s, 9 H). ¹³C NMR (151 MHz, CDCl₃): δ = 151.86, 141.73, 131.86, 130.50, 124.87, 123.76, 115.00, 100.87, 82.28, 67.79, 61.77, 45.09, 28.43; ee for 1.0 equiv DBDMH, 96%; ee for 0.5 equiv DBDMH, 96%; determined by HPLC (Daicel Chirapak IC, hexane/isopropanol = 70:30, flow rate 1.0 mL/min, T = 30 °C, 254 nm): t _maj = 4.41 min, t _min = 4.04 min.
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