Diethyl Ether → O-allyl L-seryl L-valyl L-valyl O-allyl L-seryl glycine methyl ester trifluoroacetate

HRID 2370907Notes

Reaction equation

HRID 2370907 reaction equation
[CH3:1][O:2][C:3](=[O:45])[CH2:4][NH:5][C:6](=[O:44])[C@H:7]([CH2:39][O:40][CH2:41][CH:42]=[CH2:43])[NH:8][C:9](=[O:38])[C@H:10]([CH:35]([CH3:37])[CH3:36])[NH:11][C:12](=[O:34])[C@H:13]([CH:31]([CH3:33])[CH3:32])[NH:14][C:15](=[O:30])[C@H:16]([CH2:25][O:26][CH2:27][CH:28]=[CH2:29])[NH:17]C(OC(C)(C)C)=O.CCOCC.[C:51]([OH:57])([C:53]([F:56])([F:55])[F:54])=[O:52]>C(Cl)Cl>[F:54][C:53]([F:56])([F:55])[C:51]([OH:57])=[O:52].[CH3:1][O:2][C:3](=[O:45])[CH2:4][NH:5][C:6](=[O:44])[C@H:7]([CH2:39][O:40][CH2:41][CH:42]=[CH2:43])[NH:8][C:9](=[O:38])[C@H:10]([CH:35]([CH3:36])[CH3:37])[NH:11][C:12](=[O:34])[C@H:13]([CH:31]([CH3:33])[CH3:32])[NH:14][C:15](=[O:30])[C@H:16]([CH2:25][O:26][CH2:27][CH:28]=[CH2:29])[NH2:17]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 6422Trifluoroacetic acid2×HCID 86671359N-tert-butoxycarbonyl O-allyl L-seryl L-valyl L-valyl O-allyl L-seryl glycine methyl ester

Product 1

HCID 86671361O-allyl L-seryl L-valyl L-valyl O-allyl L-seryl glycine methyl ester trifluoroacetateYield 96%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

N-tert-butoxycarbonyl O-allyl L-seryl L-valyl L-valyl O-allyl L-seryl glycine methyl ester 22 (SEQ ID NO: 1) (0.734 g, 1.14 mmol) was dissolved in a 50% (v/v) solution of TFA in CH2Cl2 (16 mL). The reaction mixture was stirred for 1 h 30 min before the solvent and bulk of excess TFA were evaporated affording an oil. Addition of Et2O (25 mL) resulted in the precipitation of a white solid. The mixture was centrifuged and the Et2O decanted off. The residue was washed with an additional 2×25 mL Et2O and dried under reduced pressure overnight affording a fine white powder (0.719 g, 96%); δH (300 MHz; d6-DMSO) 8.48 (1H, d, J 9, NH(Valx)), 8.41 (1H, t, J 6, NH(Gly)), 8.24 (3H, br s, NH3+), 8.01-7.98 (2H, m, NH(Valy)/NH(Ser(All)2)), 5.90-5.77 (2H, m, CH═CH2), 5.30-5.10 (4H, m, CH═CH2), 4.56-4.50 (1H, m, CαH(Ser(All)2)), 4.32 (1H, dd, J 7 and 9, CαH(Valx)), 4.24 (1H, dd, J 7 and 8, CαH(Valy)), 4.10 (1H, br s, CαH(Ser(All)1)), 3.98-3.93 (4H, m, CH2CH═CH2), 3.86-3.84 (2H, m, CαH2(Gly)), 3.72-3.52 (4H, m, CH2(Ser(All)1)/CH2(Ser(All)2)), 3.61 (3H, s, OCH3), 2.08-1.89 (2H, m, CH(CH3)2), 0.88-0.80 (12H, m, CH3); δC (75 MHz; d6-DMSO) 170.6, 170.4, 169.9, 169.8, 166.2, 158.3 (q, JCF 37) 134.8, 134.4, 117.1, 116.9 (q, JCF 293), 116.5, 71.4, 71.0, 69.5, 68.3, 57.9, 57.6, 52.4, 52.2, 51.6, 40.6, 30.6, 30.4, 19.1, 18.1, 17.9; m/z (ESI) 542.3181 (M+; C25H44N5O8 requires 542.3189)

Workup

  1. customwere evaporated
  2. customaffording an oil
  3. customresulted in the precipitation of a white solid
  4. customthe Et2O decanted off
  5. washThe residue was washed with an additional 2×25 mL Et2O
  6. customdried under reduced pressure overnight

Sources & evidence

ORD record
ord-85da5706f2a941929afe3ca1e79d666a
Source dataset
uspto-grants-2014_04
Patent number
US08710008B2

Reaction notes

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