Chemistry Reference
In-Depth Information
the
para
-fluoride of a pentafluorophenylporphyrin precursor [
79
]. Using this
methodology, boronated porphyrins
36
-
42
bearing linear polyamines were also
synthesized in high yields [
79
]. The tricarboranylporphyrin precursor to porphyrins
35
-
42
was obtained in 30% yield from reaction of
meso
-tetra(pentafluorophenyl)
porphyrin with 1-mercaptomethyl-
para
-carborane. Conjugation of this porphyrin
with the corresponding Boc-protected polyamines or
tert
-butyl-protected PEG using
NMP at 100
C, followed by deprotection with TFA gave porphyrins
35
-
42
in
>
90%
yields.
The BOPP derivative
43
(as regioisomeric mixture) conjugated to a NLS was
synthesized from
m
-BOPP (
meta
-carborane analogue of BOPP) by conjugation of a
mixture of mono-methyl ester
m
-BOPP to the NLS peptide on rink amide resin,
using HATU as the coupling agent [
80
].
Porphyrin
44
containing the cell-penetrating peptide HIV-1 Tat (48-60) with the
sequence GRKKRRQRRRPPQ was prepared by conjugation of a porphyrin bearing
three Co(III)-bis(dicarbollides) and a free carboxylic acid with the pegylated
peptide on PAL-PEG-PS resin using HOBt/TBTU/DIPEA [
59
]. After cleavage
from the solid support and deprotection using a mixture consisting of TFA/TIS/
H
2
O/phenol 88:2:5:5, porphyrin
44
was obtained in 8% yield.
