Diazomethane → HCID 86691260, compound

HRID 2037283Notes

Reaction equation

HRID 2037283 reaction equation
[N+](=[CH2:3])=[N-].[OH-].[K+].CN(N=O)C(N[N+]([O-])=O)=N.[C:16]([O:20][C:21]([NH:23][C@@:24]1([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[CH2:29][C:28](=[CH2:30])[C@@H:27]2[C@H:25]1[C@H:26]2[C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])=[O:22])([CH3:19])([CH3:18])[CH3:17]>C(OCC)C.O.C(OCCOCCO)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)C>[C:16]([O:20][C:21]([NH:23][C@@:24]1([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[CH2:29][C:28]2([CH2:3][CH2:30]2)[C@@H:27]2[C@H:25]1[C@H:26]2[C:31]([O:33][C:34]([CH3:35])([CH3:37])[CH3:36])=[O:32])=[O:22])([CH3:19])([CH3:17])[CH3:18]

Participants

10

Reactant 4

HCID 9550Diazomethane2×HCID 14797Potassium HydroxideHCID 60149759HCID 60149759, compoundHCID 135436526N-Methyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 86691260HCID 86691260, compound

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent4×HCID 8146Diethylene Glycol Monoethyl EtherSolvent2×

Procedure

Prepare an ethanol free solution of diazomethane in diethyl ether from a solution of potassium hydroxide (2.5 g, 44.6 mmol) in water (4 mL), diethylene glycol monoethyl ether (14 mL) and diethyl ether (8 mL) and N-methyl-N′-nitro-N-nitrosoguanidine (4 g, 27.2 mmol) in a mixture of diethyl ether (30 mL) and diethylene glycol monoethyl ether (15 mL). Take the resulting solution of diazomethane and add it portion wise over 30 minutes to a suspension of palladium acetate (20 mg, 89.1 μmol) in a solution of the previously prepared mixture of unreacted ditert-butyl (1S,2S,5R,6S)-2-(tert-butoxycarbonylamino)-4-methylene-bicyclo[3.1.0]hexane-2,6-dicarboxylate and title compound (260 mg) in diethyl ether (3 mL). Once gas evolution has ceased, leave to stand overnight, then filter through a phase separator frit and concentrate under reduced pressure to yield a dark oil. Purify by flash chromatography eluting with ethyl acetate:iso-hexane (0:100 to 75:25) to yield 185 mg of a mixture of unreacted ditert-butyl (1S,2S,5R,6S)-2-(tert-butoxycarbonylamino)-4-methylene-bicyclo[3.1.0]hexane-2,6-dicarboxylate and title compound.

Workup

  1. additionadd it portion wise over 30 minutes

Sources & evidence

ORD record
ord-acb4c8bc403b41cda0b9b30027353e1b
Source dataset
uspto-grants-2013_11
Patent number
US08575214B2

Reaction notes

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