Compound 10

View in PubChem | MDL Molfile | Chemdraw file

Compound data: 1H NMR

Compound data: 13C NMR

Compound data: 19F NMR

Compound data: Crystallographic data

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

In a 15-mL scintillation vial, a mixture of 2c (47.4 mg, 20 µmol) and trans-3-hexene (100 mg, 1.2 mmol, distilled from calcium hydride and stored over 3Å molecular sieves) was chilled for 1 hour in a glovebox coldwell cooled with dry ice/acetone bath. A pre-cooled solution of KHMDS (6.0 mg, 30 µmol) in MTBE (2.0 mL) was added, and the mixture was stirred with cooling for 30 minutes. ¹³C NMR analysis of the crude mixture suggested the formation of a single major product and a minor side product (judging from quaternary carbon signals alpha to the nitrogen atom. See Supplementary Figure 48.). Then, the resulting mixture was passed through a glass filter, and evaporated to dryness. The solid residue was analysed by quantitative ¹H NMR using 1,3,5-trimethoxybenzene as an internal standard, and the NMR yield of 10 was determined to be 72% (See Supplementary Figure 50.). The formation of 10 as a major product was also confirmed by ¹⁹F NMR analysis of the same mixture (See Supplementary Figure 51.). The same reaction was repeated and the obtained solid residue was recrystallized from chloroform/hexane (vapour diffusion) at room temperature, to afford 10 as pale yellow crystals suitable for X-ray crystallographic analysis. The crystals were grounded and dried in vacuo at 120 °C overnight, to afford 10 as a yellowish powder (22.3 mg, 10 µmol, 50% yield). ¹H NMR (500 MHz, C₆D₆) δ 7.98 (s, 4H), 7.77 (s, 8H), 7.73 (s, 4H), 7.72 (s, 4H), 7.66 (s, 4H), 7.59 (s, 8H), 7.33 (s, 2H), 7.05 (s, 2H), 6.98 (m, 4H), 2.37 (dd, J = 6.3, 4.9 Hz, 1H), 1.48 (m, 1H), 1.18 (m, 3H), 0.99 (t, J = 7.2 Hz, 3H), 0.66–0.49 (m, 5H); ¹³C NMR (126 MHz, CDCl₃) δ 147.2 (2C, 4°), 145.5 (2C, 4°), 144.9 (2C, 4°), 141.9 (4C, 4°), 141.8 (4C, 4°), 139.0 (br, 8C, 4°), 132.6 (q, ²J_C-F =33.4 Hz, 8C, 4°), 132.4 (q, ²J_C-F =33.4 Hz, 8C, 4°), 129.7 (3°), 129.5 (4C, 3°), 129.4 (4C, 3°), 129.1 (3°), 126.8 (br s, 16C, 3°), 125.8–125.4 (overlapped peaks, 6C, 3°), 123.1 (q, ¹J_C-F = 274 Hz, 8C, 4°), 123.0 (q, ¹J_C-F = 274 Hz, 8C, 4°), 122.0 (br s, 8C, 3°), 82.1 (2C, 4°), 46.4 (1C, NCHR₂), 31.3 (1C, 3°), 29.4 (1C, 3°), 27.0 (1C, 2°), 24.0 (1C, 2°), 14.2 (1C, 1°), 12.4 (1C, 1°); ¹⁹F NMR (471 MHz, CDCl₃) δ −62.97, −63.04; HRMS (m/z): [M+TFA−H]⁻ calcd. for C₁₀₃H₅₃F₄₈N·CF₃CO₂, 2328.3267; found, 2328.3274.