Compound 9 P1

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

TBS ether 23 P1 (17 mg, 0.024 mmol, 1 equiv.) was dissolved in anhydrous THF (1.3 mL) under argon at rt. 3HF∙Et₃N (215 µL) was dissolved with anhydrous THF (2.8 mL) in a dry flask under argon. From this solution was taken 0.3 mL (containing approx. 21.5 µL, 0.129 mmol, 5.4 equiv. of 3HF∙Et₃N) and added to the solution of 23 P1. After 18 h water was added to the reaction and the mixture was extracted four times with CH₂Cl₂. The combined organic phases were dried over Na₂SO₄, filtered, and concentrated to yield the product 9 P1 in quantitative yield pure enough to continue with. For data the product was purified by FC (0.3x5 cm) 95:5 CH₂Cl₂/MeOH to yield the product 9 P1 (13.8 mg, 0.024 mmol, 97 %) as a white solid. R_f 0.14 (EtOAc/MeOH 95:5, UV and CAM). Opt. Rot. [α]²⁶_D = -44.4 (c = 0.35, CHCl₃). ¹H NMR (400 MHz, CDCl₃) δ 8.13 (brs, 1H), 7.56 (d, J = 8.6 Hz, 1H), 6.67 (dd, J = 15.1, 3.1 Hz, 1H), 5.97 (dd, J = 15.1, 2.1 Hz, 1H), 4.99 (ddd, J = 10.2, 7.0, 3.3 Hz, 1H), 4.74 (brs, 1H), 4.59 (d, J = 19.3 Hz, 1H), 4.47 (s, 1H), 4.27 (dd, J = 17.2, 6.9 Hz, 1H), 3.97 – 3.86 (m, 1H), 3.86 – 3.54 (m, 5H), 2.97 (s, 3H), 1.68 (s, 3H), 1.51 (dh, J = 13.2, 6.7 Hz, 1H), 1.25 (s, 18H), 1.20 – 1.08 (m, 5H), 0.86 (d, J = 6.6 Hz, 6H). (400 MHz, DMSO) δ 8.59 (dd, J = 7.2, 5.2 Hz, 1H), 7.52 (d, J = 8.6 Hz, 1H), 6.70 (dd, J = 15.1, 3.3 Hz, 1H), 6.35 (brs, 1H), 6.17 (dd, J = 15.1, 2.1 Hz, 1H), 5.01 (brs, 1H), 4.94 – 4.86 (m, 1H), 4.55 – 4.42 (m, 1H), 4.17 (s, 2H), 3.94 (dd, J = 16.3, 7.2 Hz, 1H), 3.57 (dd, J = 16.3, 5.3 Hz, 1H), 3.52 – 3.28 (m, 3H), 2.84 (s, 3H), 1.68 – 1.55 (m, 1H), 1.55 – 1.35 (m, 1H) 1.48 (dh, J = 13.3, 6.7 Hz, 2H), 1.43 (s, 3H), 1.29 – 1.10 (m, 18H), 1.05 (d, J = 6.9 Hz, 3H), 0.84 (d, J = 6.6 Hz, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 216.8, 172.8, 168.9, 168.1, 167.8, 120.2, 110.0, 80.6, 78.2, 63.4, 51.4, 50.9, 44.1, 41.3, 39.0, 36.0, 31.9, 29.9, 29.7, 29.6, 29.6, 29.5, 29.5, 28.0, 27.4, 24.2, 22.7, 20.7, 15.7. (101 MHz, DMSO) δ 211.3, 171.8, 168.2, 168.0, 166.2, 142.8, 119.5, 99.5, 80.3, 75.0, 62.7, 52.0, 50.8, 42.8, 42.5, 38.5, 34.6, 30.8, 29.3, 29.1, 29.1, 28.9, 28.9, 27.4, 26.8, 24.0, 22.5, 21.3, 15.4. HRMS Calc.: C₃₀H₅₁N₃O₈Na⁺ 604.3568; found 604.3571. IR (neat) νmax / cm^-1 3345, 2924, 1751, 1657, 1537, 1261, 1192, 1019, 800.