Sustainable Organocatalyzed Enantioselective Catalytic Michael Additions in Betaine-Derived Deep Eutectic Solvents

Daniela P. Fonseca; Ana C. Amorim; Elisabete P. Carreiro; João P. Prates Ramalho; Gesine J. Hermann; Hans-Jürgen Federsel; Ana Rita C. Duarte; Anthony J. Burke

doi:10.1055/a-2117-9971

SynOpen, Table of Contents

CC BY 4.0 · SynOpen 2023; 07(03): 374-380
DOI: 10.1055/a-2117-9971

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Sustainable Organocatalyzed Enantioselective Catalytic Michael Additions in Betaine-Derived Deep Eutectic Solvents

Daniela P. Fonseca

^aChemistry and Biochemistry Department, School of Science and Technology, University of Évora, Évora, Portugal

,

Ana C. Amorim

^bChiratecnics, LDA, PO, Rossio, Évora, 7006-802, Portugal Laboratory 007, Building A. Colégio Pedro de Fonseca, University of Évora, PITE Industrial and Technological Park, 7000 Évora, Portugal

,

Elisabete P. Carreiro

^cLAQV-REQUIMTE, Institute for Research and Advanced Studies, University of Évora, Rua Romão Ramalho 59, 7000-671 Évora, Portugal

,

João P. Prates Ramalho

^aChemistry and Biochemistry Department, School of Science and Technology, University of Évora, Évora, Portugal

^cLAQV-REQUIMTE, Institute for Research and Advanced Studies, University of Évora, Rua Romão Ramalho 59, 7000-671 Évora, Portugal

,

Gesine J. Hermann

^bChiratecnics, LDA, PO, Rossio, Évora, 7006-802, Portugal Laboratory 007, Building A. Colégio Pedro de Fonseca, University of Évora, PITE Industrial and Technological Park, 7000 Évora, Portugal

,

Hans-Jürgen Federsel

^dRISE, Research Institutes of Sweden, Box 5607, 114 86 Stockholm, Sweden

,

Ana Rita C. Duarte

^eLAQV/REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

,

Anthony J. Burke∗

^aChemistry and Biochemistry Department, School of Science and Technology, University of Évora, Évora, Portugal

^cLAQV-REQUIMTE, Institute for Research and Advanced Studies, University of Évora, Rua Romão Ramalho 59, 7000-671 Évora, Portugal

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Abstract

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Abstract

The organocatalyst cinchonidine-squaramide was immobilized within three different deep eutectic solvents (DESs): betaine:d-sorbitol:water, betaine: d-xylitol:water, and betaine:d-mannitol:water and evaluated in a well-known asymmetric Michael addition. These reactions provided excellent yields (up to 99%) and enantioselectivities (up to 98%) using only 1 mol% of organocatalyst. It was also possible to achieve 9 cycles in reactions with DES (betaine:d-sorbitol:water), proving the high recyclability of this system. In the reactions realized with only 0.5 mol% of organocatalyst, it was possible to achieve 5 cycles, and the products were obtained with high yields (up to 95%) and excellent enantioselectivities (up to 94%), using DES (betaine:d-sorbitol:water).

Keywords

cinchonidine-squaramide - betaine - deep eutectic solvent (DES) - immobilization - organocatalysis

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References

References and Notes
1 Current address: Faculty Pharmacy, University of Coimbra, Pólo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548 Coimbra, Portugal; e-mail: ajburke@ff.uc.pt.
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18 General Procedure for Producing DESs In general, DESs result from the mixture of several components in the appropriate amounts to obtain the DES in the desired ratios. The conditions presented were optimized for each DES. The specific DES resulted from mixing 1 equiv of betaine with 1 equiv of the desired sugar and 3 equiv of water, in the case of DESs produced in the ratio 1:1:3.
19 General Procedure for Asymmetric Catalytic Michael Additions 2 mL of DES solvent was added to a 25 mL round-bottom flask containing a magnetic stirring bar. 1 equiv of trans-β-nitrostyrene (2, 0.25 mmol) and 1.1 equiv of acetylacetone (1) or methyl 2-oxocyclopentane-1-carboxylate (4, 0.275 mmol) were added to the DES. Finally, 5, 1, or 0.5 mol% of cinchonidine-squaramide (catalyst A in the Supporting Information) were added to the mixture and allowed to react for 24 h at 40 °C under sufficient stirring (this is very important as the DES by nature is viscous). The reaction was monitored by TLC and after total consumption of the starting material, extraction was performed with Hex:AcOEt (1:1, 2 × 2 mL). The crude products 3 (yellowish solid) or 5 (colorless opaque oil) isolated from the reaction mixture were directly analyzed by ¹H NMR spectroscopy and HPLC without further purification. The previously described procedure was repeated for several reaction cycles until the catalyst no longer showed catalytic activity.
20 Product 3 Yellow solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.35–7.16 (m, 5 H, ArH), 4.65 (m, 2 H, CH₂), 4.38 (m, 1 H, CH), 4.27 (m, 1 H, CH), 2.29 (s, 3 H, CH₃), 1.94 (s, 3 H, CH₃) ppm. ¹³C APT-NMR (100 MHz, CDCl₃): δ = 201.80 (C), 201.03 (C), 135.99 (CH), 129.36 (2 × CH), 128.58 (CH), 127.95 (2 × CH), 78.20 (CH₂), 70.74 (CH), 42.80 (CH), 30.45 (CH₃), 29.55 (CH₃) ppm.
21 Product 5 ¹H NMR (400 MHz, CDCl₃): δ = 1.81–2.07 (m, 4 H, 2 CH₂), 2.31–3.39 (m, 2 H, CH₂), 3.75 (s, 3 H, CH₃), 4.08 (dd, J = 4, 12 Hz, 1 H, CH), 4.98–5.04 (m, 1 H, CH₂), 5.14–5.18 (m, 1 H, CH₂), 7.23–7.33 (m, 5 H, ArH) ppm.¹² HPLC: Daicel Chiralpak OD-H column, n-hexane/i-propanol = 95/5, 1 mL/min, 220 nm. Retention times: t _major = 15.747 min, t _minor = 26.280 min (minor diastereomer); t _major (S,R) = 19.040 min, t _minor = 27.487 min (major diastereomer).¹²

Supplementary Material

Supporting Information