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DOI: 10.1055/s-2005-862391
Synthesis of the C13-C23 Segment of Tedanolide
Publication History
Publication Date:
22 February 2005 (online)
Abstract
The synthesis of the C13-C23 segment of tedanolide is described making use of orthogonal protecting groups in the construction of the carbon skeleton and for the selective liberation of hydroxyl groups in the endgame of the total synthesis.
Key words
tedanolide - natural product - aldol - protecting groups
- 1 Tedanolide was isolated from Tedania ignis:
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References
Spectroscopic analysis for 20:
1H NMR (400 MHz, CDCl3): δ = 7.23 (d, J = 8.0 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 5.30 (dq, J = 10.9 Hz, J = 6.6 Hz, 1 H), 5.25-5.21 (m, 2 H), 4.59 (s, 2 H), 4.55 (d, J = 11.2 Hz, 1 H), 4.36 (d, J = 11.2 Hz, 1 H), 4.12 (m, 1 H), 3.78 (s, 3 H), 3.77-3.73 (m, 1 H), 3.68-3.56 (m, 4 H), 3.49 (t, J = 4.6 Hz, 2 H), 3.47-3.42 (m, 1 H), 3.40-3.35 (m, 1 H), 3.34 (s, 3 H), 3.31 (dd, J = 9.7 Hz, J = 6.6 Hz, 1 H), 2.40 (br s, 1 H), 2.37-2.30 (m, 1 H), 2.13-2.03 (m, 1 H), 1.63-1.58 (m, 6 H), 0.97 (d, J = 6.8 Hz, 3 H), 0.95 (d, J = 7.0 Hz, 3 H), 0.83 (s, 9 H), -0.02 (s, 3 H), -0.07 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 159.1 (s), 135.0 (d), 133.8 (s), 132.1 (d), 130.9 (s), 129.2 (d, 2 C), 121.8 (d), 113.7 (d, 2 C), 95.9 (t), 79.5 (d), 77.5 (d), 71.8 (t), 67.7 (t), 66.8 (t), 66.1 (t), 59.0 (q), 55.2 (q), 44.1 (d), 37.7 (d), 30.3 (d), 25.9 (q, 3 C), 21.0 (q), 18.1 (s), 13.0 (q), 12.9 (q), 12.2 (q), -4.3 (q), -5.1 (q).
HRMS (LC-MS, ESI): m/z calcd for C33H58O7SiNa+: 617.3850; found: 617.3864.
IR: 3455 (br), 3010 (w), 2956 (s), 2928 (s), 2888 (s), 2858 (s), 1613 (w), 1514 (m), 1463 (w), 1363 (w), 1301 (w), 1248 (s), 1174 (w), 1040 (ss), 837 (m), 776 (m), 740 (m) cm-1. [α]D
25 +21.9 (c 1.04, CHCl3).