90
3 In-Tether Chiral Center Induced Helical Peptide Modulators …
H2N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
MMP, MAP
365nm, hv
DMF
FmocHN
COOH
SH
H 2 N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
S
NHFmoc
HOOC
PyBOP, HATU,NMM
DMF
H
N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
FmocHN
O
S
H
N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
N
H
O
S
deprotection,
coupling,
...
H
N
N
H
H 2 N
O
O
OH
O
acetylation or FITC conjugation
Scheme 3.1 Schematic presentation of the synthesis process of peptides. Here take PhR
as an example, the thiol-ene click reaction was performed in a photo-reactor under a
wavelength of 365nm violet light. The photoreaction was repeated for three times, each
time last for 1hour. The yield of the photoreaction step reached to 90%. The unnatural amino acids were epimer and were synthesized followed the previous reported procedures. For each peptide sequences, we got two diastereomers which we named as S
or R. (Abbreviation: MMP: 2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiophenone; MAP:
4-methoxyacetophenone; PyBOP: benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate; NMM: N-Methylmorpholine; HATU: N-[(Dimethylamino)-1H-1,2,3-triazolo-[4,5b]pyridin-1-ylmethylene]-N-methylmethanaminium hexafluorophosphate N-oxide; FITC: fluorescein isothiocyanate; DMF: dimethylformamide)
3 In-Tether Chiral Center Induced Helical Peptide Modulators …
H2N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
MMP, MAP
365nm, hv
DMF
FmocHN
COOH
SH
H 2 N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
S
NHFmoc
HOOC
PyBOP, HATU,NMM
DMF
H
N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
FmocHN
O
S
H
N
N
H
H
N
N
H
O
O
O
O
H
N
N
H
H
N
N
H
O
O
O
O
(S/R)
HO
OH
NH2
O
HN
HO
N
NH
N
H
O
S
deprotection,
coupling,
...
H
N
N
H
H 2 N
O
O
OH
O
acetylation or FITC conjugation
Scheme 3.1 Schematic presentation of the synthesis process of peptides. Here take PhR
as an example, the thiol-ene click reaction was performed in a photo-reactor under a
wavelength of 365nm violet light. The photoreaction was repeated for three times, each
time last for 1hour. The yield of the photoreaction step reached to 90%. The unnatural amino acids were epimer and were synthesized followed the previous reported procedures. For each peptide sequences, we got two diastereomers which we named as S
or R. (Abbreviation: MMP: 2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiophenone; MAP:
4-methoxyacetophenone; PyBOP: benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate; NMM: N-Methylmorpholine; HATU: N-[(Dimethylamino)-1H-1,2,3-triazolo-[4,5b]pyridin-1-ylmethylene]-N-methylmethanaminium hexafluorophosphate N-oxide; FITC: fluorescein isothiocyanate; DMF: dimethylformamide)