2,6-Lutidine → Hexamethyldisiloxane

HRID 1720103Notes

Reaction equation

N1C(C)=CC=CC=1C.[Si:9]([O:13]S(C(F)(F)F)(=O)=O)([CH3:12])([CH3:11])[CH3:10]>ClCCCl.C(OCC)C>[Si:9]([O:13][Si:9]([CH3:12])([CH3:11])[CH3:10])([CH3:12])([CH3:11])[CH3:10]

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of hydroxy aldehyde 54 (21 mg, 41 μmol) in 1,2-dichloroethane (4 mL) was added 2,6-lutidine (72 μL, 620 μmol) and TMSOTf (79 μL, 410 μmol). The mixture was heated at 70° C. for 4.5 h before being cooled, diluted with ethyl ether (50 mL), washed with CuSO4 (20 mL), NaHCO3 (20 mL) and dried (MgSO4). Concentration under reduced pressure and purification by flash chromatography (silica gel, 10% ethyl acetate in toluene) gave pure silyl ether 55 (14 mg; 60%): Colorless oil; Rf =0.29 (silica gel, 70% ethyl ether in petroleum ether); 1H NMR (500 MHz, C6D6) δ9.61 (s, 1 h, CHO), 7.25 (d, J=8.7 hz, 2 h, Ar), 6.79 (d, J=8.7 hz, 2 h, Ar), 5.32 (s, 1 h, CHCN), 5.08 (d, J=14.0 hz, 1 h, allylic CH2), 4.85 (d, J=15.1 hz, 1 h, benzylic CH2), 4.75 (d, J=15.1 hz, 1 h, benzylic CH2), 4.60 (d, J=14.0 hz, 1 h, allylic CH2), 4.24 (dd, J=8.5, 2.2 hz, 1 h, THP anomeric CH), 3.93 (s, 1 h, CHOTHP), 3.74-3.68 (m, 1 h, ketal), 3.58-3.54 (m, 1 h, ketal), 3.30-3.24 (m, 3 h, ketal and THP), 3.29 (s, 3 h, OCH3), 3.03-2.96 (m, 1 h, THP), 1.4-0.9 (m, 6 h, THP), 0.34 (s, 9 h, TMS); IR (film) νmax 2929, 2856, 2211, 1734, 1616, 1513, 1424, 1376, 1247, 1180, 1118, 1035, 946, 910, 847 cm-1 ; HRMS Calcd. for C29H36O9N2Si (M+Na+): 607.2088. Found: 607.2080.

Workup

temperaturebefore being cooled
washwashed with CuSO4 (20 mL), NaHCO3 (20 mL)
dry with materialdried (MgSO4)
concentrationConcentration
customunder reduced pressure and purification by flash chromatography (silica gel, 10% ethyl acetate in toluene)

Sources & evidence

ORD record: ord-ff8e164417f94e2984f265bc2fb4178b
Source dataset: uspto-grants-1996_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05504206

Reaction notes

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