Isopropenyl chloroformate → HCID 10326313, compound

HRID 1727167Notes

Reaction equation

HRID 1727167 reaction equation
[Cl:1][C:2]1[C:11]2[N:10]([CH3:12])[O:9][C@H:8]3[NH:13][C@H:14]([C:16]([O:18][C@@H:19]4[C@:28]5([OH:29])[C@@H:23]([C@H:24]([CH:31]([CH3:33])[CH3:32])[CH2:25][CH2:26][CH:27]5[CH3:30])[CH:22]=[C:21]([CH3:34])[CH:20]4[OH:35])=[O:17])[CH2:15][C@@:7]3([OH:36])[C:6]=2[CH:5]=[CH:4][CH:3]=1.Cl[C:38]([O:40][C:41]([CH3:43])=[CH2:42])=[O:39]>CN(C)C1C=CN=CC=1.ClCCl>[Cl:1][C:2]1[C:11]2[N:10]([CH3:12])[O:9][C@H:8]3[NH:13][C@H:14]([C:16]([O:18][C@@H:19]4[C@:28]5([OH:29])[C@@H:23]([C@H:24]([CH:31]([CH3:32])[CH3:33])[CH2:25][CH2:26][C@H:27]5[CH3:30])[CH:22]=[C:21]([CH3:34])[C@H:20]4[O:35][C:38]([O:40][C:41]([CH3:43])=[CH2:42])=[O:39])=[O:17])[CH2:15][C@@:7]3([OH:36])[C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 93846Isopropenyl chloroformateHCID 86614040HCID 86614040, compound

Product 1

HCID 10326313HCID 10326313, compoundYield 96.4%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To (1S,4aS,5S,8aR)-2,8a-dihydroxy-3,8-dimethyl-5-(1-methylethyl)-1,2,4a,5,6,7,8,8a-octahydronaphthalen-1-yl (2S,3aR,9bR)-6-chloro-9b-hydroxy-5-methyl-1,2,3,3a,5,9b-hexahydropyrrolo[2,3-c][2,1]benzoxazine-2-carboxylate (Preparation 144, 50 mg, 0.096 mmol) and 4-dimethylaminopyridine (35 mg, 0.29 mmol) in dichloromethane (5 ml) at 0° C. under nitrogen was added isopropenyl chloroformate (17.4 mg, 0.144 mmol) and the resulting mixture stirred at 0° C. for 30 minutes and at room temperature for 2 hours. The reaction mixture was diluted with dichloromethane (25 ml) and washed with citric acid solution (3×15 ml), dried (MgSO4) and concentrated in vacuo. The crude product was purified by chromatography on silica (5 g) eluting with hexane:ethyl acetate (1:1). The pure fractions were combined and concentrated in vacuo to give the title product (56 mg, 96%).

Workup

  1. washwashed with citric acid solution (3×15 ml)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by chromatography on silica (5 g)
  5. washeluting with hexane:ethyl acetate (1:1)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b0cd34d36572401c8d00f8d5aa66a69d
Source dataset
uspto-grants-2009_02
Patent number
US07494992B2

Reaction notes

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