Enantioselective Oxidative Homocoupling of 2-Oxindoles with a Chiral Bisguanidinium Hypoiodite Catalyst

Abstract

The bisoxindole motif is present in a variety of biologically active compounds. Here, we report an enantioselective oxidative homocoupling reaction of 2-oxindoles in the presence of a chiral bisguanidinium hypoiodite catalyst, providing access to the corresponding optically active bisoxindoles in excellent yields and with moderate to high diastereo- and enantioselectivities.

Key words

guanidinium compounds - hypoiodites - oxidative coupling - enolate coupling - bisoxindoles - asymmetric catalysis

Publication History

Received: 18 June 2024

Accepted after revision: 31 July 2024

Article published online:
20 August 2024

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• 14 Homocoupling Reactions of Oxindoles 7; General Procedure TBHP (0.00136 mL, 0.075 mmol) was added to a stirred mixture of the appropriate indolinecarboxylate 7 (0.100 mmol) and chiral catalyst la (0.0040 g, 0.0025 mmol) in toluene (1.0 mL) at 0 °C. When the reaction was complete (TLC, hexane–EtOAc, 1:1), the solvent was removed in vacuo and the residue was analyzed by ¹H NMR to determine the ratio of the dl and meso isomers. The residue was then purified by flash column chromatography [silica gel, hexane–EtOAc (1:1 to 1:2)]. Dimethyl 1,1′-Diallyl-5,5′-dimethyl-2,2′-dioxo-1,1′,2,2′-tetrahydro-3H,3′H-3,3'-biindole-3,3′-dicarboxylate (8e) Yield: 88%; [α]_D ³⁰ –19.0 (c 1.17, CHCl₃, 70% ee). HPLC [Daicel Chiralpak OD-H, hexane/i-PrOH (8:20), 1 mL/min]: τ_min = 7.45 min, τ_maj = 13.1 min. ¹H NMR (400 MHz, CDCl₃, dl/meso = 17:1): δ = 7.20–7.17 (m, 2.0 H), 7.00–6.96 (m, 2.0 H), 6.62 (d, J = 7.8 Hz, 0.1 H), 6.51 (q, J = 3.8 Hz, 2.0 H), 5.77–5.67 (m, 1.9 H), 5.18–5.13 (m, 3.9 H), 4.40–4.15 (m, 4.0 H), 3.79 (s, 0.3 H), 3.75 (t, J = 2.1 Hz, 5.8 H), 2.21 (d, J = 16.5 Hz, 6.2 H).¹³C NMR (125 MHz, CDCl₃): δ = 169.9, 167.1, 140.9, 131.6, 130.9, 129.9, 127.1, 123.6, 117.8, 108.5, 77.3, 77.2, 77.0, 76.7, 61.5, 53.3, 42.7, 21.1. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₂₈H₂₈N₂NaO₆: 511.18451; found 511.18860.