Compound 33

(1S,3R,3aS,6S,6aR,9R,12bR)-3-((1R,2R)-2-(Hydroxymethyl)cyclopropyl)-11-methoxy-3a,10,10-trimethyl-1,6-bis((trimethylsilyl)oxy)-1,2,3,3a,4,5,9,10-octahydro-6a,9-epoxy-3,12b-methanobenzo[4,5]cyclohepta[1,2-e]indene-8,12,13(6H,7H)-trione

From: Total synthesis of solanoeclepin A

View in PubChem | MDL Molfile | ChemDraw

InChIKey GSJHCOSAQQYYMF-PLKWEVPNSA-N

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

To a mixture of the crude product 32 and imidazole (22.4 mg, 329 μmol) in DMF (0.45 mL) was added trimethylsilyl chloride (25.0 μL, 200 μmol) at room temperature. After being stirred for 15 min, water (0.23 mL) and THF (0.5 mL) were added. After additional 15 min, an excess amount of water was added. The mixture was separated, and the aqueous layer was extracted with ether. The combined organic layer was dried over MgSO4 and concentrated under reduced pressure. Purification by silica gel column chromatography (EtOAc/hexane 1:4 then 1:1.5) afforded alcohol 33 (12.3 mg, 19.6 μmol, 88% for 3 steps) as a colorless oil: [α]27D (deg cm3 g–1 dm–1)= +226 (c=0.46 g cm–3 in CHCl3); IR (film): 3444, 2957, 1769, 1635, 1253, 1093, 844 cm–1; 1H-NMR (500 MHz, CDCl3): δ 4.47 (dd, J=7.4, 3.3 Hz, 1H), 4.20 (s, 1H), 3.84 (s, 1H), 3.78 (s, 3H), 3.56 (dd, J=10.9, 6.0 Hz, 1H), 3.36 (dd, J=10.9, 7.4 Hz, 1H), 2.50–2.38 (m, 2H), 2.33 (dd, J=16.6, 1.1 Hz, 1H), 2.10 (dd, J=12.5, 7.4 Hz, 1H), 2.07 (d, J=16.6 Hz, 1H), 1.88–1.83 (m, 1H), 1.87 (dd, J=12.5, 3.3 Hz, 1H), 1.56–1.50 (m, 1H), 1.40 (s, 3H), 1.34–1.28 (m, 1H), 1.24 (s, 3H), 1.21 (s, 3H), 0.73–0.65 (m, 2H), 0.41–0.38 (m, 1H), 0.10 (s, 9H), –0.03 (s, 9H); 13C-NMR (125 MHz, CDCl3): δ 208.73, 200.18, 187.24, 147.25, 144.77, 144.62, 131.86, 90.05, 89.23, 73.77, 73.47, 66.93, 66.56, 65.56, 61.07, 46.67, 44.67, 37.78, 31.16, 29.90, 29.68, 23.85, 20.76, 17.05, 12.97, 11.48, 5.60, 0.17 (3C), 0.07 (3C); HRMS (EI, m/z): [M+] calcd for C33H48O8Si2, 628.2888; found, 628.2852.

Back to article page