E. Graf, M. W. Hosseini et al.
and not refined (riding model). Owing to the presence of disordered sol-
vent molecules, the SQUEEZE[28] command was used.
OCH2n), 3.72 (m; OCH2m), 4.00 (m, 4H; OCH2l), 4.56 (m, 4H; OCH2k),
5.87 (t, 2H, NHt; 3J=6.0 Hz), 7.43 (dd, 2H, 3J=8.5 Hz, 4J=2.5 Hz; Arj),
7.67 (t, 1H, 3J=7.5 Hz; Pys), 7.69 (t, 2H, 3J=8.0 Hz; Ari), 7.75 (d, 2H,
3J=7.5 Hz; Pyr), 7.77 (d, 2H, 3J=7.5 Hz; Arh), 8.10 (dd, 2H, 3J=8.0 Hz,
4J=1.5 Hz; Ara), 8.18 (dd, 2H, 3J=8.0 Hz, 4J=1.5 Hz; Ara’), 8.19 (br s,
2H; Arg), 8.30 (dd, 2H, 3J=8.0 Hz, 4J=1.5 Hz; Arb), 8.51 (dd, 2H, 3J=
Crystallographic data for strapped porphyrin 2: C69H61Cl2N9O10Sn; Mw =
1365.86; monoclinic; space group: C2/c; a=63.9066(17), b=10.1342(3),
c=25.7502(8) ꢂ; Z=8;
b=105.579(2)8;
U=16064.2(8) ꢂ3;
m=
0.438 mmÀ1; total reflns: 72794; unique reflns: 19772 [R
ACHTUNGTERN(NGNU int)=0.0648];
8.0 Hz, 4J=1.5 Hz; Arb’), 8.96 (d, 4H, 3J=4.5 Hz, J
pyrc), 9.20 ppm (d, 4H, 3J=5.0 Hz, J(Sn,H)=15.0 Hz; b-pyrd); 13C NMR
ACHTUNGTREN(NUGN Sn,H)=15.0 Hz; b-
final R indices [I> 2s(I)]: R1 =0.1138; wR2 =0.3093; R indices (all data):
R1 =0.1737; wR2 =0.3159; GOF on F2: 1.319. CCDC-867898 (2) contains
the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Synthesis: Compounds 6,[20b] 10,[22] and 15[19] were prepared according to
literature procedures.
AHCTUNGTRENNUNG
(CD2Cl2, 150 MHz): d=37.4, 68.4, 68.8, 69.8, 70.0, 70.7, 70.8, 71.4, 112.8,
115.8, 119.2, 119.7, 122.5, 122.9, 123.8, 128.3, 128.8, 131.2, 131.4, 132.3,
133.9, 135.7, 136.3, 138.2, 142.1, 146.0, 146.5, 147.0, 148.2, 158.3,
163.3 ppm; IR (ATR): 2229 (CN), 1673 cmÀ1 (CO amide); UV/Vis
(CH2Cl2): lmax (e)=430 (5.6), 560 (4.2), 600 nm (3.9 molÀ1 dm3 cmÀ1).
1H NMR ([D6]DMSO, 600 MHz): d=À6.21 (br s, 1H; OH), À5.21 (br s,
1H; OH), 1.98 (q, 4H, 3J=6.5 Hz; NCH2v), OCH2q overlapped with
DMSO signal, 3.07 (m, 4H; OCH2p), OCH2o overlapped with water
signal, 3.46 (m, 4H; OCH2n), 3.63 (m; OCH2m), 3.90 (m, 4H; OCH2l),
4.46 (m, 4H; OCH2k), 7.09 (t, 2H, 3J=6.0 Hz; NHt), 7.47 (dd, 2H, 3J=
8.0 Hz, 4J=1.5 Hz; Arj), 7.75 (t, 2H, 3J=8.0 Hz; Ari), 7.78 (m, 4H; Pyr,
Compound 1: Compound 13 (650 mg, 896 mmol, 1 equiv) and compound
15 (443 mg, 1.8 mmol, 2 equiv) were dissolved under an argon atmos-
phere in CH2Cl2/EtOH (95:5, 100 mL) in a 250 mL dry two-necked
round-bottomed flask. In the dark, TFA (200 mL, 2.7 mmol, 3 equiv) was
added and the reaction mixture was stirred at RT for 2 days. First, trie-
thylamine was added to neutralize any excess TFA; then, a solution of
DDQ (610 mg, 2.7 mmol, 3 equiv) in THF (20 mL) was added and the
mixture was stirred overnight. After evaporation under reduced pressure,
the crude product was purified by column chromatography on silica gel
(CH2Cl2 to CH2Cl2/MeOH, 95:5) to yield compound 1 (100 mg, 9%) as
a purple powder.
3
3
Arh), 7.87 (t, 1H, J=7.5 Hz; Pys), 7.99 (br s, 2H; Arg), 8.31 (dd, 2H, J=
7.5 Hz, 4J=1.5 Hz; Ara), 8.36 (m, 4H; Ara’, Arb), 8.48 (dd, 2H, 3J=
7.5 Hz, 4J=1.5 Hz; Arb’), 8.93 (d, 4H, 3J=4.5 Hz, J
ACTHNUTRGNE(NUG Sn,H)=13.5 Hz; b-
pyrc), 9.05 ppm (d, 4H, 3J=5.0 Hz, J
ACTHNUTRGNEU(NG Sn,H)=13.5 Hz; b-pyrd). MS (ESI):
m/z calcd for C69H63N9O12Sn: 1330.371 [M+H]+; found: 1130.289.
Compound 7: Compound 6 (15.4 g, 44 mmol, 1 equiv) was dissolved in
dry DMF (150 mL) in a 500 mL two-necked round-bottomed flask. Potas-
sium phthalate (10 g, 54 mmol, 1.2 equiv) was added and the mixture was
heated under an argon atmosphere at 1208C overnight. After removal of
the solvent under vacuum, the residue was dissolved in distilled water
(250 mL) and extracted with CH2Cl2 (3ꢄ150 mL). The organic layer was
dried over MgSO4 and the solvent was removed under vacuum to afford
compound 7 (14.6 g, 73%) as an oil.
1H NMR (CDCl3, 300 MHz): d=3.54–3.76 (m, 14H; OCH2), 3.90 (t, 2H,
3J=6.0 Hz; OCH2), 7.69–7.72 (m, 2H; Ar), 7.83–7.86 ppm (m, 2H; Ar);
13C NMR (CDCl3, 75 MHz): d=37.4, 61.9, 68.1, 70.2, 70.5, 70.6, 70.8,
72.6, 123.4, 132.3, 134.1, 168.4 ppm; elemental analysis calcd (%) for
C16H21NO6: C 59.43, H 6.55, N 4.33; found: C 59.34, H 6.54, N 4.55.
1H NMR (CD2Cl2, 400 MHz): d=À2.92 (br s, 2H; NH), 2.29 (m, 4H;
3
OCH2p), 2.48 (t, 4H, J=6.0 Hz; OCH2q), 2.69 (m, 4H; OCH2o), 2.73 (q,
4H, 3J=6.0 Hz; NCH2v), 3.18 (m, 4H; OCH2n), 3.44 (m; OCH2m), 3.76
(m, 4H; OCH2l), 4.31 (m, 4H; OCH2k), 7.16 (m, 2H; NHt), 7.35 (dd, 2H,
3J=8.5 Hz, 4J=2.0 Hz; Arj), 7.45 (m, 1H; Pys), 7.70 (t, 2H, 3J=8.0 Hz;
Ari), 7.75 (d, 2H, 3J=8.0 Hz; Pyr), 7.81 (br s, 2H; Arg), 7.98 (d, 2H, 3J=
7.5 Hz; Arh), 8.08 (m, 4H; Araa’), 8.28 (m, 2H; Arb), 8.45 (m, 2H; Arb’),
8.78 (d, 4H, 3J=5.0 Hz; b-pyrc), 8.95 ppm (d, 4H, 3J=5.0 Hz; b-pyrd);
13C NMR (CD2Cl2, 100 MHz): d=38.5, 68.4, 68.7, 69.2, 69.9, 70.2, 70.3,
70.9, 115.3, 122.6, 124.2, 127.3, 128.0, 131.1, 132.3, 135.4, 138.4, 148.5,
157.9, 163.2; IR (ATR): 2228 (CN), 1674 cmÀ1 (CO amide); UV/Vis
(CH2Cl2): lmax (e)=418 (5.6), 516 (4.3), 550 (3.9), 589 (3.8), 646 nm
(3.6 molÀ1 dm3 cmÀ1); MS (MALDI-TOF): m/z calcd for C69H63N9O10
1178.478 [M+H]+; found: 1178.481.
:
Compound 8: Compound 7 (13 g, 40 mmol, 1 equiv) was dissolved in
EtOH (250 mL) in a 500 mL two-necked round-bottomed flask under an
argon atmosphere. Hydrazine monohydrate (4 mL, 82 mmol, 2 equiv)
was added and the solution was heated at reflux overnight. The reaction
mixture was acidified with 6m HCl (15 mL) and filtered. After removal
of the solvent, the residue was dissolved in EtOH (50 mL) and filtered
before distilled water (50 mL) was added and the mixture was filtered
again. Evaporation of the solvent under reduced pressure afforded a resi-
due that was dissolved in water and purified on a Dowex 50WX8 column
to afford compound 8 (7.1 g, 90%) as an oil.
1H NMR (CDCl3, 300 MHz): d=3.11 (t, 2H, 3J=5.0 Hz; OCH2), 3.60–
3.71 (m, 10H; NCH2, OCH2), 3.75–3.79 ppm (m, 4H; OCH2); 13C NMR
(CDCl3, 75 MHz): d=40.4, 61.2, 68.7, 69.9, 70.1, 70.4, 70.4, 72.7 ppm; ele-
mental analysis calcd (%) for C8H19NO4·0.5HCl·0.75H2O: C 42.71,
H 9.41, N 6.23; found: C 42.73, H 9.37, N 6.59.
Compound 2: In a 50 mL round-bottom flask, compound 1 (30 mg,
25 mmol, 1 equiv) and SnCl2·2H2O (23 mg, 100 mmol, 4 equiv) were dis-
solved in pyridine (15 mL) and the solution was refluxed overnight. The
solvent was removed under vacuum and the residue was filtered over
celite and the latter was washed with CH2Cl2. Removal of the solvent af-
forded the compound 2 (20 mg, 57%) as a purple solid.
1H NMR (CD2Cl2, 400 MHz): d=2.28 (br s, 4H; NCH2v), 2.60 (br s, 4H;
OCH2q), 3.05 (br s, 4H; OCH2p), 3.31 (br s, 4H; OCH2o), 3.45 (br s, 4H;
OCH2n), 3.65 (br s; OCH2m), 3.94 (br s, 4H; OCH2l), 4.42 (br s, 4H;
OCH2k), 6.13 (br s, 2H; NHt), 7.45 (d, 2H, 3J=8.0 Hz; Arj), 7.75 (t, 2H,
3J=8.0 Hz; Ari), 7.89 (m, 3H; Arh, Pys), 8.02 (br s, 2H; Arg), 8.06 (d, 2H,
3J=7.5 Hz; Pyr), 8.12 (d, 4H, 3J=7.5 Hz; Araa’), 8.21 (m, 2H; Arb), 8.34
(m, 2H; Arb’), 9.12 (d, 4H, 3J=5.0 Hz; b-pyrc), 9.37 ppm (d, 4H, 3J=
5.0 Hz; b-pyrd); 13C NMR (CD2Cl2, 100 MHz): d=38.1, 68.4, 68.8, 69.9,
70.1, 70.5, 71.3, 113.2, 115.3, 118.7, 122.9, 124.7, 128.5, 131.4, 132.4, 133.9,
135.3, 135.9, 138.8, 141.3, 144.8, 145.8, 146.8, 148.5, 158.0, 162.8 ppm; UV/
Vis (CH2Cl2): lmax (e)=431 (5.6), 562 (4.3), 602 nm (4.0 molÀ1 dm3 cmÀ1);
MS (ESI): m/z calcd for C69H61Cl2N9O10Sn: 1388.284 [M+Na]+; found:
1388.256.
Compound 11: Compound 8 (3.1 g, 16 mmol, 1.9 equiv) and triethylamine
(7 mL, 50 mmol, 6.3 equiv) were dissolved in dry CH2Cl2 (200 mL) in
a dry 500 mL two-necked round-bottomed flask under an argon atmos-
phere. Compound 10 (1.7 g, 8 mmol, 1 equiv) was dissolved under an
argon atmosphere in dry CH2Cl2 (100 mL) and added dropwise via a can-
nula. The reaction mixture was stirred overnight under an argon atmos-
phere at RT. After removal of the solvent under vacuum, the crude prod-
uct was purified by column chromatography on alumina (CH2Cl2 to
CH2Cl2/MeOH, 95:5) to afford compound 11 (4 g, 96%) as an oil.
Compound 3: Compound 2 (20 mg, 15 mmol, 1 equiv) and potassium car-
bonate (87 mg, 660 mmol, 44 equiv) were dissolved in CH2Cl2/MeOH
(4:1, 20 mL) in a 50 mL round-bottomed flask and heated to reflux for
5 h. The organic layer was washed with distilled water and dried over
MgSO4. After removal of the solvent under vacuum, the residue was pu-
rified by column chromatography on alumina (CHCl3 to CHCl3/MeOH,
98:2) to yield the desired compound 3 (7 mg, 37%) as a purple solid.
1H NMR (CD2Cl2, 600 MHz): d=À7.51 (br s, 1H; OHw), À6.49 (br s,
1H; OHw’), 1.67 (q, 4H, 3J=6.5 Hz; NCH2v), 2.34 (t, 4H, 3J=7.0 Hz;
OCH2q), 2.96 (m, 4H; OCH2p), 3.28 (m, 4H; OCH2o), 3.54 (m, 4H;
1H NMR (CDCl3, 300 MHz): d=3.36 (br s, 2H; OH), 3.58–3.71 (m, 32H;
3
3
NCH2, OCH2), 7.99 (t, 1H, J=8.0 Hz; Py), 8.32 (d, 2H, J=8.0 Hz; Py),
8.95 ppm (br s, 2H; NH). 13C NMR (CDCl3, 75 MHz): d=39.8, 61.9, 70.4,
70.4, 70.5, 70.6, 72.7, 124.9, 138.8, 149.1, 164.2 ppm; elemental analysis
calcd (%) for C23H39N3O10·0.5H2O: C 52.46, H 7.66, N 7.98; found:
C 52.55, H 7.90, N 7.95.
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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