Diastereo- and Enantioselective Assembly of Spirooxindole Tetrahydroquinoline Skeletons through Asymmetric Binary Acid Catalyzed Hydride Transfer–Cyclization

Abstract

An efficient binary acid catalyzed asymmetric intramolecular tandem 1,5-hydride transfer/ring-closure reaction was achieved. The process is catalyzed by the combination of a chiral spirocyclic phospho­ric acid and magnesium chloride to afford structurally diverse spirooxindole tetrahydroquinolines in good yields with high diastereo- and enantioselectivities.

Key words

asymmetric catalysis - phosphoric acid - Lewis acid - spiro­oxindoles - quaternary stereocenter

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• 10 CCDC-1059197 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: [phone]; or [e-mail]].
• 11 General Procedure for the Synthesis of 3: Phosphoric acid catalyst 1i (10 mol%, 3.3 mg), a solution of MgCl₂ in EtOH (2.5 mol%, 0.12 mg, 0.1 mL, 1.2 mg/mL), and 4 Å molecular sieves (15 mg) were added to a Schlenk-type flask and the mixture was dried under vacuum. Toluene (0.3 mL) was then added and the resulting mixture was stirred for 1 h under Ar. A solution of 2 in toluene (0.05 mmol, 0.4 mL) was added and the resulting mixture was heated to 80 °C until the starting material disappeared. The product was purified by silica gel column chromatography (EtOAc–PE, 1:4) to afford the desired product 3. Compound 3a: Yield: 92%; off-white solid; m.p. 149–150 °C; HPLC analysis: 90% ee {Chiralpak AD-H (hexane–i-PrOH, 90:10; 0.8 mL/min): t_R = 12.4 (major), 16.8 (minor) min}; [α]_D ²⁰ 42.9 (c = 1.2, CH₂Cl₂). ¹H NMR (400 MHz, CDCl₃): δ = 7.96 (d, J = 8.0 Hz, 1 H), 7.29–7.20 (m, 2 H), 7.02 (d, J = 7.6 Hz, 1 H), 6.96–6.92 (m, 1 H), 6.67–6.63 (m, 1 H), 6.59 (d, J = 8.0 Hz, 1 H), 6.45 (dd, J = 7.6, 1.2 Hz, 1 H), 4.05 (s, 3 H), 3.77 (q, J = 9.6 Hz, 1 H), 3.54–3.44 (m, 1 H), 3.26–3.20 (m, 1 H), 2.75 (d, J = 15.6 Hz, 1 H), 1.92–1.81 (m, 3 H), 0.93–0.88 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 177.26, 151.34, 143.46, 139.02, 129.64, 128.39, 128.11, 127.99, 124.95, 124.51, 117.83, 115.90, 114.51, 110.26, 62.88, 53.94, 47.09, 46.79, 37.76, 27.04, 23.24. IR (film): 2965, 1760, 1738, 1604, 1479, 1462, 1360, 1287, 1243, 1160, 1072, 746 cm^–1. HRMS (EI-TOF): m/z calcd for C₂₁H₂₀N₂O₃: 348.1474; found: 348.1476.