Hydride → [2-(tert-butoxycarbonylamino-methyl)-4-hydroxy-but-2-enyl]-carbamic Acid Tert-Butyl Ester

HRID 899705Notes

Reaction equation

HRID 899705 reaction equation
C([O:3][C:4](=O)[CH:5]=[C:6]([CH2:16][NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:7][NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])C.C(=O)=O.CC(C)=O.[H-]>O1CCCC1>[C:12]([O:11][C:9](=[O:10])[NH:8][CH2:7][C:6]([CH2:16][NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[CH:5][CH2:4][OH:3])([CH3:14])([CH3:15])[CH3:13]

Participants

5

Reactant 3

HCID 166653HydrideHCID 18522661Acetone cardiceHCID 865903194-tert-butoxycarbonylamino-3-(tert-butoxycarbonylamino-methyl)-but-2-enoic Acid Ethyl Ester

Product 1

HCID 86590320[2-(tert-butoxycarbonylamino-methyl)-4-hydroxy-but-2-enyl]-carbamic Acid Tert-Butyl EsterYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 4-tert-butoxycarbonylamino-3-(tert-butoxycarbonylamino-methyl)-but-2-enoic acid ethyl ester (7.0 g, 19.5 mmol) in tetrahydrofuran (195 ml), at a reaction temperature of −78° C. (dry ice/acetone) was added a solution of diissobutylaluminum hydride (1 M in CH2Cl2, 59 ml, 59 mmol) and the reaction mixture stirred at −78° C. for 2 hours under a N2 atmosphere. The reaction was quenched with a saturated solution of sodium tartrate tetrahydrate (300 ml), stirred vigorously until the layers clarified then extracted with methylene chloride (2×100 ml). The combined organic extracts were dried (Na2SO4), filtered, and concentrated in vacuo to afford a yellow oil. Purification via column chromatography on silica gel (ethyl acetate:hexane, 1:1, v/v) afforded the product as a yellow oil (5.90 g, 96%). 1HNMR (CDCl3) δ 1.43 (s, 18H), 3.72 (s, 4H), 4.18 (t, 2H), 4.76 (s, 1H), 5.54 (s, 1H), 5.96 (t, 1H).

Workup

  1. customThe reaction was quenched with a saturated solution of sodium tartrate tetrahydrate (300 ml)
  2. stirringstirred vigorously until the layers
  3. extractionclarified then extracted with methylene chloride (2×100 ml)
  4. dry with materialThe combined organic extracts were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto afford a yellow oil
  8. customPurification via column chromatography on silica gel (ethyl acetate

Sources & evidence

ORD record
ord-a4ec5a2e877349c9b35e5fac5385c108
Source dataset
uspto-grants-2008_04
Patent number
US07354932B2

Reaction notes

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