Multiple Activation Catalyst for Asymmetric [4+2] Cycloaddition of Aldehydes with Dienes

Abstract

The enantioselective oxa-Diels–Alder reaction of nonactivated substrates by utilizing FeCl₃ and a 1,1′-bi-2-naphthol (BINOL) derived chiral phosphoric acid as a multiple activation catalyst is reported. Various oxygen-containing six-membered heterocycles were obtained in high yields and in an enantioselective manner. Density functional theory (DFT) calculations elucidate that both Lewis acidic and Brønsted acidic moieties in the catalyst system synergistically activate two lone pairs of an aldehyde to facilitate enantioselective addition reaction of dienes.

Key words

operando XAFS - DFT - iron - asymmetric cycloaddition - Diels–Alder

Publication History

Received: 15 July 2021

Accepted after revision: 25 August 2021

Article published online:
09 September 2021

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• 13 General Procedure for the Synthesis of 4aa The reaction was performed in a 15 mL sealed tube equipped with a Teflon-coated magnetic stirrer bar. In a glove box, FeCl₃ (0.0075 mmol, 5 mol%) and chiral phosphoric acid (0.00375 mmol, 2.5 mol%) were stirred in toluene (1 mL) at –50 °C. After FeCl₃ was dissolved completely, aldehydes (0.15 mmol) were added and stirred for a while, then dienes (0.3 mmol) were added to a solution. After the reaction mixture was stirred at –50 °C for the indicated time, the solution was passed through a short silica gel pad, washed with ethyl acetate, and concentrated in vacuo. The crude product was purified by silica gel column chromatography with hexanes–EtOAc as eluent to afford the desired products 4aa. Compound 4aa: yield 53%, 66% ee, white solid; [α]_D ²³ +25.8 (c 0.83, CH₂Cl₂); mp 83–84 °C (hexane). TLC: R_f = 0.25 (hexane/ethyl acetate = 30:1). ¹H NMR (500 MHz CDCl₃): δ = 7.84–7.92 (m, 4 H), 7.57 (dd, J = 8.4, 1.5 Hz, 1 H), 7.47–7.50 (m, 2 H), 7.42–7.55 (m, 2 H), 7.33–7.39 (m, 2 H), 7.28 (dt, J = 7.0, 1.5 Hz, 1 H), 6.24–6.28 (m, 1 H), 4.85 (dd, J = 9.5, 4.5 Hz, 1 H), 4.55–4.67 (m, 2 H), 2.73–2.85 (m, 2 H). ¹³C NMR (125.7 MHz CDCl₃): δ = 140.0, 139.7, 134.4, 133.3, 132.9, 128.5, 128.2, 128.0, 127.7, 127.4, 126.1, 125.8, 124.8, 124.5, 124.1, 122.2, 76.0, 66.9, 35.9. IR (KBr): 2824, 1600, 1446, 1372, 1119, 826, 752, 693 cm^–1. HRMS (ESI⁺): m/z calcd for [M + H]⁺: 285.1285; found: 285.1278. HPLC (Daicel Chiralpak IB, hexane/i-PrOH = 98.5:1.5, flow rate = 1.0 mL/min, λ = 254 nm, 40 °C): t _R (minor) = 13.1 min, t _R (major) = 16.0 min.