Compound C1-1a

(t-BuXantphos)Pd(CF2H)(Ph4B5O6)

From: Controllable catalytic difluorocarbene transfer enables access to diversified fluoroalkylated arenes

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Compound data: Crystallographic data

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

To a solution of palladium difluorocarbene complex A1-1 (0.05 mmol, 32.8 mg, 1.0 equiv) in degassed anhydrous 1,4-dioxane (2.5 mL) was added PhB(OH)2 (0.1 mmol, 2.0 equiv) under Ar. The resulting mixture was stirred at room temperature for 5 min. The reaction mixture was filtered by Celite. The filtrate was evaporated and the residue was washed by Et2O several times to provide a mixture of cationic difluoromethyl palladium complexes C1-1 (full conversion, determined by 19F NMR) with counter anions as pentaborate monoanion (C1-1a) or other polyborate anions. Complex C1-1 of C1-1a was separated from the mixture and characterized by its X-ray crystal structure (Supplementary Figure 1). 1H NMR (400 MHz, THF) δ 8.09 – 8.03 (m, 2 H, t-Bu-Xantphos), 8.03 – 7.96 (m, 2 H, t-Bu-Xantphos), 7.93 (m, 3 H, phenyl boronate), 7.77 (tt, J = 52.0, 12.0 Hz, 1 H, CF2H), 7.55 (t, J = 7.8 Hz, 2 H, t-Bu-Xantphos), 7.28 – 7.09 (m, 6.5 H, phenyl boronate), 6.95 (t, J = 7.2 Hz,1 H, phenyl boronate), 6.84 – 6.81 (m, 0.5 H, phenyl boronate), 1.63 (s, 6 H, t-Bu-Xantphos), 1.48 (d, J = 8.0 Hz 18 H, t-Bu-Xantphos), 1.46 (d, J = 8.0 Hz 18 H, t-Bu-Xantphos). 19F NMR (376 MHz, CDCl3) δ -65.0 (dt, J = 54.0 Hz, 28.2 Hz, 2 F). 31P NMR (162 MHz, CDCl3) δ 47.7 (t, J = 28.1 Hz, 2 P). Sample for the X-ray crystal structure analysis was recrystallized from CHCl3/Et2O.