Allylpalladium(II) Chloride Dimer

Typical Procedure:
Substrate (0.1 mmol), [Pd(allyl)Cl]₂ (1.8 mg, 0.005 mmol), tris[3,5-bis(trifluoromethyl)phenyl]phosphine (13.4 mg, 0.02 mmol), O-benzoyl hydroxylamine (0.4 mmol), 4Å molecular sieves (50 mg), and Cs₂CO₃ (130 mg, 0.4 mmol) are weighed in air and placed in a Schlenk tube (50 mL) with a magnetic stir bar. The reaction vessel is evacuated and backfilled with nitrogen (×3), and DCM (1.5 mL) is added afterwards. The reaction mixture is heated to 120 °C for 16 hours under vigorous stirring. Upon completion, the reaction mixture is cooled to room temperature. The solvents are removed under reduced pressure and the resulting mixture is purified by a silica gel-packed flash chromatography column using hexane/EtOAc/DCM mixtures as the eluent.

Typical procedure (Step 3, Ar³ = Ph, R = H): A glass vessel is flame-dried under vacuum and filled with argon after cooling to room temperature. To the glass vessel are added [PdCl(allyl)]₂ (5.5 mg, 30 µmol), SIPr⋅HCl (12.8 mg, 30 µmol), dry dioxane (0.75 mL), and 1M NaOH aq. solution (0.9 mL, 0.9 mmol). After stirring the mixture at this temperature for 30 min, diphenylmethyl phenyl sulfone (92.4 mg, 0.3 mmol), phenylboronic acid (73.2 mg, 0.6 mmol), and dry dioxane (0.75 mL) are added, and then the vessel is sealed. The mixture is stirred at 120 °C for 12 h. After cooling to room temperature, the mixture is passed through a pad of silica gel washed with EtOAc (~20 mL). The filtrate is concentrated under reduced pressure. The crude product is purified by PTLC (eluent: hexane) to afford triphenylmethane (66 mg, 90%) as a white solid.

Typical Procedure:
A THF solution of TASF (1.0 M solution, 0.40 mL, 0.40 mmol) is added to trimethylvinylsilane (40 mg, 0.40 mmol) and allylpalladium chloride dimer (2.7 mg, 0.0075 mmol) dissolved in HMPA (0.3 mL) at 0 °C under an argon atmosphere. 1-Iodonaphthalene (76 mg, 0.30 mmol) is injected to the resulting solution, and the mixture is stirred at 50 °C for 2 h. After completion of the reaction, the bulk of the solvent is removed by passing the reaction mixture through a silica gel column with pentane as the eluent. Evaporation of the pentane under reduced pressure gives pure 1-vinylnaphthalene (42 mg, Y. 98%).