Enantioselective Heterogeneous Heck–Matsuda Reaction with Polymer-Supported PyOx Ligands

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 resin

• References and Notes

• 1 Current addresses: Institute of Low Temperature and Structure Research, Polish Academy of Sciences ul. Okólna 2, 50-422 Wrocław Poland and Departamento de Química Fundamental, Universidade Federal de Pernambuco, Recife, Brazil.
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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.