L-Lysine → Ninhydrin

HRID 929370Notes

Reaction equation

HRID 929370 reaction equation
N[C@H:2]([C:11]([O:13]CC=C)=[O:12])[CH2:3][CH2:4][C:5]([O:7]CC=C)=O.ClC(Cl)([O:20]C(=O)OC(Cl)(Cl)Cl)Cl.CCN(CC)CC.N[C@H:37]([C:43](O)=O)[CH2:38][CH2:39]CCN>C(Cl)Cl>[CH:37]1[CH:43]=[C:4]2[C:5]([C:11]([OH:12])([OH:13])[C:2](=[O:20])[C:3]2=[CH:39][CH:38]=1)=[O:7]

Participants

6

Reactant 4

HCID 5962L-LysineHCID 8471TriethylamineHCID 94429TriphosgeneHCID 11053369diallyl L-glutamate

Product 1

HCID 10236Ninhydrin

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

To a stirred solution of diallyl glutamate (3.96 g, 15 mmol) and triphosgene (1.47 g, 4.95 mmol) in CH2Cl2 (143 mL) at −78° C. was added Et3N (6.4 mL, 46 mmol) in CH2Cl2 (28 mL). The reaction mixture was allowed to warm to room temperature and stirred for 1.5 h. The Lysine derivative (2.6 g, 9.09 mmol) in a solution of CH2Cl2 (36 mL) was then added at −78° C. and the reaction was stirred at room temperature for 12 h. The solution was diluted with CH2Cl2, washed twice with H2O, dried over MgSO4 (anh.) and purified by column chromatography (Hexane:AcOEt 3:1→2:1→AcOEt) to give 4 g (82%) (TLC in CH2Cl2:MeOH 20:1 Rf=0.3, revealed with ninhydrin). 1H-NMR (CDCl3, 300 MHz) δ 5.97-5.84 (m, 3H, 3-CH2CHCH2), 5.50 (bt, 2H, 2NHurea), 5.36-5.20 (m, 6H, 3-CH2CHCH2), 4.81 (bs, 1H, NHBoc), 4.68-4.40 (m, 8H, 3-CH2CHCH2, CH(Lys), CH(glu)), 3.09-3.05 (m, 2H, CH2NHBoc), 2.52-2.39 (m, 2H, CH2(glu.)), 2.25-2.14 and 2.02-1.92 (2m, 2H, CH2(glu.)), 1.87-1.64 (m, 4H, 2CH2(Lys)), 1.51-1.35 (m, 2H, CH2(Lys)), 1.44 (s, 9H, Boc).

Workup

  1. stirringthe reaction was stirred at room temperature for 12 h
  2. washwashed twice with H2O
  3. dry with materialdried over MgSO4 (anh.)
  4. custompurified by column chromatography (Hexane:AcOEt 3:1→2:1→AcOEt)

Sources & evidence

ORD record
ord-7265ee73d65d42bea61193e2f561a54b
Source dataset
uspto-grants-2016_03
Patent number
US09295727B2

Reaction notes

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