Compound 35

(1R,2R)-2-((1S,3R,3aS,6S,6aR,9R,12bR)-11-Methoxy-3a,10,10-trimethyl-8,12,13-trioxo-1,6-bis((trimethylsilyl)oxy)-1,2,3,3a,4,5,6,7,8,9,10,12-dodecahydro-6a,9-epoxy-3,12b-methanobenzo[4,5]cyclohepta[1,2-e]inden-3-yl)cyclopropanecarboxylic acid

From: Total synthesis of solanoeclepin A

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InChIKey KKYPJJIYXFTTER-AXVSQRIFSA-N

Compound data: CIF

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

To a mixture of the crude aldehyde 34, 2-methyl-2-butene (42 μL, 392 μmol), and NaH2PO4 (13.5 mg, 86.5 μmol) in tBuOH-H2O (3:1, 0.4 mL) was added NaClO2 (18.1 mg, 200 μmol) at room temperature. After being stirred for 15 min, brine was added. The mixture was separated, and the aqueous layer was extracted with ethyl acetate. Concentration of the combined organic layer afforded solanoeclepin A bis-TMS ether 35 (12.2 mg, 19.0 μmol, 97% for 2 steps) as a white solid: m.p.: 168–170 ºC; [α]27D (deg cm3 g–1 dm–1)= +241 (c=0.39 g cm–3 in CHCl3); IR (film): 2959, 2931, 1768, 1698, 1636, 1254, 1102, 1089, 845 cm–1; 1H-NMR (500 MHz, CDCl3): δ 4.52 (dd, J=7.4, 3.2 Hz, 1H), 4.24 (s, 1H), 3.87 (s, 1H), 3.81 (s, 3H), 2.47 (dd, J=8.5, 3.2 Hz, 2H), 2.36 (dd, J=16.6, 1.1 Hz, 1H), 2.22 (dd, J=12.3, 7.4 Hz, 1H), 2.09 (d, J=16.6 Hz, 1H), 1.99 (dd, J=12.3, 3.3 Hz, 1H), 1.98–1.94 (m, 1H), 1.91 (dt, J=13.0, 3.3 Hz, 1H), 1.59–1.48 (m, 2H), 1.43 (s, 3H), 1.27 (s, 3H), 1.25 (s, 3H), 1.22–1.18 (m, 1H), 1.16–1.11 (m, 1H), 0.13 (s, 9H), 0.00 (s, 9H); 13C-NMR (125 MHz, CDCl3): δ 208.64, 198.48, 187.17, 178.82, 147.26, 144.93, 144.86, 131.63, 90.04, 89.24, 73.75, 73.45, 65.78, 65.47, 61.12, 46.71, 44.65, 38.59, 38.13, 31.12, 29.83, 23.88, 20.76, 18.18, 15.98, 12.85, 11.20, 0.18 (3C), 0.04 (3C); HRMS (EI, m/z): [M+] calcd for C33H46O9Si2, 642.2680; found, 642.2705.

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