Benzyl chloroformate → HCID 67093120, compound

HRID 1261851Notes

Reaction equation

HRID 1261851 reaction equation
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[C:15]([O:19][C:20]([N:22]1[C@H:27]([CH:28]=O)[CH2:26][O:25][CH2:24][C@@H:23]1[CH2:30][CH:31]=[CH2:32])=[O:21])([CH3:18])([CH3:17])[CH3:16].Cl.[CH3:34][O:35][C:36](=[O:40])[C@H:37]([CH3:39])[NH2:38].C(=O)([O-])O.[Na+].Cl[C:47]([O:49][CH2:50][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)=[O:48]>C(Cl)Cl.O>[C:15]([O:19][C:20]([N:22]1[C@H:27]([CH2:28][N:38]([C:47]([O:49][CH2:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)=[O:48])[C@H:37]([C:36]([O:35][CH3:34])=[O:40])[CH3:39])[CH2:26][O:25][CH2:24][C@@H:23]1[CH2:30][CH:31]=[CH2:32])=[O:21])([CH3:18])([CH3:17])[CH3:16]

Participants

8

Reactant 5

HCID 10387Benzyl chloroformateHCID 516892Sodium BicarbonateHCID 2733257Alanine methyl ester hydrochlorideHCID 5049666Sodium triacetoxyborohydrideHCID 86652423HCID 86652423, compound

Product 1

HCID 67093120HCID 67093120, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Sodium triacetoxyborohydride (628 mg, 2.96 mmol) were added at 0° C. to a solution of (3S,5S)-3-allyl-5-formyl-morpholine-4-carboxylic acid tert-butyl ester (608 mg, 2.12 mmol) and L-alanine methyl ester hydrochloride (295 mg, 2.12 mmol) in DCM (8 mL), then after 16 h the reaction mixture was partitioned between sat. aq. sodium hydrogencarbonate solution and DCM. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and evaporated. The residue [(3S,5R)-3-allyl-5-[((S)-1-methoxycarbonyl-ethylamino)-methyl]-morpholine-4-carboxylic acid tert-butyl ester, MS: 343.3 (M+H)|] was taken up in acetone (3.5 mL) and water (3.5 mL), then after addition of sodium hydrogencarbonate (355 mg, 4.23 mmol), the reaction mixture was cooled to 0° C. and treated with benzyl chloroformate (380 mg, 2.12 mmol). The ice bath was removed, then after 1 h the reaction mixture was partitioned between EtOAc and water. The organic layer was dried over magnesium sulfate, filtered, and evaporated to afford the title compound (1.01 g, 100%). Light yellow oil, MS: 477.3 (M+H)+.

Workup

  1. customafter 16 h the reaction mixture was partitioned between sat. aq. sodium hydrogencarbonate solution and DCM
  2. washThe organic layer was washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customThe ice bath was removed
  7. customafter 1 h the reaction mixture was partitioned between EtOAc and water
  8. dry with materialThe organic layer was dried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-3efe0e23c6f2496e84273caac137b4e6
Source dataset
uspto-grants-2013_06
Patent number
US08471004B2

Reaction notes

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