Aluminium lithium hydride → 1-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butanol

HRID 1062494Notes

Reaction equation

HRID 1062494 reaction equation
[CH2:1]([Si:5]([CH3:18])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6](=[O:11])[CH2:7][CH:8]([CH3:10])[CH3:9])[CH2:2][CH:3]=[CH2:4].[H-].[Al+3].[Li+].[H-].[H-].[H-]>C(OCC)C>[CH2:1]([Si:5]([CH3:18])([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[CH:6]([OH:11])[CH2:7][CH:8]([CH3:10])[CH3:9])[CH2:2][CH:3]=[CH2:4]

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 222870621-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butanone

Product 1

HCID 229671631-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butanol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 45 (4.60 g, 17.7 mmol) in ethyl ether (150 mL) at 0° C. was added dropwise over 5 min lithium aluminum hydride (1 M in ethyl ether, 88.3 mmol). After stirring for 15 min at 0° C. under argon, the reaction mixture was diluted with ethyl ether (200 mL) and quenched with saturated Na2SO4 solution until evolution of hydrogen had ceased. The mixture was dried with solid Na2SO4 and filtered. The residue was extracted with ether (50 mL) and the organic extracts combined. Concentration provided a yellow oil of 46 as a mixture of diastereomers (3.6 g, 78%). This product was used in the next reaction without further purification: Rf=0.50 (1/9 EtOAc:hexane); 1H NMR (300 MHz, CDCl3) δ 7.58-7.53 (m, 2H), 7.39-7.34 (m, 3H), 5.95-5.82 (m, 1H), 5.03-4.89 (m, 2H), 3.70 (dd, J=12.0, 2.3 Hz, 1H), 2.15-2.07 (m, 2H), 1.86-1.76 (m, IH), 1.59-1.49 (m, 2H), 1.23-1.12 (m, 1H), 1.03-0.84 (m, 7H), 0.33 and 0.34 (two singlets due to diastereomers, 3H); 13C NMR (75 MHz, CDCl3) δ 141.5, 135.8, 135.6, 134.7, 134.6, 129.6, 129.5, 128.2, 128.1, 113.2, 62.5, 62.1, 42.3, 42.2, 27.5, 24.2, 24.1, 23.6, 20.7, 20.8, 10.7, 10.5, −7.9, −8.0; IR (neat) 3571 (w), 3434 (m, br), 3069 (m), 2954 (s), 2913 (s), 2872 (m), 1638 (m), 1466 (m), 1427 (m), 1366 (w), 1251 (m), 1111 (s), 993 (m), 902 (m), 790 (s), 736 (s), 700 cm−1; MS (CI/CH4) m/e (rel. intensity) 263 (M++1, 2), 247 (13), 235 (10), 233 (12), 231 (13), 207 (13), 187 (11), 177 (20), 176 (15), 175 (69), (69), 151 (23), 137 (100), 131 (12), 115 (41). Anal. Calcd for C16H26OSi: C, 73.22; H, 9.98. Found: C, 72.85; H, 10.24.

Workup

  1. customquenched with saturated Na2SO4 solution until evolution of hydrogen
  2. dry with materialThe mixture was dried with solid Na2SO4
  3. filtrationfiltered
  4. extractionThe residue was extracted with ether (50 mL)
  5. concentrationConcentration

Sources & evidence

ORD record
ord-22d423298e0041b8b26d387d55a7f27c
Source dataset
uspto-grants-2005_11
Patent number
US06960678B2

Reaction notes

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