Sulfuric acid magnesium salt (1:1) → (2S,9S)-7-Benzyl-2-[(tert-butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid, tert-Butyl Ester

HRID 2298494Notes

Reaction equation

HRID 2298494 reaction equation
[C:1]([O:5][C:6](=[O:28])[C@H:7]([CH2:16][CH2:17][CH2:18][CH2:19][NH:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])([CH3:4])([CH3:3])[CH3:2].[CH2:29]([C@H:31]1[O:33][CH2:32]1)[Cl:30].[O-]S([O-])(=O)=O.[Mg+2]>CO>[CH2:21]([N:20]([CH2:32][C@H:31]([OH:33])[CH2:29][Cl:30])[CH2:19][CH2:18][CH2:17][CH2:16][C@H:7]([NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:28])[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

Participants

5

Reactant 3

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 149428(+)-EpichlorohydrinHCID 10786720NepsilonBenzyl-Nalpha-BOC-L-Lysine tert-Butyl Ester

Product 1

HCID 10600926(2S,9S)-7-Benzyl-2-[(tert-butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid, tert-Butyl EsterYield 77%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of Nε-benzyl-Nα-BOC-L-lysine t-butyl ester (24) (16.0 g, 40.76 mmol), CH3OH (40 ml), (S)-(+)-epichlorohydrin (4.17 g, 45.0 mmol) and anhydrous MgSO4 (5.33 g. 44.28 mmol) was stirred under N2 for three days. The solids were filtered off and washed with CH3OH. The filtrate was concentrated at room temperature to give a yellow oil. The resulting oil was purified by flash chromatography on silica gel (66% hexane/ethyl acetate) to give 13.23 g of (25) (77%) as a colorless oil. 1H NMR (C6D6) δ7.18 (m, 5H), 5.00 (br d, 1H), 4.40 (m, 1H), 3.62 (m, 1H), 3.40-3.10 (m, 4H), 2.20-2.00 (m, 4H), 1.63 (m, 1H), 1.40 (s, 9H), 1.31 (s, 9H), 1.20 (m, 2H). 13C NMR (C6D6) δ171.7, 155.2, 138.8, 128.8, 127.9, 127.0, 80.8, 78.8, 67.7, 58.8, 57.2, 53.9, 53.7, 47.3, 32.5, 28.0, 27.5, 26.3, 22.8. HRMS m/z calcd. for C25H42ClN2O5 485.2782, found 485.2775. [α]25D+5.3° (c=1.00, CHCl3).

Workup

  1. filtrationThe solids were filtered off
  2. washwashed with CH3OH
  3. concentrationThe filtrate was concentrated at room temperature
  4. customto give a yellow oil
  5. customThe resulting oil was purified by flash chromatography on silica gel (66% hexane/ethyl acetate)

Sources & evidence

ORD record
ord-9dfe7bba867041a5852400aa3dbd0f3e
Source dataset
uspto-grants-2002_12
Patent number
US06492489B1

Reaction notes

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