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 1741435Notes

Reaction equation

HRID 1741435 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 (4) (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 (5) (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-cb6d2c23a64048858607271730d08b0c
Source dataset
uspto-grants-1999_10
Patent number
US05973113

Reaction notes

Loading…