[CH2:1]([Si:5]([CH3:22])([C:12]1([CH2:18][CH:19]([CH3:21])[CH3:20])SCCCS1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH2:2][CH:3]=[CH2:4].[OH2:23]>CC#N.Cl[Hg]Cl>[CH2:1]([Si:5]([CH3:22])([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C:12](=[O:23])[CH2:18][CH:19]([CH3:21])[CH3:20])[CH2:2][CH:3]=[CH2:4]To a solution of 44 (6.19 g, 177 mmol) in CH3CN (200 mL) was added water (10 mL) and HgCl2 (24 g, 88 mmol). After stirring overnight at rt, the mixture was concentrated and partitioned between water (100 mL) and hexane (200 mL). The organic layer was isolated and the aqueous layer extracted twice with 50-mL portions of hexane. The combined organic extracts were washed with saturated aqueous NaCl and dried over Na2SO4. Concennation to dryness in vacuo at rt gave quantitatively crude ketone 45 as a yellow oil. This ketone was used in the next reaction without further purification: Rf=0.75 (1/19 EtOAc:hexane); 1H NMR (300 MHz, CDCl3) δ 7.54–7.51 (m, 2H), 7.41–7.35 (m, 3H), 5.91–5.78 (m, 1H), 4.99 (dd, J=17.0, 1.7 Hz, 1H), 4.90 (dd, J=10.0, 1.7 Hz, 1H), 2.44 (d, J=6.7 Hz, 2H), 2.16–2.06 (m, 3H), 1.16–1.07 (m, 2H), 0.78 (pd. J=6.7 Hz, 6H), 0.51 (s, 3H).
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