Allyl bromide → HCID 70003054, compound

HRID 1264399Notes

Reaction equation

HRID 1264399 reaction equation
[C:1]([O:5][C:6](=[O:49])[CH2:7][NH:8][C:9]([C@@H:11]1[CH2:15][C@@H:14]([S:16][C:17]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH2:13][N:12]1[S:36]([C:39]1[CH:48]=[CH:47][C:46]2[C:41](=[CH:42][CH:43]=[CH:44][CH:45]=2)[CH:40]=1)(=[O:38])=[O:37])=[O:10])([CH3:4])([CH3:3])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:60](Br)[CH:61]=[CH2:62]>C1COCC1>[C:1]([O:5][C:6](=[O:49])[CH:7]([NH:8][C:9]([C@@H:11]1[CH2:15][C@@H:14]([S:16][C:17]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:13][N:12]1[S:36]([C:39]1[CH:48]=[CH:47][C:46]2[C:41](=[CH:42][CH:43]=[CH:44][CH:45]=2)[CH:40]=1)(=[O:38])=[O:37])=[O:10])[CH2:62][CH:61]=[CH2:60])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 2733832Lithium HexamethyldisilazideHCID 70001149HCID 70001149, compound

Product 1

HCID 70003054HCID 70003054, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 346 mg (0.5 mmol) (2S,4R)-{[1-(Naphthalene-2-sulfonyl)-4-tritylsulfanyl-pyrrolidine-2-carbonyl]-amino}-acetic acid tert-butyl ester in 10 ml THF at −78° C. was treated with 1.1 ml (1M in THF, 1.1 mmol) Lithium bis(trimethlsilyl)amide solution (LiHMDS). 0.127 ml (1.5 mmol) Allylbromide was added after 30 min and the reaction was warmed up to RT over night. The reaction was partitioned between aqueous 10% KHSO4/EtOAc (4×), the organic phases were washed with aqueous 10% NaCl, dried over Na2SO4 and evaporated. Purification by flash-chromatography on silicagel (Hexane/EtOAc 2:1) and precipitation with Et2O/pentane gave 76 mg (21%) (2RS)-2-{(2S,4R)-[1-(Naphthalene-2-sulfonyl)-4-tritylsulfanyl-pyrrolidine-2-carbonyl]-amino}-pent-4-enoic acid tert-butyl ester, MS: 733 (MH+).

Workup

  1. customThe reaction was partitioned between aqueous 10% KHSO4/EtOAc (4×)
  2. washthe organic phases were washed with aqueous 10% NaCl
  3. dry with materialdried over Na2SO4
  4. customevaporated
  5. customPurification by flash-chromatography
  6. customon silicagel (Hexane/EtOAc 2:1) and precipitation with Et2O/pentane

Sources & evidence

ORD record
ord-f6c9b7dd44064f39ad7865bf987303a7
Source dataset
uspto-grants-2003_04
Patent number
US06541638B2

Reaction notes

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