Nalpha-(9-fluorenylmethoxycarbonyl)-Nepsilon-(4,4-bis(diallylphosphoryl)butyryl)-L-lysine → Nepsilon-(4,4-bis(diallylphosphoryl)butyryl)-L-lysine

HRID 39270

Reaction equation

HRID 39270 reaction equation
C1C2C(COC([NH:18][C@H:19]([C:46]([OH:48])=[O:47])[CH2:20][CH2:21][CH2:22][CH2:23][NH:24][C:25](=[O:45])[CH2:26][CH2:27][CH:28]([P:37]([CH2:42][CH:43]=[CH2:44])([CH2:39][CH:40]=[CH2:41])=[O:38])[P:29]([CH2:34][CH:35]=[CH2:36])([CH2:31][CH:32]=[CH2:33])=[O:30])=O)C3C(=CC=CC=3)C=2C=CC=1>N1CCCCC1.CN(C=O)C.C(OCC)(=O)C>[CH2:31]([P:29]([CH:28]([P:37]([CH2:39][CH:40]=[CH2:41])([CH2:42][CH:43]=[CH2:44])=[O:38])[CH2:27][CH2:26][C:25]([NH:24][CH2:23][CH2:22][CH2:21][CH2:20][C@@H:19]([C:46]([OH:48])=[O:47])[NH2:18])=[O:45])([CH2:34][CH:35]=[CH2:36])=[O:30])[CH:32]=[CH2:33]

Participants

4

Reactant 1

HCID 86762028Nalpha-(9-fluorenylmethoxycarbonyl)-Nepsilon-(4,4-bis(diallylphosphoryl)butyryl)-L-lysine

Product 1

HCID 86762027Nepsilon-(4,4-bis(diallylphosphoryl)butyryl)-L-lysineYield 85.6%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 23501187piperidine N,N-dimethylformamideSolvent

Procedure

A solution of 90 (502 mg, 0.616 mmol) in piperidine/DMF (0.05:1, 5 mL) was stirred at room temperature for 18 hr. After diluting with ethyl acetate (40 mL) the organic layer was washed with water and brine then dried over Na2SO4 and concentrated in vacuo. The crude material was purified by silica gel chromatography (methanol in ethyl acetate, 5% over 5 column volumes then 5 to 30% over 10 column volumes) using a Biotage Horizon™ apparatus resulting in the colourless liquid 91 (249 mg, 68%): 1H NMR (400 MHz, CDCl3) δ 1.39-1.74 (m, 6H), 1.45 (s, 9H), 2.21-2.35 (m, 2H), 2.51 (t, J=7.4, 2H), 2.55 (tt, J=6.9, 23.9, 1H), 3.19-3.25 (m, 2H), 3.29 (dd, J=5.2, 7.6, 1H), 4.58-4.63 (m, 8H), 5.25 (dq, J=1.3, 10.3, 4H), 5.38 (dq, J=1.4, 17.1, 4H), 5.90-6.00 (m, 4H), 6.14 (bd, J=4.9, 1H): 31P (162 MHz, CDCl3) δ 24.67 (s, 2P).

Workup

  1. washwas washed with water and brine
  2. dry with materialthen dried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe crude material was purified by silica gel chromatography (methanol in ethyl acetate, 5% over 5 column volumes

Sources & evidence

ORD record
ord-9ace8feb681144c797b9b24e1829a87f
Source dataset
uspto-grants-2013_09
Patent number
US08524691B2

Linked notes

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