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DOI: 10.1055/a-1996-8940
Organocatalytic Synthesis of γ-Amino Acid Precursors via Masked Acetaldehyde under Micellar Catalysis
G.G. is grateful to Ministero dell'Università e della Ricerca (PON-DOT13OV2OC) for an industrial PhD fellowship. F.P. also thanks Ministero dell'Università e della Ricerca (PON-AIM1842894, CUP-E18D19000560001) for funding this research.
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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 chemistrySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1996-8940.
- Supporting Information
Publication History
Received: 15 November 2022
Accepted after revision: 12 December 2022
Accepted Manuscript online:
12 December 2022
Article published online:
30 January 2023
© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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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): tR = 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
For selected examples of organocatalytic reactions under micellar catalysis, where the catalyst is covalently bound with the surfactant, see: