Hybrid Molecules Consisting of a CoII Mononuclear Complex and Porphyrins
FULL PAPER
NHCH2CH
NHCH2CH(CH3)2), 1.40 (s, 9H; Boc), 0.95, 0.97 (two singlets, 6H;
NHCH2CH
G
3J(H,H)=5.8 Hz, 1H; CONHiBu), 7.97 (t, 3J
ACTHNGUTRENNUG CAHTUNGTRENNUNG
NHCH2CH2CH2O), 7.43 (dd, 3J(H,H)=8.2 Hz, 4J
ACTHNGUTRENNUG CAHTUNGTRENNUNG
C5 H), 4.39 (t, 3J
A
G
ꢀ
C6 H), 8.67–8.70 (overlapping multiplet (om), 1H; bpy C6’ H), 8.43 (d,
(H,H)=6.3 Hz, 2H; NHCH2CH2CH2O), 3.30 (t, 3J
G
ꢀ
ꢀ
3J
(H,H)=8.0 Hz, 1H; bpy C3’ H), 8.40 (d, 3J
G
NHCH2CH
NHCH2CH2CH2O), 1.92 (nonet, 3J
(CH3)2), 0.99 (d, 3J
(H,H)=6.8 Hz, 6H; NHCH2CH
CO): 9.01 (d, 4J
A
ꢀ
C3 H), 8.18 (dd, 3J
E
(H,H)=2.8 Hz, 1H; bpy C4 H),
ꢀ
ꢀ
ꢀ
7.90–7.85 (om, 1H; bpy C4’ H), 7.36–7.33 (om, 1H; bpy C5’ H); trpy
R
ACHTUGNTREN(UNNG CH3)2); bpy (bpy
ꢀ
ꢀ
(trpy C6H3C(O)O
(CH2)4NH): 8.67–8.70 (om, 4H; trpy C3 H, trpy C3“
A
H, trpy C6 H, trpy C6” H), 8.63 (s, 2H; trpy C3’ H, trpy C5’ H), 8.12
H), 8.37 (d, 3J
N
A
ꢀ
(dd, 3J
(H,H)=8.0 Hz, 4J
(H,H)=2.0 Hz, 1H; Ar C4 H), 7.90–7.85 (om,
1H; bpy C3’ H), 8.14 (dd, 3J
ꢀ
2H; trpy C4 H, trpy C4“ H), 7.82 (dd, 3J
(H,H)=8.0 Hz, 4J
C4 H), 7.62 (td, 3J
ꢀ
ꢀ
ꢀ
2.0 Hz, 1H; Ar C6 H), 7.62 (dd, J
(H,H)=1.6 Hz, 1H;
7.16 (ddd, 3J
A
ꢀ
Ar C5 H), 7.36–7.33 (om, 2H; trpy C5 H, trpy C5” H), 3.29 (t, 3J-
C5’ H); trpy (trpy C6H3(CO)O
G
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
(H,H)=6.4 Hz, 2H; NHCH2CH2CH2CH2O), 3.12 (q, 3J
C5’ H), 8.62 (d, J
N
3
ꢀ
ꢀ
ꢀ
2H; NHCH2CH2CH2CH2O), 1.35–1.46 ppm (m, 3J
NHCH2CH2CH2CH2O).
E
(m, 2H; trpy C6 H and trpy C6” H), 8.06 (dd, 3J
(H,H)=7.6 Hz, 4J-
(H,H)=
(H,H)=7.4 Hz, 4J-
ꢀ
ꢀ
(H,H)=1.9 Hz, 1H; Ar C6 H), 7.74 (td, 3J
(H,H)=7.8 Hz, 4J
N
ꢀ
1.7 Hz, 2H; trpy C4 H, trpy C4“ H), 7.62 (dd, 3J
R
ꢀ
ꢀ
Compound 13a: Compound 10 (30.4 mg, 0.031 mmol) was dissolved in
trifluoroacetic acid (TFA, 2 mL) and the solution was stirred at RT.
After stirring for 2 h, the resulting solution was neutralized by the addi-
tion of saturated aqueous NaHCO3. The mixture was extracted with
CH2Cl2 and the organic phase was separated, evaporated, and dried
under vacuum. The deprotected compound 11 was obtained as a colorless
oil. The oil was dissolved in CH2Cl2 and compound 12a (24.9 mg,
0.030 mmol), DMAP (2.0 mg, 0.016 mmol), bis(2-oxo-3-oxazolidinyl)-
phosphinic chloride (BOP-Cl, 17.6 mg, 0.069 mmol), and N,N-diisopropy-
lethylamine (DIPEA, 30 mL, 0.17 mmol) were added to the solution, and
the mixture was stirred at RT. After 12 h, CH2Cl2 and saturated aqueous
NaHCO3 were added to the solution and the organic phase was separated
and the solvent was evaporated. Purification was performed by olumn
chromatography on alumina (CH2Cl2/MeOH 99:1), followed by recrystal-
lization from CH2Cl2/n-hexane. Yield: 29.7 mg (0.0176 mmol, 57%);
(H,H)=1.8 Hz, 1H; Ar C4 H), 7.39 (t, 3J
(H,H)=5.7 Hz, 1H; NH-
ꢀ
ꢀ
3
3
(CH2)4O), 7.33 (t, J
(H,H)=7.5 Hz, 1H; Ar C5 H), 7.19 (ddd, J
(H,H)=
3
4
ꢀ
ꢀ
7.4 Hz, J
U
ACHTUNGTRENNUNG
3.61 (t, 3J
U
ACHTUNGTRENNUNG
6.6 Hz, 2H; NHCH2CH2CH2CH2O), 1.51 (overlapping multiplets, 2H;
NHCH2CH2CH2CH2O), 1.39 (quintet, 2H; NHCH2CH2CH2CH2O); por-
phyrin: 8.89 (br s, 4H; bH), 8.84 (br s, 2H; bH), 8.67 (br s, 2H; bH), 8.20
4
(AA’BB’ system, 4H; C6H4CO), 8.08 (d, J
(H,H)=1.8 Hz, 2H; di-tert-bu-
tylphenyl C2 H and C6 H), 8.07 (d, 4J
ACTHNUTRGNEU(GN H,H)=1.8 Hz, 4H; di-tert-butyl-
phenyl C2 H and C6 H), 7.84 (m, 3H; di-tert-butylphenyl C4 H), 1.52
(s, 54H; C
(CH3)3), ꢀ2.81 ppm (s, 2H, inner NH).
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
AHCTUNGTRENNUNG
Compound 13c: This compound was synthesized according to the same
procedure as compound 13a using compound 9 (46.3 mg, 0.0477 mmol)
and TFA (3 mL); then compound 12c (34.5 mg, 0.0450 mmol), BOP-Cl
(26.5 mg, 0.104 mmol), DMAP (6.1 mg, 0.050 mmol), and DIPEA (35 mL,
0.200 mmol) in CH2Cl2 (5 mL). Yield: 59.6 mg (0.0368 mmol, 77%).
1H NMR (920 MHz, CD2Cl2, 258C): linker (NHC6H
G
3
A
G
C6 H), 8.03 (d, 4J
5.5 Hz, 1H; CONHiBu), 7.92 (t, 3J
7.41 (dd, 3J(H,H)=8.2 Hz, 4J(H,H)=1.6 Hz, 1H; Ar C5 H), 4.40 (t, 3J-
(H,H)=6.3 Hz, 2H; NHCH2CH2CH2O), 3.66 (q, 3J
(H,H)=6.2 Hz, 2H;
NHCH2CH2CH2O), 3.29 (t, 3J
(H,H)=6.4 Hz, 2H; NHCH2CH(CH3)2),
2.26 (quintet, 3J(H,H)=6.4 Hz, 2H; NHCH2CH2CH2O), 1.90 (nonet, 3J-
1H NMR (920 MHz, CD2Cl2, 258C): linker (NHC6H
(CH2)3NH): d 9.76 (s, 1H; NHC6H3), 8.14 (d, 3J
(H,H)=8.2 Hz, 1H; Ar
3ACHTUNGTRENUN(NG CONHiBu)O-
A
ACHTUNGTRENNUNG
C6 H), 8.06 (d, 4J(H,H)=1.8 Hz, 1H; Ar C3 H), 7.97 (t, 3J
AHTCUNGTRENNUGN ACHTUNGTRENNUNG
ꢀ
ꢀ
R
5.6 Hz,
1H;
CONHiBu),
7.89
(t,
3J
ACHTUNGTRENNUNG
NHCH2CH2CH2O), 7.44 (dd, 3J
A
ACHTUNGTRENNUNG
C5 H), 4.42 (t, 3J
(H,H)=6.0 Hz, 2H; NHCH2CH2CH2O), 3.65 (q, 3J-
ꢀ
A
A
R
NHCH2CH
NHCH2CH
NHCH2CH2CH2O), 1.90 (nonet, 3J
(CH3)2), 0.97 (d, 3J
(H,H)=6.5 Hz, 6H; NHCH2CH
CO): 9.00 (d, 4J
R
2.26
(quintet,
3J
ACHTUNGTRENNUNG
C6 H), 8.55 (m, 1H; bpy C6’ H), 8.40 (d, 3J
ACHTUNGTRENNUNG
C3 H), 8.36 (d, 3J
E
T
ACHTUGNTREN(UNNG CH3)2); bpy (bpy
ꢀ
8.1 Hz, 4J
(H,H)=1.8 Hz, 1H; bpy C6 H), 8.46 (m, 1H; bpy C6’
ꢀ
ꢀ
H), 8.35 (d, 3J
(H,H)=8.2 Hz, 1H; bpy C3 H), 8.28 (d, 3J
(H,H)=7.8 Hz,
ꢀ
A
1H; bpy C3’ H), 8.13 (d, 3J
(H,H)=8.2 Hz, 1H; bpy C4 H), 7.58 (t, 3J-
ꢀ
ꢀ
1.8 Hz, 1H; bpy C4’ H); trpy (trpy C6H3(CO)O
3
ꢀ
ꢀ
trpy C3’ H, trpy 5’ H), 8.62–8.65 (overlapping multiplet, 4H; trpy C3
A
(H,H)=5.9 Hz, 1H; bpy C5’
(CH2)4NH): 8.66 (s, 2H; trpy C3’ H, trpy
H, trpy C3“ H, trpy C6 H, trpy C6” H), 8.04 (dd, 3J
H); trpy (trpy C6H3(CO)O
E
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
A
C5’ H), 8.62 (d, J
(H,H)=7.6 Hz, 2H; trpy C3 H, trpy C3“ H), 8.61 (m,
1.6 Hz, 2H; trpy C4 H, trpy C4“ H), 7.62 (dd, 3J
2H; trpy C6 H, trpy C6” H), 8.04 (dd, 3J
(H,H)=7.6 Hz, 4J
(H,H)=1.8 Hz, 2H;
(H,H)=7.4 Hz, 4J
(H,H)=
(CH2)4O),
ACHTUNGTRENNUNG(H,H)=
ꢀ
ꢀ
(H,H)=1.6 Hz, 1H; Ar C4 H), 7.38 (t, 3J
1.8 Hz, 1H; Ar C6 H), 7.74 (td, 3J
(H,H)=7.6 Hz, 4J
G
ꢀ
trpy C4 H and trpy C4“ H), 7.61 (dd, 3J
E
ACHTUNGTRENNUNG
ꢀ
ꢀ
G
ꢀ
ꢀ
ꢀ
G
1.7 Hz, 1H; Ar C4 H), 7.39 (overlapping multiplet, 1H; NH
7.31 (t, J
N
C
3
U
(H,H)=7.6 Hz, 1H; Ar C5 H), 7.20 (ddd, 3J
(H,H)=7.4 Hz, 3J-
ꢀ
ꢀ
ꢀ
R
(H,H)=1.2 Hz, 2H; trpy C5 H, trpy C5” H), 3.59 (t,
C
R
ACHTUNGTREN(NUNG H,H)=7.1 Hz,
NHCH2CH2CH2CH2O); porphyrin: 8.68 (br s, 4H; bH), 8.62–8.65 (om,
A
2H; bH), 8.52 (br s, 2H; bH), 8.12 (d, 3J
G
NHCH2CH2CH2CH2O), 1.39 (quintet, 2H; NHCH2CH2CH2CH2O); por-
phyrin: 8.88 (br s, 4H; bH), 8.72 (br s, 2H; bH), 8.64 (br S, 2H; bH), 8.09
(AA’BB’ system, 4H; C6H4CO), 7.79–7.83 (m, 3H; di-fluorophenyl C4
ꢀ
Ar C6 H), 8.08 (d, 3J
(H,H)=7.6 Hz, 2H; Ar C3 H, Ar 5 H), 7.74 and
ꢀ
7.73 (2ꢂt, 3J
(H,H)=8.9 Hz, 3H; C6H
3A
ꢀ
ꢀ
ꢀ
ꢀ
br s, 6H; C6H
U
H), 7.39 (overlapping multiplet, 6H; di-fluorophenyl C3 H, di-fluoro-
ꢀ
phenyl C5 H), ꢀ2.92 ppm (s, 2H; inner NH).
Compound 13b: This compound was synthesized according to the same
procedure as compound 13a using compound 9 (42.5 mg, 0.0438 mmol)
and TFA (3 mL); then compound 12b (40.1 mg, 0.0403 mmol), BOP-Cl
(22.2 mg, 0.0871 mmol), DMAP (5.2 mg, 0.0426 mmol), and DIPEA
(35 mL, 0.200 mmol) in CH2Cl2 (5 mL). Yield: 51.5 mg (0.0279 mmol,
64%); 1H NMR (920 MHz, CD2Cl2, 258C): linker (NHC6H3-
Compound 1a: Compound 13a (16.0 mg, 0.0095 mmol) and zinc acetate
dihydrate (ZnACHTNUTRGNEUNG(OAc)2·2H2O, 16.7 mg, 0.076 mmol) were dissolved in
CH2Cl2/EtOH (1:1 wt%, 20 mL) and stirred for 5 h at 508C. After the re-
action had been completed, the solution was washed once with saturated
aqueous disodium dihydrogen ethylenediaminetetraacetate, and the or-
ganic phase was separated and evaporated to reduce the volume. The
zinc porphyrin compound 14a was precipitated by the addition of n-
ACHTUNGTRENNUNG(CONHiBu)OACHTUNGTRENNUNG ACUTHNGTRENNNUG
(CH2)3NH): d=9.53 (s, 1H; NHC6H3), 8.13 (d, 3J
4
ꢀ
ꢀ
8.2 Hz, 1H; Ar C6 H), 7.99 (d, J
ACHTUNGTRENNUNG
Chem. Eur. J. 2012, 18, 1781 – 1788
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1787