t-Butyl bromide → N-[(phenylmethoxy)carbonyl]-L-tryptophan 1,1-dimethylethyl ester

HRID 2185587Notes

Reaction equation

[C:1]1([CH2:7][O:8][C:9]([NH:11][C@H:12]([C:23]([OH:25])=[O:24])[CH2:13][C:14]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[NH:16][CH:15]=2)=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([O-])([O-])=O.[K+].[K+].[C:32](Br)([CH3:35])([CH3:34])[CH3:33]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.CC(N(C)C)=O.O>[CH3:33][C:32]([O:24][C:23](=[O:25])[C@H:12]([CH2:13][C:14]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[NH:16][CH:15]=1)[NH:11][C:9]([O:8][CH2:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)=[O:10])([CH3:35])[CH3:34]

Participants

Conditions

Temperature: 550 °C

Procedure

Into a suspension of N-[(phenylmethoxy)carbonyl]-L-tryptophan (33.27 g; 98.32 mmol), benzyltriethylammonium chloride (BTEAC) (22.4 g; 98.32 mmol) and K2CO3 (176.91 g; 1.28 mol) in dimethylacetamide (750 mL), tert-butyl bromide (265 mL; 2.36 mol) was dropped. The solution was heated to 550° C. and maintained under vigorous stirring for 19 h. The reaction was monitored by HPLC (Chromatographic method of Example 3, A)). The solution was cooled to r.t., diluted with H2O (3 L) and then extracted with EtOAc (2 L). The organic layer was washed with H2O (2 L) and, after elimination of the solvent, N-[(phenylmethoxy)carbonyl]-L-tryptophan 1,1-dimethylethyl ester (36 g) was obtained and used in the following step without further purification.

Workup

additionwas dropped
temperaturemaintained
temperatureThe solution was cooled to r.t.
extractionextracted with EtOAc (2 L)
washThe organic layer was washed with H2O (2 L)

Sources & evidence

ORD record: ord-9749adb8d9f04bbc848be37946077e0c
Source dataset: uspto-grants-2002_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06403055B1

Reaction notes

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