Catalytic Asymmetric Ring-Opening of σ-Symmetric Cyclic Carbonates with Chiral Brønsted Acid Catalysts

Abstract

Enantioselective ring-opening of σ-symmetric six-membered cyclic carbonates with benzyl alcohol catalyzed by BINOL-based chiral phosphoric acids was achieved in up to 81% enantiomeric excess at 5 mol% catalyst loading.

Key words

ring opening - cyclic carbonate - Brønsted acid - phosphoric acid - asymmetric synthesis - organocatalyst

• References and Notes


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Chiral Brønsted acids 3a–e, 3g, 3h, and 3j–l were prepared according to previously reported methods. Catalysts 3f and 3i were purchased from a commercial source.
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• 14 Catalytic Asymmetric Ring-Opening of Cyclic Carbonates; Typical Procedure: To a solution of cyclic carbonate 1c (33.9 mg, 0.1 mmol) and chiral Brønsted acid catalyst 3k (4.1 mg, 0.005 mmol) in CH₂Cl₂ (1 mL), was added BnOH (52 μL, 0.5 mmol) at r.t. After stirring at r.t. for 20 h, the reaction mixture was treated with sat. aq NaHCO₃ (2 mL) followed by extraction with CHCl₃ (24 mL). The extract was dried over anhydrous MgSO₄, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (n-hexane–EtOAc, 1:1) to afford acylic carbonate 2c (41.8 mg, 94% yield, 81% ee) as a white solid. The ee of 2c was determined by HPLC analysis on a Chiralpak AD-H column (n-hexane–EtOH, 1:1; flow rate = 1 mL/min; detection = 254 nm). The retention times were 9.2 min (minor product) and 11.9 min (major product).
• 15 Spectroscopic Data of 2c: White solid; mp 81.0–82.5 °C; [α]_D ²⁷ –4.3 (c 1.02, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 2.20 (br. s, 1 H), 3.60–3.78 (m, 2 H), 3.91–4.01 (m, 1 H), 4.20 (t, J = 6.7 Hz, 1 H), 4.23–4.36 (m, 2 H), 4.42 (d, J = 6.4 Hz, 2 H), 5.15–5.23 (m, 1 H), 5.17 (s, 2 H), 7.31 (dt, J = 1.1, 7.5 Hz, 2 H), 7.33–7.42 (m, 7 H), 7.57 (d, J = 7.5 Hz, 2 H), 7.76 (d, J = 7.6 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 47.2, 51.5, 61.5, 66.3, 67.0, 70.2, 120.0, 125.0, 127.1, 127.7, 128.5, 128.7, 128.8, 134.8, 141.3, 143.78, 143.81, 155.3, 156.2. IR (KBr): 3322, 2960, 1744, 1692, 1538, 1270 cm^–1. MS (ESI): m/z [M⁺ + Na] calcd for C₂₆H₂₅NNaO₆: 470.1580; found: 470.1583.