Diisopropylamine → HCID 53906880, compound

HRID 1493080Notes

Reaction equation

HRID 1493080 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][O:14][C:15](=[O:31])[CH2:16][N:17]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[O:32]([C@H:40]([CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[CH2:41][CH:42]=[O:43])[Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34].S([O-])(O)(=O)=O.[K+]>C1COCC1.CCCCCC>[CH2:24]([N:17]([CH:16]([CH:42]([OH:43])[CH2:41][C@H:40]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[C:15]([O:14][CH3:13])=[O:31])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 516920Potassium bisulfateHCID 10893271HCID 10893271, compoundHCID 19373179Methyl N-benzyl-N-phenylglycinateHCID 178418339Butyllithium

Product 1

HCID 53906880HCID 53906880, compoundYield 7.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-75 °C

Procedure

A solution of 0.5 ml of diisopropylamine in 15 ml of THF was treated at 0° C. with 2.0 ml of a solution of 1.6M n-butyllithium in hexane and, after stirring, cooled to -75° C. Then, a solution of 765 mg of N-benzyl-N-phenylglycine methyl ester in 3 ml of THF was added. After stirring a solution of 700 mg of (R)-3-(t-butyl-dimethylsiloxy)tetradecanal (Example Bb)) in 5 ml of THF was added dropwise. After stirring at -75° C. the reaction mixture was poured into aqueous potassium hydrogen sulphate and extracted with ether. The ether phase was dried, concentrated, partitioned between hexane and methanol/water (7:3), the hexane phase was dried and concentrated and the residue was chromatographed on silica gel with pentane/ether (5:1). There were obtained 96.3 mg of methyl (5R)-2-(N-benzylanilino)-5-(t-butyldimethylsiloxy)-3-hydroxyhexadecanoate, diastereomer A, MS: 540 (M+ ·-C4H9 ·), and 142.8 mg of methyl (5R)-2-(N-benzylanilino)-5-(t-butyldimethylsiloxy)-3-hydroxyhexadecanoate, diastereomer B, MS: 540 (M+ ·-C4H9 ·), and 313.4 g of a mixture of the above two diastereomers.

Workup

  1. additionwas added dropwise
  2. stirringAfter stirring at -75° C. the reaction mixture
  3. extractionextracted with ether
  4. dry with materialThe ether phase was dried
  5. concentrationconcentrated
  6. custompartitioned between hexane and methanol/water (7:3)
  7. dry with materialthe hexane phase was dried
  8. concentrationconcentrated
  9. customthe residue was chromatographed on silica gel with pentane/ether (5:1)

Sources & evidence

ORD record
ord-0ac69948c6ef4f2f9a2efe8b7b3f65d6
Source dataset
uspto-grants-1994_12
Patent number
US05376674

Reaction notes

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