Diisopropylamine → ethyl (E,E,Z)-7-{3-[5-(tert-butyldimethylsilyloxy)-pentyloxy]-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl}-3-methyl-2,4,6,-octatrienoate

HRID 1415910Notes

Reaction equation

HRID 1415910 reaction equation
[Li]CCCC.CCCCCC.C(NC(C)C)(C)C.[CH3:19][CH2:20][O:21][C:22](/[CH:24]=[C:25](/[CH2:27]P(OCC)(OCC)=O)\[CH3:26])=[O:23].[Si:36]([O:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][O:49][C:50]1[C:51](/[C:64](/[CH3:68])=[CH:65]\[CH:66]=O)=[CH:52][C:53]2[C:54]([CH3:63])([CH3:62])[CH2:55][CH2:56][C:57]([CH3:61])([CH3:60])[C:58]=2[CH:59]=1)([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37]>C1COCC1.C(OCC)(=O)C.O.CN1CCCN(C)C1=O>[Si:36]([O:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][O:49][C:50]1[C:51](/[C:64](/[CH3:68])=[CH:65]\[CH:66]=[CH:27]\[C:25](\[CH3:26])=[CH:24]\[C:22]([O:21][CH2:20][CH3:19])=[O:23])=[CH:52][C:53]2[C:54]([CH3:63])([CH3:62])[CH2:55][CH2:56][C:57]([CH3:61])([CH3:60])[C:58]=2[CH:59]=1)([C:39]([CH3:40])([CH3:42])[CH3:41])([CH3:37])[CH3:38]

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 8058HexaneHCID 6000084Ethyl 4-(diethoxyphosphoryl)-3-methylbut-2-enoateHCID 88199402(Z)-3-{3-[5-(tert-butyldimethylsilyloxy)pentyloxy]-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl}-2-butenalHCID 178418339Butyllithium

Product 1

HCID 131721278ethyl (E,E,Z)-7-{3-[5-(tert-butyldimethylsilyloxy)-pentyloxy]-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl}-3-methyl-2,4,6,-octatrienoate

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-SolventHCID 22728543Water ethylacetateSolvent

Conditions

Temperature
-20 °C

Procedure

A 2.5M solution of BuLi in hexane (1.12 mmol) was added dropwise to a solution of diisopropylamine (387 μl) in a 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU)/THF (10 ml/10 ml) mixture at -20° C. The mixture was stirred for 30 min at -20° C., and triethyl 3-methyl-4-phosphonocrotonate (0.68 ml) was then added. The mixture was stirred for 1 h at -20° C. and was added to a solution of (Z)-3-{3-[5-(tert-butyldimethylsilyloxy)pentyloxy]-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl}-2-butenal (1.1 g, 2.3 mmol) in THF (5 ml). The reaction medium was permitted to warm to room temperature and was then treated with ethyl acetate/water. After settling, the organic phase was separated and washed twice with water, dried over anhydrous magnesium sulfate and concentrated in a rotary evaporator under vacuum at 40° C. The desired compound was purified by flash chromatography on a silica column.

Workup

  1. stirringThe mixture was stirred for 1 h at -20° C.
  2. temperatureto warm to room temperature
  3. customthe organic phase was separated
  4. washwashed twice with water
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated in a rotary evaporator under vacuum at 40° C
  7. customThe desired compound was purified by flash chromatography on a silica column

Sources & evidence

ORD record
ord-accd816f77bd4a91ba27ae8dd2fb1ceb
Source dataset
uspto-grants-1999_06
Patent number
US05910508

Reaction notes

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