Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
Pure (S,P)-1 was obtained via the C–H activation – ligand exchange – reduction sequence described in Supplementary Section 4. Rf (ethyl acetate in pentane, 30%): 0.61; m.p. 87.7 – 88.7 °C; 1H NMR (400 MHz, CDCl3) δ: 7.97 (d, J = 8.1 Hz, 1H, H3), 7.64 (ddd, J = 8.2, 8.2, 5.1 Hz, 1H, H2), 7.51 (d, J = 7.8 Hz, 1H, H4), 7.47-7.46 (m, 2H, H6 & H7), 7.31 (dt, J = 8.1, 4.5 Hz, 1H, H5), 7.23 (app. t, J = 8.5 Hz, 1H, H1), 7.08 (d, J = 8.2 Hz, 2H, H8), 6.99 (d, J = 8.2 Hz, 2H, H9), 2.32 (s, 3H, H10); 13C NMR (100 MHz, CDCl3) δ: 159.4 (d, 1JC–F = 250.0 Hz, C15), 146.3 (d, 3JC–F = 2.0 Hz, C13), 142.5 (C11), 140.0 (C12), 133.0 (C4), 132.44 (C7), 132.39 (d, 3JC–F = 7.3 Hz, C16), 130.9 (d, 3JC–F = 8.3 Hz, C2), 130.8 (C5), 130.1 (C8), 127.6 (C6), 126.8 (d, 2JC–F = 19.2 Hz, C14), 126.4 (C9), 125.9 (d, 4JC–F = 1.2 Hz, C17), 119.9 (d, 4JC–F = 3.4 Hz, C3), 117.9 (d, 2JC–F = 22.7 Hz, C1), 21.7 (C10); [α]20D = –95.6 (c = 0.19, CHCl3); HRMS (ESI): calcd. for C19H15BrFOS 389.00055, found 389.00016; HPLC analysis: OZ-H column, 40 °C, 0.5 mL min–1, heptane/isopropanol = 80/20, λ = 215 nm, t1= 20.2 min, t2 = 26.7 min, t3 = 34.4 min, t4 = 42.2 min.
A single crystal could be grown by vapour diffusion: heptane into ethyl acetate at room temperature. A single crystal of compound (S,P)-1, was mounted on top of a cryoloop and transferred into the cold nitrogen stream (100 K) of a Bruker-AXS D8 Venture diffractometer. Data collection and reduction was done using the Bruker software suite APEX2 (Bruker, (2012). APEX2 (v2012.4-3), SAINT (Version 8.18C) and SADABS (Version 2012/1). Bruker AXS Inc., Madison, Wisconsin, USA). The final unit cell was obtained from the xyz centroids of 9985 reflections after integration. A multiscan absorption correction was applied, based on the intensities of symmetry-related reflections measured at different angular settings (SADABS). The structures were solved by direct methods using SHELXS, and refinement of the structure was performed using SHELXL (Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122). The hydrogen atoms were generated by geometrical considerations, constrained to idealised geometries and allowed to ride on their carrier atoms with an isotropic displacement parameter related to the equivalent displacement parameter of their carrier atoms. The absolute configuration that was chosen was suggested based on the anomalous scattering; refinement of the inverted structure resulted in significantly higher R-values. Final refinement gave a Flack x-parameter of 0.024(7) using Parsons’ method. While this Flack x value is slightly too high (3.4 x s.u.) (resulting in a B-level alert when using the online IUCr CheckCIF routine), its small absolute value together with a comparison to the inverted structure (which refined to Flack x = 0.983(2) indicates the model to be correct. Crystal data and details on data collection and refinement are presented in Supplementary Table 2. The data have been deposited in the Cambridge Crystallographic Data Centre, CCDC deposition number: 1473304.