Synthesis of the C13-C23 Segment of Tedanolide

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.

tedanolide - natural product - aldol - protecting groups

References

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5

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).