Enantioselective Oxidative Dearomatization of 2-Naphthols ­Enabled by Chiral Organoiodine Catalysis

Abstract

An asymmetric dearomatizative oxidation of 2-naphthol derivatives has been established by organoiodine catalysis, enabling a series of chiral spirooxindoles with various functional groups to be accessed in high yields and high enantioselectivities under mild conditions.

Key words

oxidation - dearomatization - 2-naphthols - spirooxindole - organoiodine catalysis

Publication History

Received: 06 April 2022

Accepted after revision: 05 July 2022

Article published online:
01 August 2022

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• 17 Typical Procedure for the Synthesis of (S)-1-methyl-2′H-spiro[indoline-3,1′-naphthalene]-2,2′-dione (2a)Under N₂, the Schlenk tube was charged with 3-chloroperoxybenzoic acid (26.3 mg, 0.13 mmol, 1.3 equiv), 1a (27.7 mg, 0.1 mmol, 1.0 equiv), and organoiodine 3f (12.0 mg, 0.02 mmol, 0.2 equiv). Then, trifluoromethanesulfonic acid (5.3 mg, 0.035 mmol, 0.35 equiv) was added with MeNO₂ (1.0 mL) dropwise to the reaction mixture at 25 °C. After the addition was complete, the resulting mixture was stirred at room temperature for 6 h. Afterwards, the solvent was evaporated, and the residue was purified by column chromatography on silica gel (EtOAc/dichloromethane = 1/20) to give the product 2a; yield 80%, 22.1 mg.¹H NMR (500 MHz, CDCl₃): δ = 7.58–7.56 (m, 1 H), 7.37–7.12 (m, 4 H), 6.98–6.81 (m, 3 H), 6.68 (m, 1 H), 6.18 (d, J = 9.9 Hz, 1 H), 3.22 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 193.6, 171.9, 146.0, 143.7, 137.5, 129.7, 129.6, 129.1, 129.0, 128.2, 127.4, 126.5, 123.5, 122.7, 122.3, 108.0, 66.1, 25.9. IR (KBr): ν = 1719, 1707, 1655, 1600, 1560, 1229, 747, 736, 457 cm^–1. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₇H₁₈ONa: 261.1255; found: 261.1249. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₈H₁₄NO₂: 276.1025; found: 276.1023. Enantiomeric ratio: 95.4:4.6, determined by HPLC (Daicel Chirapak IE, hexane/isopropanol = 70/30, flow rate 1.0 mL/min, T = 30 °C, 254 nm): t_maj = 17.72 min, t_min = 25.20 min. [α]20_D = –133.1 (c = 0.40, acetone).
• 18 CCDC 2110235 ((S)-2a) contains the supplementary crystallographic data for this paper. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures