Compound (±)-5b

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InChIKey PFQLQDFVZBEURX-UHFFFAOYSA-N

Compound data: CIF

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

An oven-dried, two-necked, round-bottomed flask equipped with a magnetic stir bar was charged with (±)-3b (146 mg, 0.308 mmol) and NaBArF₂₄ (273 mg, 0.308 mmol, 1.00 equiv). The flask was evacuated, backfilled with argon (2 ×) and CH₂Cl₂ (5.0 mL) was added resulting in the formation of a white suspension. The reaction mixture was cooled to 0 °C (external temperature) using an ice/water bath, and PhSCl (35.0 μL, 0.304 mmol, 0.99 equiv) was added neat affording a brown, turbid solution. The mixture was stirred at 0 °C for 10 min and warmed to room temperature. Stirring was continued for 1 h during which the formation of a fine precipitate (NaCl) was observed. A second oven-dried, two-neck round-bottom flask was evacuated and backfilled with argon (1 ×) and used as a receiver flask for transferring the supernatant from the reaction flask. The transfer of the supernatant was accomplished using a syringe cannula. For that purpose, the end of the cannula (where usually the syringe is attached) was wrapped with a glass fiber filter (Fisher brand, G6), which was tied up with Teflon tape. This end was put into the reaction flask (without touching the suspension yet) and the sharp end was placed into the receiver flask. To moisten the glass fiber filter, CH₂Cl₂ (2.0 mL) was added to the receiver flask and transferred into the reaction flask. After this, the supernatant was transferred from the reaction flask into the receiver flask (by applying vacuum to the receiver flask). The reaction flask was rinsed with CH₂Cl₂ (2 × 3 mL) and the washings were transferred to the receiver flask. The cannula was removed from the receiver flask and the solvent was evaporated slowly (using the vacuum from the Schlenk line) to give a brown oil. Pentane (5.0 mL) was added and removed on high vacuum to give (±)-5b (399 mg, 90%) as a pale yellow, fluffy solid. Crystals suitable for single crystal X-ray diffraction were obtained by dissolving (±)-5b (120 mg) in CH₂Cl₂ (70 μL) followed by slow evaporation of the solvent at room temperature. ¹H NMR: (500 MHz, CDCl₃) δ 8.13 (d, J = 9.0 Hz, 1H, HC(4,4')), 8.05 (d, J = 9.0 Hz, 1H, HC(4',4)), 8.01 (d, J = 8.1 Hz, 1H, HC(6,6')), 7.93 (d, J = 8.1 Hz, 1H, HC(6',6)), 7.74 (d, J = 9.2 Hz, 1H, HC(aryl)), 7.75 (br s, 8H, HC(19)), 7.61–7.48 (m, 3H, HC(aryl)), 7.55 (br s, 4H, HC(21)), 7.39 (t, J = 7.7 Hz, 1H, HC(aryl)), 7.32 (t, J = 7.6 Hz, 1H, HC(aryl)), 7.19 (t, J = 7.5 Hz, 1H, HC(aryl)), 7.12 (t, J = 8.4 Hz, 2H, HC(aryl)), 7.03 (t, J = 7.8 Hz, 2H, HC(aryl)), 6.71 (d, J = 7.8 Hz, 2H, HC(aryl)), 3.72–3.57 (m, 2H, HC(16), HC(16')), 3.33 (d, J = 13.4 Hz, 3H, HC(11,11')), 2.69 (d, J = 13.2 Hz, 3H, HC(11',11)), 1.32 (d, J = 6.8 Hz, 6H, HC(17,17')), 1.30 (d, J = 6.9 Hz, 6H, HC(18,18')); ¹³C NMR: (125 MHz, CDCl₃); δ 161.8 (q, J = 49.9 Hz, (C(20)), 138.7 (C(aryl)), 137.4 (C(aryl)), 134.8 (C(aryl)), 134.2 (C(aryl)), 132.8 (C(aryl)), 132.6 (C(aryl)), 132.5 (C(aryl)), 132.1 (C(aryl)), 131.8 (C(aryl)), 131.6 (C(aryl)), 131.5 (C(aryl)), 131.4 (C(aryl)), 130.6 (C(aryl)), 129.7 (C(aryl)), 128.9 (qq, J = 32.8, 2.9 Hz, C(19)), 128.6 (C(aryl)), 128.4 (C(aryl)), 127.9 (C(aryl)), 127.6 (C(aryl)), 127.2 (C(aryl)), 125.7 (C(aryl)), 124.6 (q, J = 272 Hz, C(22)), 122.3 (C(aryl)), 120.4 (C(aryl)), 117.5 (C(aryl)), 50.5 (C(16), C(16')), 37.9 (br s, (C(11,11')), 37.7 (d, J = 11.0 Hz, C(11',11)), 23.8 (C(17)), 23.0 (C(18)); ³¹P NMR: (202 MHz, CDCl₃) δ 65.8