Potassium tert-Butoxide Mediated Reductive C–P Cross-Coupling of Arylvinyl Sulfides through C–S Bond Cleavage

Abstract

A transition-metal-free t-BuOK-mediated reductive C–P cross-coupling reaction of arylvinyl sulfides with diarylphosphine oxides through C–S bond cleavage has been developed. This protocol not only permits the synthesis of diaryl(2-arylethyl)phosphine oxides, but also achieves an unprecedented construction of a C–P bond through C–S bond cleavage and reduction of a C–C double bond in one pot.

Key words

alkenyl sulfides - C–S bond cleavage - C–P bond formation - potassium butoxide - transition-metal-free synthesis

Publication History

Received: 18 August 2020

Accepted after revision: 08 September 2020

Article published online:
13 October 2020

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• 30 Trisubstituted Phosphine Oxides 3a–i; General Procedure An oven-dried standard 25 mL ground-mouth test tube equipped with a stirrer bar was charged with the appropriate disubstituted phosphine oxide 2 (2.0 mmol, 2.0 equiv), alkenyl sulfide 1 (1.0 mmol, 1.0 equiv), t-BuOK (2.5 mmol, 2.5 equiv), and toluene (12 mL). The test tube was sealed with a sleeve rubber stopper and then evacuated and refilled with argon for three cycles. The mixture was stirred at 120 °C for 24 h, then cooled to r.t. The mixture was diluted with EtOAc and washed with H₂O, and the aqueous layer was extracted with EtOAc (×3). The combined organic layer was dried (MgSO₄) and concentrated under vacuum on a rotary evaporator, and the residue was purified by column chromatography (silica gel, PE–EtOAc gradient).
• 31 [2-(3-Fluorophenyl)ethyl](diphenyl)phosphine Oxide (3e) White crystals; yield: 276 mg (85%); mp 101–102 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.81–7.67 (m, 4 H), 7.54–7.39 (m, 6 H), 7.22–7.11 (m, 1 H), 6.98–6.87 (m, 1 H), 6.87–6.78 (m, 2 H), 2.97–2.81 (m, 2 H), 2.60–2.47 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 162.84 (d, J _C–F = 246.0 Hz), 143.57 (dd, J _C–P = 15.2 Hz, J _C–F =7.2 Hz), 132.50 (d, J _C–P = 98.7 Hz), 131.88 (d, J _C–P = 2.7 Hz), 130.70 (d, J _C–P = 9.3 Hz), 130.03 (d, J _C–F = 8.3 Hz), 128.73 (d, J _C–P = 11.6 Hz), 123.73 (d, J _C–F = 2.8 Hz), 114.92 (d, J _C–F = 21.2 Hz), 113.19 (d, J _C–F = 21.0 Hz), 31.53 (d, J _C–P = 70.0 Hz), 27.30 (dd, J _C–P = 2.9, 1.8 Hz). ¹⁹F NMR (376 MHz, CDCl₃): δ = –113.15. ³¹P NMR (162 MHz, CDCl₃): δ = 31.22. HRMS (ESI-MS): m/z [M + Na]⁺ calcd for C₂₀H₁₈FNaOP: 347.0972; found: 347.0951.
• 32 [(6,6′-Difluorobiphenyl-2,2′-diyl)bis(ethane-2,1-diyl)]bis(diphenylphosphine) Dioxide (4) An oven-dried standard 25 mL ground-mouth test tube equipped with a stirrer bar was charged with phosphine oxide 3e (0.324 g, 1.0 mmol), (diacetoxyiodo)benzene (0.805 g, 2.5 mmol), I₂ (0.051 g, 0.2 mmol), p-toluenesulfonamide (0.034 g, 0.2 mmol), and DCE (5 mL). The test tube was sealed with a sleeve rubber stopper and then evacuated and refilled with argon for three cycles. The mixture was stirred at 60 °C for 10 h, then cooled to r.t. The reaction was quenched with aq Na₂S₂O₃, and the mixture was extracted with EtOAc and washed with H₂O. The aqueous layer was extracted with EtOAc (×3), and the combined organic layer was dried (MgSO₄) and concentrated in vacuum on a rotary evaporator. The residue was purified by column chromatography (silica gel, PE–EtOAc gradient) to give a white solid; 349 mg (54%); mp 101–102 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.86–7.73 (m, 8 H), 7.67 (dd, J = 8.7, 5.7 Hz, 2 H), 7.58–7.41 (m, 12 H), 6.96 (dd, J = 9.4, 3.0 Hz, 2 H), 6.62 (td, J = 8.3, 3.0 Hz, 2 H), 3.06–2.92 (m, 4 H), 2.54 (ddd, J = 10.8, 8.9, 4.7 Hz, 4 H). ¹³C NMR (101 MHz, CDCl₃): δ = 163.05 (d, J _C–F = 248.2 Hz), 145.84 (dd, J _C–P = 14.9 Hz, J _C–F =7.2 Hz), 140.55 (d, J _C–F = 7.8 Hz), 132.74 (s), 131.95 (d, J _C–F = 2.8 Hz), 131.75 (s), 130.84 (d, J _C–P = 9.5 Hz), 128.70 (d, J _C–P = 11.7 Hz), 116.83 (d, J _C–F = 22.2 Hz), 115.68 (d, J _C–F = 21.7 Hz), 32.97 (s), 30.10 (d, J _C–P = 69.4 Hz). ¹⁹F NMR (376 MHz, CDCl₃): δ = –113.56 to –113.67 (m). ³¹P NMR (162 MHz, CDCl₃): δ = 31.46 (s). HRMS (ESI-MS): m/z [M + Na + I₂]⁺ calcd for C₄₀H₃₄F₂I₂NaO₂P₂: 922.9984; found: 922.9956.