Trimethylsilyldiazomethane → Ethyl (S)-2-(Boc-amino)-6-diazo-5-oxohexanoate

HRID 870810Notes

Reaction equation

[Li]CCCC.[Si]([CH:10]=[N+:11]=[N-:12])(C)(C)C.[O:13]=[C:14]1[N:18]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C@H:17]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH2:16][CH2:15]1>C1COCC1>[C:22]([O:21][C:19]([NH:18][C@@H:17]([CH2:16][CH2:15][C:14](=[O:13])[CH:10]=[N+:11]=[N-:12])[C:26]([O:28][CH2:29][CH3:30])=[O:27])=[O:20])([CH3:23])([CH3:25])[CH3:24]

Participants

Conditions

Temperature: -78 °C

Procedure

n-BuLi was added dropwise to a solution of TMSCHN2 (690 mL, 1.38 mol) in dry THF (3 L) (600 mL, 1.5 mol) at −78° C., and the mixture was stirred at −78° C. for 30 min. The mixture was then transferred to a solution of (S)-1-tert-butyl 2-ethyl 5-oxopyrrolidine-1,2-dicarboxylate (300 g, 1.17 mol) in dry THF (3 L) via cannula, and the mixture was stirred at −78° C. for 30 min. The reaction mixture was then quenched with sat. NH4Cl solution, and extracted with DCM three times. The combined organic layer was concentrated in vacuum and the crude product was purified by silica gel column chromatography (3:1 petroleum ether:EtOAc) to afford (S)-ethyl 2-((tert-butoxycarbonyl)amino)-6-diazo-5-oxohexanoate (262 g, 75%) as a yellow solid.

Workup

stirringthe mixture was stirred at −78° C. for 30 min
customThe reaction mixture was then quenched with sat. NH4Cl solution
extractionextracted with DCM three times
concentrationThe combined organic layer was concentrated in vacuum
customthe crude product was purified by silica gel column chromatography (3:1 petroleum ether:EtOAc)

Sources & evidence

ORD record: ord-6188485e02bd48f492cb0c17b608465e
Source dataset: uspto-grants-2015_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08969570B2

Reaction notes

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