Nickel-Catalyzed Asymmetric Arylation of H-Phosphinates

Abstract

An asymmetric arylation of H-phosphinates with aromatic iodo or bromo compounds, catalyzed by cheap and easily available nickel(II) salts, provides access to P-stereogenic phosphinates. This method features mild reaction conditions and a good functional-group compatibility that includes aniline and phenol derivatives.

Key words

phosphinates - P-stereogenic centers - phosphinates - nickel catalysis - cross-coupling - asymmetric catalysis

Publication History

Received: 18 March 2023

Accepted after revision: 19 April 2023

Article published online:
22 May 2023

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• 13 Diaryl Phosphinates 1–30; General Procedure In a N₂-flushed glovebox, a 4 mL vial equipped with a stirrer bar was charged with Ni(acac)₂ (2.8 mg, 10 mol%), ligand L2 (4.0 mg, 12 mol%), PhCO₂K (32.0 mg, 2.0 equiv), Zn powder (7.8 mg, 1.2 equiv), and EtOAc (0.5 mL), and the mixture was stirred for 10 min. The appropriate H-phosphinate (0.2 mmol) and aryl iodide (0.1 mmol) were added to the vial, which was then capped and removed from the glovebox. The mixture was stirred for 48 h at rt, then purified directly by preparative TLC. Isopropyl (R)-Phenyl(4-tolyl)phosphinate (3) Colorless solid; yield: 25.8 mg (94%, 85% ee); [α]_D ²⁰ –3.24 (c = 0.21, acetone). HPLC [Daicel Chiralcel AD-H, hexane–i-PrOH (90:10), 1 mL/min, λ = 254 nm]: t _R (major) = 12.17 min, t _R (minor) = 13.49 min. ¹H NMR (400 MHz, CDCl₃): δ = 7.84–7.76 (m, 2 H), 7.75–7.66 (m, 2 H), 7.52–7.46 (m, 1 H), 7.45–7.39 (m, 2 H), 7.25 (dd, J = 8.1, 3.4 Hz, 2 H), 4.72–4.59 (m, 1 H), 2.38 (s, 3 H), 1.34 (dd, J = 6.2, 3.5 Hz, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 142.5 (d, J = 3.1 Hz), 132.6 (d, J = 137.7 Hz), 131.8 (d, J = 2.9 Hz), 131.7 (d, J = 10.5 Hz), 131.5 (d, J = 10.1 Hz), 129.2 (d, J = 13.4 Hz), 128.9 (d, J = 139.9 Hz), 128.3 (d, J = 13.2 Hz), 70.1 (d, J = 5.9 Hz), 24.3, 21.6. ³¹P NMR (162 MHz, CDCl₃): δ = 30.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₆H₁₉NaO₂P: 297.1015; found: 297.1021 (S)-Isopropyl(phenyl)(4-tolyl)phosphine Oxide (17) Colorless solid; yield: 13.5 mg (52%; 84% ee); [α]_D ²⁰ –12.0 (c = 0.22, acetone). HPLC [Daicel Chiralcel AY-H (84% ee), hexane–i-PrOH (80:20), 1 mL/min, λ = 254 nm]: t _R (major) = 10.58 min, t _R (minor) = 11.45 min. ¹H NMR (500 MHz, CDCl₃): δ = 7.81–7.73 (m, 2 H), 7.67 (dd, J = 10.6, 7.9 Hz, 2 H), 7.52–7.42 (m, 3 H), 7.30–7.25 (m, 2 H), 2.57–2.46 (m, 1 H), 2.39 (s, 3 H), 1.21–1.14 (m, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 141.9 (d, J = 2.8 Hz), 132.4 (d, J = 94.7 Hz), 131.4 (d, J = 2.7 Hz), 131.0 (d, J = 8.2 Hz), 131.0 (d, J = 8.2 Hz), 129.3 (d, J = 11.5 Hz), 128.7 (d, J = 97.1 Hz), 128.5 (d, J = 11.2 Hz), 27.1 (d, J = 73.0 Hz), 21.5, 15.3 (d, J = 2.2 Hz), 15.2 (d, J = 2.2 Hz). ³¹P NMR (202 MHz, CDCl₃): δ = 37.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₂₀OP: 259.1246; found: 259.1256. 4-[Isopropoxy(phenyl)phosphoryl]phenyl 2-(4-Isobutylphenyl)propanoate (29) Colorless solid; yield: 26.9 mg (58%); [α]_D ²⁰ –0.708 (c = 0.24, acetone). ¹H NMR (400 MHz, CDCl₃): δ = 7.78 (ddd, J = 12.5, 8.0, 6.2 Hz, 4 H), 7.50 (t, J = 7.5 Hz, 1 H), 7.43 (dd, J = 7.7, 3.4 Hz, 2 H), 7.28 (s, 2 H), 7.13 (d, J = 7.8 Hz, 2 H), 7.08 (dd, J = 8.6, 2.6 Hz, 2 H), 4.65 (tt, J = 12.9, 5.9 Hz, 1 H), 3.93 (q, J = 7.1 Hz, 1 H), 2.46 (d, J = 7.2 Hz, 2 H), 1.85 (dq, J = 13.4, 6.7 Hz, 1 H), 1.59 (d, J = 7.1 Hz, 3 H), 1.33 (t, J = 5.7 Hz, 6 H), 0.90 (d, J = 6.6 Hz, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 172.7, 153.7 (d, J = 3.3 Hz), 141.0, 136.8, 133.1 (d, J = 11.1 Hz), 132.1 (d, J = 138.6 Hz), 132.0 (d, J = 3.0 Hz), 131.5 (d, J = 10.1 Hz), 129.7 (d, J = 139.2 Hz), 129.6, 128.4 (d, J = 13.1 Hz), 127.1, 121.6 (d, J = 14.0 Hz), 70.4 (d, J = 6.0 Hz), 45.2, 45.0, 30.2, 24.3 (d, J = 3.7 Hz), 22.4, 18.4. ³¹P NMR (202 MHz, CDCl₃): δ = 29.1. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₃₄O₄P: 465.2189; found: 465.2194. Diisopropyl (R,R)-1,4-Phenylenebis[phenyl(phosphinate)] (30) Colorless solid; yield: 21.6 mg (49%, 95% ee); [α]_D ²⁰ –1.35 (c = 0.51, acetone).HPLC [Daicel Chiralcel AD-H, hexane–i-PrOH (70:30), 1 mL/min, λ = 254 nm]: t _R (major) = 15.94 min, t _R (minor) = 9.33 min. ¹H NMR (500 MHz, CDCl₃): δ = 7.89–7.84 (m, 4 H), 7.83–7.77 (m, 4 H), 7.55–7.50 (m, 2 H), 7.47–7.41 (m, 4 H), 4.72–4.62 (m, 2 H), 1.35 (dd, J = 6.2, 4.8 Hz, 12 H). ³¹P NMR (202 MHz, CDCl₃): δ = 28.5. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₄H₂₈NaO₄P₂: 465.1355; found: 465.1360.