Diazomethane → HCID 86691260, compound

HRID 2037284Notes

Reaction equation

HRID 2037284 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 (3.2 g, 57 mmol) in water (5 mL), diethylene glycol monoethyl ether (4 mL) and diethyl ether (10 mL) and N-methyl-N′-nitro-N-nitrosoguanidine (5 g, 34 mmoles) in a mixture of diethyl ether (35 mL) and diethylene glycol monoethyl ether (15 mL). Take the resulting solution of diazomethane and add it portionwise over 60 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 (185 mg) in diethyl ether (2 mL). Once gas evolution has ceased, leave to stand for 30 minutes, filter and concentrate under reduced pressure to yield a yellow oil. Purify by mass guided HPLC (RT=6.4 minutes (UV), 6.37 minutes (MS); LC Column: Waters XBridge™ 30 mm×100 mm Sum; water w/0.1% formic acid; gradient: 28-62% acetonitrile w/0.1% formic acid in 1.35 minutes then 62-95% in 6.65 minutes, then held at 95% for 3.55 minutes. Column temperature: ambient; flow rate: 45 mL/minute) to yield the title compound as a colorless oil (55.3 mg, 130.6 μmol). MS (m/z): 446 (M+23).

Workup

  1. additionadd it portionwise over 60 minutes

Sources & evidence

ORD record
ord-1aee069c2d7d473b84f94e4d26322214
Source dataset
uspto-grants-2013_11
Patent number
US08575214B2

Reaction notes

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