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

Yiqun Zeng; Chao Fei; Xiao Zhou; Jisheng Luo; Li Deng

doi:10.1055/s-0042-1751496

Synlett, Table of Contents

Synlett 2023; 34(20): 2429-2432
DOI: 10.1055/s-0042-1751496

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Special Issue Dedicated to Prof. Hisashi Yamamoto

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

Yiqun Zeng‡

^aKey Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, P. R. of China

,

Chao Fei‡

^bDepartment of Chemistry, Brandeis University, Waltham, MA 02454-9110, USA

,

Xiao Zhou

^bDepartment of Chemistry, Brandeis University, Waltham, MA 02454-9110, USA

,

Jisheng Luo ∗

^aKey Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, P. R. of China

,

Li Deng∗

^aKey Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, P. R. of China

› Author Affiliations

Abstract

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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

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References

References and Notes
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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.

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