Allyl bromide → HCID 10925097, compound

HRID 625825Notes

Reaction equation

[C:1]([NH:8][C@H:9]([C:16]([O:18][CH3:19])=[O:17])[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:30](Br)[CH:31]=[CH2:32]>O1CCCC1>[CH2:32]([C@H:11]([C:12]([O:14][CH3:15])=[O:13])[CH2:10][C@H:9]([NH:8][C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[C:16]([O:18][CH3:19])=[O:17])[CH:31]=[CH2:30]

Participants

Conditions

Temperature: -70 °C

Procedure

11.01 g (40 mmol) of dimethyl Boc-glutamate (Advanced Chemtech) were dissolved in 160 ml of tetrahydrofuran and cooled to −70° C. 88 ml (88 mmol) of a 1M solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran were added dropwise at this temperature over a period of one hour, and the mixture was stirred at −70° C. for another 2 hours. 14.52 g (120 mmol) of allylbromide were then added dropwise, and after 2 h at this temperature, the cooling bath was removed and 200 ml of 2N aqueous hydrochloric acid and 400 ml of ethyl acetate were added. The organic phase was separated off, washed with water until neutral, dried over sodium sulphate and filtered, and the filtrate was concentrated. The crude product obtained in this manner was chromatographed in silica gel using a hexane/ethyl acetate gradient, and the appropriate fractions were combined and concentrated.

Workup

waitafter 2 h at this temperature
customthe cooling bath was removed
addition200 ml of 2N aqueous hydrochloric acid and 400 ml of ethyl acetate were added
customThe organic phase was separated off
washwashed with water until neutral,
dry with materialdried over sodium sulphate
filtrationfiltered
concentrationthe filtrate was concentrated

Sources & evidence

ORD record: ord-a93afc5edae945029d9ffa5deaf7fe91
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09308282B2

Reaction notes

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