Chiral Betaine-Mediated Efficient Organocatalytic Asymmetric Isomerization of β,γ-Unsaturated Butenolides

Dedicated to Professor Hisashi Yamamoto on the occasion of his 80th birthday.

Abstract

An asymmetric isomerization of β,γ-unsaturated butenolides with a newly developed betaine catalyst at a 0.2–2 mol% loading, an improvement upon available methods that use 0.5–2.0 mol% catalyst.

Key words

butenolides - isomerization - betaines - cinchona alkaloids - asymmetric catalysis - furanones

Publication History

Received: 03 July 2023

Accepted after revision: 22 August 2023

Article published online:
20 October 2023

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• 16 Butenolides 2A–M; General Procedure Catalyst QD-8 was mixed with KOH (5.6 mg per 0.001 mmol catalyst) in CHCl₃ (0.1 mL per 0.001 mmol catalyst), and the mixture was stirred at r.t. for 30 min. A volume of the clear solution containing the amount of catalyst indicated in Table 2 was collected and added to a solution of the appropriate butenolide 1 (0.2 mmol) in CHCl₃ (0.1 M). The resulting mixture was stirred for 10 min at the temperature indicated in Table 2. 50 wt% aq KOH (4.4 μL) was added, and the mixture was stirred for the length of time as indicated in Table 2. The reaction mixture was then passed through a plug of Celite, which was subsequently washed with Et₂O (3 × 3.0 mL). The filtrate was concentrated in vacuo, and the residue was purified by flash column chromatography [silica gel, Et₂O–hexane (1:10 to 1:3)]. (5R)-4-Ethyl-5-methylfuran-2(5H)-one (2L) Colorless oil; yield: 23 mg (90%, 96% ee). IR (CHCl₃): 751, 856, 906, 941, 1037, 1082, 1174, 1254, 1293, 1460, 1639, 1746, 2936, 2977 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 5.78 (s, 1 H), 4.94 (q, J = 6.6, 1 H), 2.46–2.36 (m, 1 H), 2.28 (m, 1 H), 1.44 (d, J = 6.6 Hz, 3 H), 1.23 (t, J = 7.2 Hz, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 175.8, 173.2, 114.4, 80.3, 21.3, 18.3, 11.3. HRMS (ESI): m/z [M + H]⁺ calcd for C₇H₁₁O₂: 127.0754; found: 127.0758.