Asymmetric Synthesis of 3-Lactone-Substituted 2-Oxindoles with Vicinal Quaternary Carbon Centers through Vinylogous Conjugate Addition

Dedicated to Professor Hisashi Yamamoto to celebrate his 80^th birthday.

Abstract

A new method has been developed for constructing vicinal quaternary stereocenters with an oxindole–butanolide hybrid framework through asymmetric vinylogous addition of a siloxyfuran to an indol-2-one in the presence of a readily available N,N′-dioxide–Ni(OTf)₂ complex catalyst. Various oxindole–lactones were obtained in up to 98% yield with >19:1 dr and 97% ee under mild reaction conditions. A possible transition-state model is proposed to explain the origin of the asymmetric induction.

Key words

asymmetric catalysis - nickel catalysis - ligands - bromooxindoles - lactones - vinylogous addition

Publication History

Received: 23 February 2023

Accepted after revision: 30 March 2023

Accepted Manuscript online:
30 March 2023

Article published online:
09 May 2023

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• 21 (3S)-3-Methyl-3-[(2S)-2-methyl-5-oxo-2,5-dihydrofuran-2-yl]-1,3-dihydro-2H-indol-2-one (3a): Typical Procedure A dry reaction tube was charged with L₃-PiMe₂ (10 mol%), Ni(OTf)₂ (10 mol%), 3-bromo-3-methyloxindole (1a; 0.10 mmol), and EtOAc (1.0 mL), and the mixture was stirred at 30 °C for 30 min, then cooled to 0 °C. The 5-methyl-substituted siloxyfuran 2a (0.11 mmol) and Et₃N (1.0 equiv) were added with stirring, and the resulting mixture was stirred at 0 °C for 12 h. The mixture was then directly purified by flash chromatography [silica gel, PE–EtOAc (2:1)] to give a colorless oil; yield: 23.8 mg (98%, 19:1 dr, 97% ee). HPLC [Daicel Chiralcel ID, hexane–i-PrOH (90:10), 1.0 mL/min, λ = 254 nm], t _R (major) = 20.23 min, t _R (minor) = 17.71 min. IR ν~(cm^–1): 3258, 1709, 1618, 1471, 1377, 1328, 1254, 1205, 1128, 1105, 958, 819, 754, 695, 606, 489 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.60 (s, 1 H), 7.27 (d, J = 5.6 Hz, 1 H), 7.24–7.18 (m, 2 H), 7.00 (td, J = 0.8 Hz, 1 H), 6.88 (dt, J = 8.0, 0.8 Hz, 1 H), 5.79 (d, J = 5.6 Hz, 1 H), 1.76 (s, 3 H), 1.62 (s, 3 H).¹³C NMR (101 MHz, CDCl₃): δ = 178.7, 172.1, 157.3, 139.6, 130.5, 128.8, 125.2, 123.1, 122.3, 109.9, 89.7, 53.6, 19.0, 18.3. ESI-HRMS: m/z [M + Na]⁺ calcd for C₁₄H₁₃NNaO₃: 266.0788; found: 266.0787.