Octyltriphenylphosphonium bromide → (2S,3R,4S,5S)-3-(tert-butyldimethylsilyloxy)-4-methoxy-5-methyl-2-[(Z)-1-nonenyl]tetrahydro-2H-pyran

HRID 863167

Reaction equation

HRID 863167 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].[Li]CCCC.[CH3:34][O:35][C@H:36]1[C@@H:41]([CH3:42])[CH2:40][O:39][C@H:38]([CH:43]=O)[C@@H:37]1[O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47]>C1COCC1.CN(P(N(C)C)(N(C)C)=O)C>[Si:46]([O:45][C@@H:37]1[C@@H:36]([O:35][CH3:34])[C@@H:41]([CH3:42])[CH2:40][O:39][C@H:38]1/[CH:43]=[CH:2]\[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:47])[CH3:48]

Participants

6

Reactant 3

HCID 3084855Octyltriphenylphosphonium bromideHCID 57231418(2S,3R,4S,5S)-4-methoxy-5-methyl-3-(tert-butyldimethylsilyloxy)tetrahydro-2H-pyran-2-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 67805109(2S,3R,4S,5S)-3-(tert-butyldimethylsilyloxy)-4-methoxy-5-methyl-2-[(Z)-1-nonenyl]tetrahydro-2H-pyranYield 90.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of n-octyltriphenylphosphonium bromide (2124 mg) in dry THF (10 ml) and dry HMPA (5 ml), there was added n-BuLi (4.0 ml, 1.6M in n-hexane) at 0° C. After the mixture was stirred at 0° C. for 30 min, a solution of (2S,3R,4S,5S)-4-methoxy-5-methyl-3-(tert-butyldimethylsilyloxy)tetrahydro-2H-pyran-2-carbaldehyde (497 mg) in dry THF (3 ml) was added to the resulting orange solution. The mixture was stirred at 0° C. for 30 min, and at room temperature for 2 hours. The reaction was quenched by addition of saturated aqueous ammonium chloride solution. The mixture was extracted with diethyl ether, and the combined ethereal extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated. Purification of the residue by silica gel chromatography gave (2S,3R,4S,5S)-3-(tert-butyldimethylsilyloxy)-4-methoxy-5-methyl-2-[(Z)-1-nonenyl]tetrahydro-2H-pyran (602 mg, 72% yield).

Workup

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

Sources & evidence

ORD record
ord-b60d30f558834f8eb9306387f9b54142
Source dataset
uspto-grants-1998_02
Patent number
US05719291

Linked notes

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