Diisopropylamine → HCID 57008527, compound

HRID 1493076Notes

Reaction equation

HRID 1493076 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH:13]1[CH:18]=[CH:17][C:16]([CH2:19][O:20][C:21]([NH:23][CH2:24][C:25]([OH:27])=[O:26])=[O:22])=[CH:15][CH:14]=1.[O:28]([C@H:36]([CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH3:50])[CH2:37][CH:38]=[O:39])[Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30].S([O-])(O)(=O)=O.[K+]>C1COCC1.CCCCCC>[CH2:19]([O:20][C:21]([NH:23][CH:24]([CH:38]([OH:39])[CH2:37][C@H:36]([O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH3:50])[C:25]([OH:27])=[O:26])=[O:22])[C:16]1[CH:17]=[CH:18][CH:13]=[CH:14][CH:15]=1

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 14349BenzyloxycarbonylglycineHCID 516920Potassium bisulfateHCID 10893271HCID 10893271, compoundHCID 178418339Butyllithium

Product 1

HCID 57008527HCID 57008527, compoundYield 47.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-75 °C

Procedure

A solution of 3.0 ml of diisopropylamine in 50 ml of THF was treated at 0° C. with 12.0 ml of a solution of 1.6M n-butyllithium in hexane and, after stirring, cooled to -75° C. A solution of 1.26 g of Z-glycine in 10 ml of THF was then added dropwise. The reaction mixture was left to warm to room temperature and again cooled to -75° C. 0.7 g of (R)-3-(t-butyldimethylsiloxy)tetradecanal in 5 ml of THF was then added dropwise at -75° C. The reaction mixture was stirred at -75° C. for 1 hour and at -40° to -50° C. for 1/2 hour, then warmed to 5° C., again cooled to -75° C., poured into dilute potassium hydrogen sulphate solution and extracted with ether. The ether phase was dried, concentrated and chromatographed on silica gel with methylene chloride/methanol. There were obtained 540 mg of (2R/S,3R/S,5R)-2-[1 -(benzyloxy)formamido]-5-(t-butyldimethylsiloxy)-3-hydroxyhexadecanoic acid as a mixture of 4 diastereomers.

Workup

  1. waitThe reaction mixture was left
  2. temperatureto warm to room temperature
  3. temperatureagain cooled to -75° C
  4. stirringThe reaction mixture was stirred at -75° C. for 1 hour and at -40° to -50° C. for 1/2 hour
  5. temperaturewarmed to 5° C.
  6. temperatureagain cooled to -75° C.
  7. extractionextracted with ether
  8. dry with materialThe ether phase was dried
  9. concentrationconcentrated
  10. customchromatographed on silica gel with methylene chloride/methanol

Sources & evidence

ORD record
ord-72ee2dad175a4e70b22f84981b68bc55
Source dataset
uspto-grants-1994_12
Patent number
US05376674

Reaction notes

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