Organocatalytic Synthesis of γ-Amino Acid Precursors via Masked Acetaldehyde under Micellar Catalysis

Abstract

The development of micellar catalysis offers a sustainable alternative to organic solvents, and represents an environmental milestone in organic synthesis. Here, the first Michael addition of masked acetaldehyde under neutral, cationic and anionic micellar catalysis is reported, affording the products in high yields and enantiomeric excess, despite the use of water as solvent.

Key words

micellar catalysis - aminocatalysis - asymmetric synthesis - γ-amino acids - green chemistry

Publication History

Received: 15 November 2022

Accepted after revision: 12 December 2022

Accepted Manuscript online:
12 December 2022

Article published online:
30 January 2023

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• 16 Asymmetric Michael Addition of Acetaldehyde Dimethyl Acetal Performed in Micelles; General Procedure: Acetaldehyde dimethyl acetal 2 (2–4 equiv) was added to a 4 mL scintillation vial equipped with a magnetic bar, containing a solution 50 mM of Triton X-100 (31 mg, 0.05 mmol, 0.25 equiv) in water (1 mL), (S)-diphenyltrimethylsiloxymethylpyrrolidine 3 (6.5 mg, 0.02 mmol, 0.1 equiv), nitroalkene 1a–e (0.2 mmol, 1 equiv), Amberlyst-15 (4.5 mg, 10 mol%), under stirring, and the reaction mixture was stirred at room temperature for the required time. Brine (1 mL) was then added and the aqueous mixture was extracted with THF (1 mL), and CHCl₃ (3 × 1 mL). The combined organic layers were dried over MgSO₄ and concentrated in vacuo after filtration. The crude mixture was purified by flash chromatography on SiO₂ using a mixture of petroleum ether/ethyl acetate 9:1 v/v to give the desired product. NMR spectra of previously reported compounds were in agreement with those of the authentic samples and/or available literature data. Information can be used for the characterization data of other products. (S)-4-Nitro-3-phenylbutanal (4a): Synthesized in accordance with the general procedure for asymmetric Michael addition of acetaldehyde dimethyl acetal performed in micelles, using acetaldehyde dimethyl acetal 2 (42.2 μL, 0.4 mmol) and trans-β-nitrostyrene 1 (30 mg, 0.2 mmol). The reaction mixture was stirred at room temperature for 20 h. The desired product (yield: 35 mg, 0.18 mmol, 90%) was obtained as a pale-yellow oil. ¹H NMR (400 MHz, CDCl₃, 303 K): δ = 9.72 (s, 1 H), 7.37 (t, J = 7.3 Hz, 2 H), 7.31 (d, J = 6.1 Hz, 1 H), 7.28–7.23 (m, 2 H), 4.68 (dd, J = 12.5, 7.2 Hz, 1 H), 4.62 (dd, J = 12.5, 7.5 Hz, 1 H), 4.10 (m, 1 H), 2.97 (d, J = 7.3 Hz, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 198.7, 138.2, 129.2, 128.1, 127.4, 79.4, 46.4, 38.0. HPLC (Lux 3μm-cellulose 1, hexane/i-propanol 90:10, flow: 0.5 mL/min, λ = 210 nm): t_R = 19.6 (minor), 24.7 (major) min. [α]^D ₂₅ = –18.13 (c = 0.0016 g/mL, CHCl₃). All analytical data were in good accordance with reported data.¹⁰