Catalytic Enantioselective Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones and Vinyl Selenides

Abstract

We report an asymmetric inverse-electron-demand Diels–Alder reaction of electron-deficient 2-pyrones with various phenyl vinyl selenides catalyzed by a chiral bis(oxazoline)/Cu(OTf)₂ complex. By using a side-arm-modified chiral bis(oxazoline)ligand, a variety of [2,2,2]-bicyclic lactones with phenyl selenide substituents were obtained in good to excellent yields (up to 99%) and enantioselectivities (up to 98% ee) under mild conditions. Based on this strategy, a highly concise enantioselective synthesis of the Corey lactone was accomplished.

Key words

asymmetric catalysis - inverse-electron-demand Diels–­Alder reaction - pyrones - phenyl vinyl selenides - Corey lactone

Publication History

Received: 09 November 2022

Accepted after revision: 30 November 2022

Accepted Manuscript online:
30 November 2022

Article published online:
12 January 2023

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• 33 Methyl 3-Oxo-8-(phenylselanyl)-2-oxabicyclo[2.2.2]oct-5-ene-4-carboxylate (3a); Typical Procedure A mixture of Cu(OTf)₂ (3.6 mg, 0.01 mmol), L11 (5.7 mg, 0.012 mmol), and freshly activated 3 Å MS (25.0 mg) in m-xylene (0.5 mL) was stirred at 25 °C for 2 h. The 2-pyrone 1a (0.2 mmol) was then added, and the mixture was stirred for 15 min before vinyl phenyl selenide (2a; 0.3 mmol) was added in one portion. When 1 was fully consumed (TLC; 4 h), the mixture was purified directly by flash column chromatography (silica gel) to give a white solid; yield: 64.7 mg (97%, 95% ee); [α]_D ²⁶ −84.70 (c 1.0, CHCl₃). HPLC [CHIRALPAK IB N-5, hexane–i-PrOH (90:10), 1.0 mL/min, λ = 210 nm, 25 °C]: t _R (minor) = 21.8 min; t _R (major) = 19.5 min. FTIR (neat): 3061, 2945, 1732, 1576, 1476, 1437, 1366, 1352, 1327, 1288, 1275, 1086, 1016, 891, 797, 735, 588 cm⁻¹. ¹H NMR (400 MHz, CDCl₃): δ = 7.56–7.54 (m, 2 H), 7.34–7.27 (m, 3 H), 6.95 (d, J = 7.6 Hz, 1 H), 6.56 (dd, J = 7.6, 5.2 Hz, 1 H), 5.26–5.24 (m, 1 H), 3.95 (dd, J = 9.2, 3.2 Hz, 1 H), 3.57 (s, 3 H), 2.95–2.88 (m, 1 H), 1.99–1.94 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 169.1, 167.2, 135.4, 131.9, 131.4, 129.3, 128.7, 128.6, 74.3, 60.1, 52.7, 37.2, 36.3. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₅O₄Se: 339.0130; found: 339.0131.