1,2-Dichloroethane → HCID 131727256, compound

HRID 1455486Notes

Reaction equation

HRID 1455486 reaction equation
[NH2:1][C@H:2]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[C@@H:3]([CH3:5])[OH:4].Cl.CCN(C(C)C)C(C)C.[NH:23]([C:35]([O:37][CH2:38][CH:39]=[CH2:40])=[O:36])[C@H:24]([C:32](O)=[O:33])[CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C(Cl)CCl>C(Cl)Cl>[NH:23]([C:35]([O:37][CH2:38][CH:39]=[CH2:40])=[O:36])[C@H:24]([C:32]([NH:1][C@H:2]([C:6]([O:8][C:9]([CH3:11])([CH3:10])[CH3:12])=[O:7])[C@@H:3]([CH3:5])[OH:4])=[O:33])[CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

6

Reactant 4

HCID 111,2-DichloroethaneHCID 81531DiisopropylethylamineHCID 13968131N-{[(Prop-2-en-1-yl)oxy]carbonyl}-L-phenylalanineHCID 4462986569320-90-7

Product 1

HCID 131727256HCID 131727256, compoundYield 72.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

H-Thr-OtBu-HCl (3.1 g, 15 mmol, 1.3 equiv) was dissolved in CH2Cl2 (30 mL) and DIEA (2.9 mL, 17 mmol, 1.5 equiv) was added and the mixture allowed to stir for 30 min. Alloc-Phe-OH (2.8 g, 11 mmol, 1 equiv) and EDC (2.8 g, 15 mmol, 1.3 equiv) in CH2Cl2 (35 mL) was then added and the reaction was stirred for 18 h. The organic reaction mixture was washed with H2O (3×25 mL), dried (MgSO4) and concentrated in vacuo. The resultant oil (4.12 g) was purified by flash chromatography [CHCl3-MeOH—HOAc (9:1:0.2)] to give the title product (3.25 g, 8 mmol, 71% yield), which was characterized by analytical HPLC (tR 20.9 min, >98% purity; Condition C); ESMS, calcd for C21H30N2O6, 406.2. Found: m/z 408.0 [M+H]+; 1H-NMR (200 MHz, CDCl3): 7.1-7.3 (5H, m, Ar); 6.89 (1H, d, J=8.8 Hz, NH); 5.7-5.9 (1H, m, CH allyl); 5.56 (1H, d, J=8.0 Hz, OH); 5.2-5.3 (2H, m, CH2 g-allyl); 4.52 (2H, d, J=5.4 Hz, CH2 a-allyl); 4.45 (1H, dd, J=8.4 Hz, 2.8 Hz, a-CH Thr); 4.22 (1H, dq, J=6.2 Hz, J=3.0 Hz, b-CH Thr); 3.0-3.2 (2H, m, b-CH2 Phe); 1.47 (9H, s, tBu); 1.15 (3H, d, J=6.6 Hz, g-CH3 Thr); 13C-NMR (50 MHz, CDCl3): 172.2 (CO), 169.5 (CO); 156.0 (CO); 136.1 (Cq, Ar); 132.5 (CH, allyl); 129.3 (CH, Ar); 128.5 (CH, Ar); 126.9 (CH, Ar); 117.7 (CH2, allyl); 82.7 (Cq, tBu); 68.5 (b-CH Thr); 65.9 (CH2, allyl); 58.0 (a-CH Thr); 56.2 (a-CH Phe); 38.3 (b-CH2 Phe); 28.0 (CH3, tBu); 20.8 (g-CH3 Thr).

Workup

  1. stirringthe reaction was stirred for 18 h
  2. washThe organic reaction mixture was washed with H2O (3×25 mL)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customThe resultant oil (4.12 g) was purified by flash chromatography [CHCl3-MeOH—HOAc (9:1:0.2)]

Sources & evidence

ORD record
ord-f2a9dc1b5f9343f8b448bee67ebbf555
Source dataset
uspto-grants-2009_01
Patent number
US07482429B2

Reaction notes

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