Compound 4

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InChIKey WWHRYPVJLKBLTR-NKSGRRHRSA-M

Compound data: CIF

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

A mixture of 3a (200 mg, 0.16 mmol) and NaSH (90 mg, 1.6 mmol) in dichloromethane (10 mL) was stirred at room temperature for five hours in air. The reaction mixture was filtered to remove the solid, and the volume of the filtrate was reduced to approximately 2 mL under vacuum. Then purified by column chromatography (neutral alumina, eluent: dichloromethane/acetone = 5:1) to give a blue solution. The blue solid of 4 (153 mg, 75%) was collected after the solvent was evaporated to dryness under vacuum. ¹H-NMR plus ¹H-¹³C HSQC (500.1 MHz, CD₂Cl₂): δ 13.56 (d, J_P-H = 14.5 Hz, 1H, H¹), 8.43 (s, 1H, H⁵), 8.29 (s, 1H, H³), 3.47 (s, 3H, COOCH₃), 7.82–6.93 ppm (m, 45H, other aromatic protons). ³¹P-NMR (202.5 MHz, CD₂Cl₂): δ 12.39 (s, CPPh₃),–12.06 ppm (s, OsPPh₃). ¹³C-NMR plus DEPT-135 and ¹H-¹³C HSQC (125.8 MHz, CD₂Cl₂): δ 243.8 (t, J_P-C = 4.6 Hz, C⁷), 240.6 (br, C¹), 183.4 (dt, J_P-C = 21.4 Hz, J_P-C = 4.4 Hz, C⁴), 167.5 (s, C⁵), 160.0 (s, COOCH₃, confirmed by ¹H-¹³C HMBC), 154.5 (d, J_P-C = 19.8 Hz, C³), 142.4 (s, C⁶), 119.0 (d, J_P-C = 89.2 Hz, C²), 51.3 (s, COOCH₃), 135.0–127.5 ppm (m, other aromatic carbons). HRMS (ESI): m/z calcd for [C₆₃H₅₁ClO₂OsP₃]⁺, 1191.2113; found, 1191.2101.