Octyltriphenylphosphonium bromide → benzyl [(1R,2R,6S)-2-methoxy-3,3-dimethyl-6-[(E)-1-nonenyl]cyclohexyl]methyl ether

HRID 2399570

Reaction equation

HRID 2399570 reaction equation
[Br-].[CH2:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9].[CH2:29]([O:36][CH2:37][C@@H:38]1[C@@H:43]([O:44][CH3:45])[C:42]([CH3:47])([CH3:46])[CH2:41][CH2:40][C@H:39]1[CH:48]=O)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>O1CCCC1.CN(P(N(C)C)(N(C)C)=O)C.[Li]CCCC>[CH3:45][O:44][C@H:43]1[C:42]([CH3:46])([CH3:47])[CH2:41][CH2:40][C@@H:39](/[CH:48]=[CH:2]/[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])[C@@H:38]1[CH2:37][O:36][CH2:29][C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

6

Reactant 2

HCID 3084855Octyltriphenylphosphonium bromideHCID 54235868(1R,2R,3R)-2-(benzyloxymethyl)-3-methoxy-4,4-dimethylcyclohexane-1-carbaldehyde

Product 1

HCID 86748974benzyl [(1R,2R,6S)-2-methoxy-3,3-dimethyl-6-[(E)-1-nonenyl]cyclohexyl]methyl etherYield 61%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolventHCID 178418339ButyllithiumSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of n-octyltriphenylphosphonium bromide (313 mg) in dry tetrahydrofuran (0.5 ml) and dry HMPA (0.5 ml), n-BuLi (0.44 ml, 1.6M solution in n-hexane) was added at 0° C. After the mixture was stirred at 0° C. for 30 min, a solution of (1R,2R,3R)-2-(benzyloxymethyl)-3-methoxy-4,4-dimethylcyclohexane-1-carbaldehyde (68 mg) in dry tetrahydrofuran (0.5 ml) was added to the resulting orange solution. The mixture was stirred at 0° C. for 30 min, and at room temperature for 2 hrs. The reaction was quenched by addition of saturated aqueous ammonium chloride solution. The mixture was extracted with diethyl ether, and the combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was chromatographed on silica gel (using n-hexane:ethyl acetate= 10:1 as an eluent) to give benzyl [(1R,2R,6S)-2-methoxy-3,3-dimethyl-6-[(E)-1-nonenyl]cyclohexyl]methyl ether (54 mg 61%).

Workup

  1. stirringThe mixture was stirred at 0° C. for 30 min
  2. waitat room temperature for 2 hrs
  3. customThe reaction was quenched by addition of saturated aqueous ammonium chloride solution
  4. extractionThe mixture was extracted with diethyl ether
  5. washthe combined organic extracts were washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was chromatographed on silica gel (

Sources & evidence

ORD record
ord-cd09cab338264b0aa38c26ea9478047d
Source dataset
uspto-grants-1995_09
Patent number
US05449785

Linked notes

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