Synthesis of Novel C ₂-Symmetric Sulfur-Based Catalysts: Asymmetric Formation of Halo- and Seleno-Functionalized Normal- and Medium-Sized Rings

Published as part of the Cluster Organosulfur and Organoselenium Compounds in Catalysis

Abstract

The synthesis of novel, highly functionalized, C ₂-symmetric sulfur-based catalysts is developed and their catalytic applications are explored in asymmetric bromo-, iodo- and seleno-functionalizations of alkenoic acids. This protocol provides the corresponding normal- and medium-sized bromo, iodo and selenolactones in up to 98% yield and 83% stereoselectivity.

Key words

alkenoic acids - organosulfur catalysts - asymmetric catalysis - halolactones - selenolactones

• References and Notes

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• 19 Catalyst Preparation To a stirred solution of 2,5-thiophenedicarbonyl dichloride (1.0 equiv, 1.0 mmol, 209 mg) in CH₂Cl₂ (20 mL) at 0 °C were added dropwise the alkyl derivative of the cinchona alkaloid (2.1 equiv, 2.1 mmol) and Et₃N (4.0 equiv, 4.0 mmol) in CH₂Cl₂ (15 mL) using a dropping funnel. After the addition was complete, the mixture was stirred for 6 h at 0 °C to room temperature. After completion of the reaction, saturated NaHCO₃ solution (20 mL) was added to the mixture. The resulting solution was extracted with CH₂Cl₂ (3 × 20 mL) and the combined organic layer washed with brine (20 mL), dried over Na₂SO₄ and concentrated on a rotary evaporator under vacuum. The resulting solid was purified by column chromatography with CH₂Cl₂/MeOH (10:1). 2-{(1S)-(6-Butoxyquinolin-4-yl)[(2S)-5-ethylquinuclidin-2-yl]methyl} 5-{(1S)-(6-Butoxyquinolin-4-yl)[(2S,4S,5R)-5-ethylquinuclidin-2-yl]methyl} Thiophene-2,5-dicarboxylate (Cat 5) White solid; yield: 576 mg (66%); mp 147–150 °C; [α]_D ¹⁹.⁴ +24.9 (c 0.33, CHCl₃). IR (plate): 1722, 1715, 1620, 1596, 1530, 1507, 1462, 1448, 1362, 1320, 1241 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.69 (d, J = 4.49 Hz, 2 H), 8.00 (d, J = 9.15 Hz, 2 H), 7.79 (s, 2 H), 7.41–7.35 (m, 6 H), 6.67 (d, J = 1.48 Hz, 2 H), 4.17–4.08 (m, 4 H), 3.43–3.38 (m, 2 H), 3.06 (q, J = 12.64 Hz, 2 H), 2.69–2.64 (m, 2 H), 2.36 (d, J = 12.96 Hz, 2 H), 1.87–1.71 (m, 12 H), 1.66–1.62 (m, 2 H), 1.58–1.49 (m, 6 H), 1.45–1.40 (m, 2 H), 1.37–1.25 (m, 4 H), 0.98 (t, J = 7.35 Hz, 6 H), 0.83 (t, J = 7.25 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 160.3, 157.7, 147.2, 144.6, 142.8, 138.8, 133.7, 131.8, 126.7, 122.4, 118.3, 101.8, 75.7, 68.1, 59.0, 58.5, 42.8, 37.3, 31.2, 28.5, 27.7, 25.3, 23.6, 19.3, 13.8, 12.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₅₂H₆₄N₄O₆S: 873.4618; found: 873.4619. Halolactones 2 and 3 To a solution of alkenoic acid (1.0 equiv, 0.1 mmol) and catalyst cat 5 (0.05 equiv, 0.005 mmol, 4.6 mg) in a mixture of CHCl₃ (2 mL) and hexane (4 mL) at –78 °C in the dark under N₂ was added N-bromosuccinimide (NBS) (1.2 equiv, 0.12 mmol, 21 mg) or N-iodosuccinimide (NIS). The resulting mixture was stirred at –78 °C and the reaction progress monitored by TLC. After completion, the reaction was quenched with saturated Na₂SO₃ (2 mL) at –78 °C and then warmed to room temperature. The solution was diluted with H₂O (3 mL) and extracted with CH₂Cl₂ (3 × 5 mL). The combined extracts were washed with brine (5 mL), dried over Na₂SO₄, filtered and concentrated in vacuo. The residue was purified by column chromatography using hexane/EtOAc to yield the corresponding halolactone. (R)-5-(Bromomethyl)-5-phenyldihydrofuran-2(3H)-one (2a) Colorless oil; yield: 24.7 mg (97%); [α]_D ²⁰.⁵ –13.95 (c 0.66, CHCl₃); 83% ee. ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.32 (m, 5 H), 3.72 (d, J = 11.31 Hz, 1 H), 3.67 (d, J = 11.31 Hz, 1 H), 2.85–2.74 (m, 2 H), 2.58–2.47 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 175.5, 140.7, 128.8, 128.6, 124.9, 86.4, 41.0, 32.3, 29.0. HPLC (Daicel ChiralPak IC-3, i-PrOH/hexane = 25:75, 0.6 mL/min, 214 nm): t ₁ = 21.8 (minor), t ₂ = 25.0 (major). 3-(Bromomethyl)-4,5-dihydrobenzo[c]oxepin-1(3H)-one (3a) White semi-solid; yield: 20.7 mg (81%); [α]_D ²⁶.¹ –3.5 (c 0.2, CHCl₃); racemic. ¹H NMR (400 MHz, CDCl₃): δ = 7.70 (dd, J = 7.5, 0.7 Hz, 1 H), 7.47 (td, J = 7.5, 1.1 Hz, 1 H), 7.35 (t, J = 7.5 Hz, 1 H), 7.20 (d, J = 7.5 Hz, 1 H), 4.30–4.17 (m, 1 H), 3.55 (dd, J = 10.8, 6.1 Hz, 1 H), 3.47 (dd, J = 10.8, 5.4 Hz, 1 H), 3.05–2.95 (m, 1 H), 2.83–2.75 (m, 1 H), 2.20–2.10 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.4, 137.7, 133.0, 131.2, 130.3, 128.8, 127.6, 77.1, 32.8, 32.6, 29.4. HPLC (Daicel ChiralPak IC-3, i-PrOH/hexane = 25:85, 0.6 mL/min, 214 nm): t ₁ = 25.0 (minor), t ₂ = 29.1 (major).