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Synlett 2024; 35(10): 1135-1140
DOI: 10.1055/a-2284-5030
DOI: 10.1055/a-2284-5030
cluster
Thieme Chemistry Journals Awardees 2023
Enantioselective Heterogeneous Heck–Matsuda Reaction with Polymer-Supported PyOx Ligands
The authors gratefully acknowledge financial support from the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) (São Paulo Research Foundation) [2014/25770-6 (to C.R.D.C.), 2015/07773-0 (to R.L.O.), 2021/06661-5 (to J.C.P.), 2023/07466-7 (to R.C.S.)], the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (Brazilian National Council for Scientific and Technological Development) [308540/2021-2 (to J.C.P.)], and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) (Coordination for the Improvement of Higher Education Personnel) [Finance Code 001 (to C.L.H.)].
Abstract
Carboxymethyl C5-functionalized pyridine-oxazoline (PyOx) ligands are immobilized onto Merrifield and Wang resins utilizing three distinct strategies. The immobilized PyOx ligands are employed in the Pd-catalyzed heterogeneous Heck–Matsuda reaction for the desymmetrization of 3-cyclopenten-1-ol, resulting in the production of 20 examples of aryl-penten-1-ols with yields reaching up to 87%, and enantiomeric ratios ranging between 90:10 and 99:1. These outcomes align with those achieved by the homogeneous counterparts, demonstrating comparable efficiency. Subsequent recycling analysis reveals a progressive decline in catalyst efficiency upon reuse, suggesting the formation of palladium black on the catalyst surface.
Key words
heterogeneous catalysis - enantioselective Heck–Matsuda - pyridine-oxazoline - polymer-supported ligand - Merrifield resinSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2284-5030.
- Supporting Information
Publication History
Received: 09 February 2024
Accepted after revision: 10 March 2024
Accepted Manuscript online:
10 March 2024
Article published online:
28 March 2024
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References and Notes
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- 30 The immobilized ligand (0.02 mmol, 0.2 eq.) and the solvent (2 mL) were added to a 4 mL vial. The suspension was stirred for 30 min at room temperature and then Pd(TFA)2 (3.32 mg, 0.01 mmol, 0.1 eq.) was added and the mixture was stirred for 90 min. Next, DTBMP (22.6 mg, 0.11 mmol, 1.1 eq.), cyclopenten-1-ol (1) (15.8 μL, 0.2 mmol, 2 eq.) and the arenediazonium salt 2 were added. After 2 h, the reaction mixture was decanted. The supernatant was removed with a pipette, filtered through a short silica gel pad (eluting with EtOAc), and the solvent was removed under reduced pressure. The residue was purified by preparative TLC (EtOAc/n-hexanes) to provide the desired Heck–Matsuda adduct. For example, compound 3a was obtained as yellow oil in 86% yield and 95:5 er. [α]D 20 +142 (c = 1.1, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 7.20–7.07 (m, 2 H), 6.90–6.79 (m, 2 H), 5.94 (tdd, J = 7.2 Hz, 3.6 Hz, 1.8 Hz, 2 H), 4.97–4.86 (m, 1 H), 3.79 (s, 3 H), 3.77–3.71 (m, 1 H), 2.83 (ddd, J = 13.7 Hz, 6.1 Hz, 5.3 Hz, 1 H), 1.62 (br s, 1 H), 1.54 (ddd, J = 13.7 Hz, 6.1 Hz, 5.3 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 158.3, 137.9, 137.4, 134.3, 128.4, 114.1, 77.6, 55.4, 49.2, 44.2. FTIR (ATR): 3337 (br), 2935, 2836, 1516, 1445, 1070, 1000, 815, 748 cm–1.