Preparation of Aryl(dicyclohexyl)phosphines by C–P Bond-Forming Cross-Coupling in Water Catalyzed by an Amphiphilic-Resin-Supported Palladium Complex

^◊ Visiting scientist from KANEKA corporation
Dedicated to Professor Victor A. Snieckus on the occasion of his 80^th birthday

Abstract

Aryl(dicyclohexyl)phosphines were prepared by a catalytic C–P bond-forming cross-coupling reaction of haloarenes with dicyclohexylphosphine under heterogeneous conditions in water containing an immobilized palladium complex coordinated to an amphiphilic polystyrene–poly(ethylene glycol) resin supported di(tert-butyl)phosphine ligand.

Key words

phosphines - haloarenes - C–P bond - cross-coupling - aqueous media - polymer support - palladium

• References and Notes


For recent reviews on C–P cross coupling, see:
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For studies on cross-coupling in water with polymeric palladium complexes from the author’s group (selected publications), see for Suzuki–Miyaura coupling:
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Heck reaction:
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Sonogashira reaction:
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Asymmetric alkylation:
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Asymmetric cross-coupling:
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Sonogashira coupling:
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Allylic arylation:
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Suzuki–Miyaura coupling:
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Heck reaction:
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Hiyama coupling:
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Asymmetric C–C coupling:
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For recent reviews on heterogeneous-switching of transition-metal catalysis, see:
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• 12 General Procedure for the Catalytic Phosphinylation of Haloarenes A mixture of L1 (480 mg, 0.10 mmol of P), [PdCl(η³-C₃H₅)]₂ (9 mg, 0.025 mmol), arylhalides (1, 0.55 mmol), and dicyclohexylphosphine (2, 99 mg, 0.50 mmol) in 20 M KOH aqueous solution (0.5–1.0 mL) under nitrogen atmosphere was agitated with shaking for several hours upon heating at 100 °C. After being cooled, the reaction mixture was filtered, and the aqueous filtrate was extracted with degassed toluene (2 × 2 mL). Recovered catalyst resin beads were extracted with degassed toluene (4 × 2 mL). The combined extract was dried over anhydrous Na₂SO₄ and concentrated in vacuo to give a crude residue. The residue was purified by silica gel flash chromatography (eluent: degassed n-hexane/Et₂O = 10:0 to 9:1) to give an aryldicyclohexylphosphine 3. Selected Data Dicyclohexylphenylphosphine (3a; Table 1 Entry 1) CAS: 6476-37-5; yellow oil; 123 mg (90% yield). ¹H NMR (500 MHz, CDCl₃, 25 °C): δ = 7.37–7.42 (m, 2 H), 7.25–7.27 (m, 3 H), 1.51–1.86 (m, 12 H), 0.88–1.29 (m, 10 H). MS (ESI⁺): m/z = 274 [M⁺]. 2-(Dicyclohexylphosphine)biphenyl (3p; Scheme 4) CAS: 247940-06-3; colorless solid; 142 mg (81% yield); mp 78–80 °C. ¹H NMR (500 MHz, CDCl₃, 25 °C): δ = 7.58–7.60 (m, 1 H), 7.25–7.38 (m, 8 H), 1.55–1.84 (m, 12 H), 1.00–1.27 (m, 10 H). MS (ESI⁺): m/z = 350 [M⁺].
• 13 Compound 3p (CAS : 247940-06-3): Kendall AJ. Zakharov LN. Tyler DR. Inorg. Chem. 2016; 55: 3079 ; and references cited therein
• 14 Compound 3q (CAS 180260-74-6): Ikeda R. Kuwano R. Chem. Eur. J. 2016; 25: 8610 ; and references cited therein
• 15 Because of the unique reactivity as well as the coordinating ability of the substrates (R₂PH) and the products (R₂ArP), thorough condition screening should be required for each individual substrate. Thus, for examples, the coupling of Ph₂PH and t-Bu₂PH with PhBr gave only 33% and <10% of the products, Ph₃P and t-Bu₂PhP, respectively, under the present conditions.