HCID 131720243, compound → HCID 22878254, compound
Reaction equation
C=C1CCCC(C)(C)[C@@H]1CC1C=C(OC)C(Br)=C(O[SiH](C)C)C=1C(C)(C)C.[CH2:28]=[C:29]1[C@@H:34]([OH:35])[CH2:33][C@H:32](Br)[C:31]([CH3:38])([CH3:37])[C@H:30]1[CH2:39][C:40]1[CH:45]=[C:44]([O:46][CH3:47])[C:43]([Br:48])=[CH:42][C:41]=1[O:49]C(=O)C.[SiH3]C1C=CC=CC=1O>>[OH:35][C@H:34]1[CH2:33][CH2:32][C:31]([CH3:37])([CH3:38])[C@H:30]([CH2:39][C:40]2[CH:45]=[C:44]([O:46][CH3:47])[C:43]([Br:48])=[CH:42][C:41]=2[OH:49])[C:29]1=[CH2:28]Participants
Procedure
This set of diastereomeric alcohols was prepared from (2S)-1-methylidene-2-[2'-(tert-butyl)dimethylsilyloxy-4'-bromo-5'-methoxyphenyl]methyl-3,3-dimethylcyclohexane (51) (0.340 g, 0.75 mmol) in the manner previously described for the synthesis of alcohol 54, affording 302 mg (86%) of an inseparable 1:1 mixture of diastereomeric allylic alcohols (58). A portion (21.6 mg, 0.046 mmol) of this diastereomeric mixture was subjected to deprotection of the silylphenol in the usual manner, yielding mixture of free phenols, separable by flash column chromatography (silica gel, hexanes lethyl acetate, gradient elution), to give 7.2 mg (44%) of the less polar 1S,3S diastereomer (59), along with 6.5 mg (40%) of the more polar 1R,3S diastereomer (60) as white solids. The 400MHz 1H NMR spectrum and TLC. elution properties of each diastereomer 59 and 60 were identical to those previously reported for their respective enantiomeric hydroxy compounds 56 and 57. [Compound 59 is hereinafter also referred to as COMPOUND "B" or 120263]
Workup
- customaffording
- customyielding
- washseparable by flash column chromatography (silica gel, hexanes lethyl acetate, gradient elution)
Sources & evidence
- ORD record
- ord-0a61dc04b5be4bd49ed8dfed6247ae8a
- Source dataset
- uspto-grants-1997_10
- Patent number
- US05677336
Reaction notes
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