Inorganic Chemistry
Article
10. A sample of Zn10 (38.5 mg, 0.064 mmol) was dissolved in
CH2Cl2 (3 mL). TFA (1 mL) was added, and the reaction mixture was
stirred at room temperature for 2.5 h. The volatile components were
removed by rotary evaporation. The residue was dissolved in a mixture
of CH2Cl2 and dilute aqueous NaHCO3. The aqueous phase was
extracted once with CH2Cl2. The combined organic layer was dried
(MgSO4), filtered, and the filtrate was concentrated. The residue was
purified by silica column chromatography [pentane/CH2Cl2 (1:1) →
(m, 2H), 8.01−8.04 (m, 2H), 8.28, 8.31 (ABq, JAB = 4.3 Hz, 2H), 8.46
(s, 1H), 8.52−8.55 (m, 3H), 8.57−5.59 (m, 2H). 13C NMR (125
MHz, CDCl3/CD3OD) δ 23.9, 29.7, 30.9, 45.2, 50.4, 93.9, 96.1, 117.9,
123.2, 123.4, 126.4, 126.8, 127.1, 128.0, 128.1, 129.7, 132.7, 132.8,
133.7, 134.1, 137.5, 139.0, 143.1, 146.0, 146.1, 147.1, 147.2, 153.4,
153.8, 159.3, 170.1, 170.7. ESI-MS obsd 612.1714, calcd 612.1736 [(M
+ H)+, M = C36H39N5OZn]. λabs (CH2Cl2) 409, 504, 562, 608 nm.
17. A sample of 16a (109 mg, 0.196 mmol) and 6 (89 mg, 0.182
mmol) were dissolved in DMF (1.5 mL) under an N2 atmosphere.
DIPEA (62 μL, 0.364 mmol) was added, and the solution was stirred
under nitrogen for 3 min at rt before being cooled to 0 °C. HATU (75
mg, 0.182 mmol) was added, and stirring was continued with cooling
for 10 min and at rt for 48 h. EtOAc was added, and the solution was
washed 3 times with water and, then, once with saturated aqueous
solution of NaHCO3. The organic phase was dried (Na2SO4) and
concentrated. Column chromatography, [silica, CH2Cl2/MeOH (0 →
1
CH2Cl2] affording a dark green solid (30.7 mg, 89%): H NMR (500
MHz, CDCl3) δ −1.94 (br 2H), 2.08 (s, 6H), 4.64 (s, 2H), 7.72−7.75
(m, 3H), 8.12−8.14 (m, 2H), 8.28−8.30 (m, 2H), 8.37 (d, J = 4.5 Hz,
1H), 8.53 (d, J = 4.5 Hz, 1H), 8.57−8.59 (m, 2H), 8.67 (d, J = 4.7 Hz,
1H), 8.79−8.83 (m, 2H), 8.90 (d, J = 4.6 Hz, 1H), 8.94 (s, 1H), 9.03
(s, 1H). 13C NMR (125 MHz, CDCl3) δ 31.1, 31.2, 46.6, 51.8, 95.2,
97.4, 118.9, 121.9, 122.0, 122.4, 123.8, 124.0, 126.8, 127.0, 127.7,
127.8, 129.2, 131.1, 132.5, 133.89, 133.92, 134.0, 134.57, 134.61,
135.4, 140.4, 141.0, 141.9, 147.7, 149.3, 150.7, 152.4, 163.9, 175.6. ESI-
MS obsd 538.2191, calcd 538.2243 [(M + H)+, M = C34H27N5O2]. λabs
(CH2Cl2) 413, 507, 589, 641.
11. A sample of 10 (44.9 mg, 0.0836 mmol) was dissolved in THF
(5.9 mL). NH4HCO2 (53 mg, 0.84 mmol) and Pd/C (10%, 53 mg)
were added, and the mixture was heated at reflux for 2 h. The reaction
mixture was cooled to room temperature, filtered, and the filtrate was
diluted with CH2Cl2 and water. The aqueous layer was extracted once
with CH2Cl2. The combined organic phase was dried (MgSO4). The
sample was >95% pure (as shown by 1H NMR and HR-ESI-MS
analysis) and could be used without further purification. Alternatively,
column chromatography [silica, CH2Cl2/MeOH (100:0 → 9:1)]
afforded a deep red solid (42 mg, 98%): 1H NMR (500 MHz, CDCl3)
δ −1.75 (br, 2H), 2.07 (s, 6H), 4.59 (s, 2H), 6.83−6.85 (m, 2H),
7.73−7.75 (m, 3H), 7.88−7.90 (m, 2H), 8.16−8.18 (m, 2H), 8.52 (d, J
= 4.4 Hz, 1H), 8.60 (d, J = 4.4 Hz, 1H), 8.78 (s, 1H), 8.85−8.88 (m,
3H), 8.92 (s, 1H). 13C NMR (125 MHz, CDCl3) δ 31.2, 46.4, 51.8,
94.6, 96.5, 113.6, 122.0, 123.0, 123.1, 123.2, 126.8, 127.6, 128.7, 128.9,
131.7, 132.2, 132.6, 134.1, 135.0, 135.04, 135.3, 140.3, 140.9, 142.3,
145.5, 152.2, 152.6, 163.5, 174.9. ESI-MS obsd 508.2495, calcd
508.2496 [(M + H)+, M = C34H29N5]. λabs (CH2Cl2) 415, 508, 538,
586, 638 nm.
12. A sample of 11 (18 mg, 0.036 mmol) was dissolved in pyridine
(2.5 mL). Ac2O (2.5 mL) was added to the solution. Stirring was
continued at room temperature for 12 h. The reaction mixture was
diluted with CH2Cl2 and saturated aqueous NaHCO3. The aqueous
layer was extracted twice with CH2Cl2. The combined organic phase
was washed with multiple portions of NaHCO3 (sat. aq.), dried
(MgSO4), filtered, and the volatiles were evaporated. The solid residue
was purified by column chromatography (silica, CH2Cl2/MeOH, 0 →
10%) affording a deep red solid (17.9 mg, 80%, one molecule of
pyridine retained after extensive drying): 1H NMR (500 MHz, CDCl3)
δ −1.87 (br, 2H), 2.05 (s, 6H), 2.21 (s, 3H), 4.60 (s, 2H), 4.69 (br,
1H), 7.31−7.34 (m, 1H), 7.66 (br, 1H), 7.68−7.75 (m, 4H), 7.76−
7.78 (m, 2H), 8.06 (d, J = 8.4 Hz, 2H), 8.09 (br, 1H), 8.12−8.14 (m,
2H), 8.47−8.50 (m, 2H), 8.61 (d, J = 4.0 Hz, 1H), 8.77−8.83 (m,
4H), 8.86 (s, 1H), 8.96 (s, 1H). 13C NMR (125 MHz, CDCl3) δ 24.7,
31.2, 46.5, 51.8, 94.9, 96.9, 118.1, 121.8, 122.0, 123.4, 124.1, 126.8,
127.7, 128.8, 129.0, 129.8, 131.7, 134.1, 134.6, 135.0, 135.1, 136.9,
137.7, 137.9, 140.4, 141.1, 142.0, 149.0, 151.6, 163.8, 165.5 (x 2),
168.7, 175.3. ESI-MS obsd 550.2640, calcd 550.2601 [(M + H)+, M =
C36H31N5O]. λabs (CH2Cl2) 416, 509, 535, 587, 639 nm.
1
5%)] gave a green solid (92 mg, 46%): H NMR (multiple isomers
detected, data reported for all, 500 MHz, CDCl3) δ −2.37 (br, 1H),
−1.97 (br, 1H), 1.27−1.50 (m, 33H), 2.05 (s, 6H), 2.52−3.72 (m,
19H), 4.60 (2s, 2H), 4.65−4.77 (2s, 2H), 7.12 (t, J = 6.1 Hz, 0.62H),
7.30 (d, J = 8.6 Hz, 1.63H), 7.72 (t, J = 3.3 Hz, 0.25H), 8.02−8.08 (m,
2H), 8.63, 8.67 (2d, J = 4.3 Hz, 1H), 8.81−8.85 (m, 2H), 8.93−9.02
(m, 4H), 9.22−9.24 (m, 1H), 9.83−9.86 (m, 1H). 13C NMR (multiple
isomers detected, data reported for all, 125 MHz, CDCl3) δ 27.6,
27.71, 27.74, 27.8, 27.9, 27.97, 28.0, 28.1, 29.3, 29.6, 31.1, 31.2, 31.3,
33.3, 35.2, 36.4, 38.6, 46.37, 46.38, 48.0, 49.2, 49.9, 50.8, 51.8, 52.3,
52.5, 53.4, 54.0, 55.2, 56.1, 56.8, 67.3, 81.96, 82.04, 82.1, 82.5, 94.2,
86.9, 107.2, 113.3, 113.4, 120.9, 121.0, 123.3, 123.4, 123.7, 128.2,
128.37, 128.44, 132.0, 132.1, 132.4, 133.99, 134.04, 134.92, 134.94,
135.19, 135.24, 135.27, 135.33, 135.35, 139.4, 140.8, 140.9, 150.8,
152.6, 152.7, 157.2, 162.5, 162.86, 162.94, 168.8, 169.4, 170.1, 172.4,
173.0, 175.4, 175.5. ESI-MS obsd 1030.6163, calcd 1030.6124 [(M +
H)+, M = C58H80N9O8] obsd 515.8131, calcd 515.8099 (M + 2H)2+.
λabs (CH2Cl2) 406, 500, 584, 635 nm.
18. A sample of 16b (109 mg, 0.196 mmol) and 11 (70 mg, 0.138
mmol) were dissolved in DMF (2.5 mL). DIPEA (63 μL, 0.37 mmol)
was added, and the solution was stirred under nitrogen for 3 min at rt
before being cooled to 0 °C. HATU (62 mg, 0.15 mmol) was added,
and the mixture was stirred at 0 °C for 10 min and, then, at rt under
nitrogen for 48 h. Water and EtOAc were added. The aqueous layer
was extracted three times with EtOAc. The combined organic phase
was washed 3 times with water and once with saturated aqueous
solution of NaHCO3. The organic phase was dried (MgSO4) and
concentrated. Column chromatography, [silica, CH2Cl2/MeOH (0 →
10%)] gave a brown-red solid (114.6 mg, 77%): 1H NMR (500 MHz,
CDCl3) δ −1.89 (br, 2H), 1.41−1.45 (m, 27H), 2.06 (s, 6H), 2.32−
3.75 (m, 24H), 4.61 (s, 2H), 7.70−7.74 (m, 3.3H), 7.95−7.96 (m,
2.2H), 8.10−8.12 (m, 3.2H), 8.45−8.56 (m, 2.4H), 8.71−8.87 (m,
5H), 8.95, 8.97 (2 × br, 1H). 13C NMR (125 MHz, CDCl3) δ 27.90,
27.92, 31.2, 31.5, 36.59, 36.63, 46.5, 48.1, 51.8, 51.9, 52.5, 54.5, 54.7,
55.4, 55.5, 55.6, 55.7, 55.8, 56.5, 81.9, 82.01, 82.04, 82.1, 82.2, 94.7,
96.8, 113.6, 118.5, 118.8, 122.0, 122.3, 123.2, 123.4, 126.8, 127.7,
128.8, 131.7, 132.0, 134.0, 134.1, 134.5, 135.0, 137.3, 138.0, 140.2,
140.9, 142.1, 152.1, 162.7, 163.6, 171.3, 172.4, 172.7, 172.8, 172.9,
173.0. ESI-MS obsd 1084.6016, calcd 1084.5995 [(M + Na)+, M =
C62H79N9O7]. λabs (CH2Cl2) 413, 639 nm. The sample retained DMF
even after extensive drying.
t
19. The Bu-protected ligand 17 (114.6 mg, 0.106 mmol) was
Zn12. A solution of 12 (10.9 mg, 0.0198 mmol) in CH2Cl2/MeOH
[4 mL (3:1)] was treated with Zn(OAc)2 (18.2 mg, 0.099 mmol, 1.5
equiv.). When UV−vis absorption spectroscopy indicated the
consumption of the starting material (λmax = 639 nm) and the
formation of a single metalated chlorin (λmax = 608 nm; approximately
3 h), the reaction mixture was diluted with CH2Cl2 and water. The
aqueous layer was extracted with CH2Cl2. The combined organic
phase was dried (MgSO4), filtered, and concentrated. The solid
residue was purified by column chromatography (silica, CH2Cl2/
MeOH, 0 → 10%) affording an iridescent blue-green solid (10.6 mg,
dissolved in CH2Cl2 (5 mL), and TFA (5 mL) was added. The mixture
was stirred at rt overnight. The mixture was concentrated to give a
dark green solid that was used without further purification (quant): 1H
NMR (400 MHz, CD3OD) δ 2.14 (s, 6H), 2.80 (s, 1H), 3.06−3.12
(m, 7H), 3.45−3.95 (m, 22H), 4.13−4.16 (m, 3 H), 4.79 (s, 2H), 4.94
(s, 2H), 7.61 (d, J = 8.8 Hz, 2H), 8.35 (d, J = 8.8 Hz, 2H), 8.64 (d, J =
4.4 Hz, 1H), 8.98 (d, J = 4.8 Hz, 2H), 9.11 (d, J = 4.8 Hz, 1H), 9.21
(d, J = 4.4 Hz, 1H), 9.31 (d, J = 4.8 Hz, 1H), 9.38 (s, 1H), 9.50 (s,
1H), 9.60 (d, J = 4.8 Hz, 1H), 10.39 (s, 1H). 13C NMR (125 MHz,
CD3OD) δ 32.0, 36.4, 39.7, 50.7−56.5 (br m), 69.3, 99.2, 102.3, 105.6,
116.6, 117.4, 119.7, 122.2, 127.7, 127.8, 128.0, 129.0, 132.2, 134.2,
135.5, 138.6, 139.4, 139.5, 141.7, 143.1, 146.2, 147.6, 161.3, 170.3,
1
88%): H NMR (500 MHz, CDCl3/CD3OD) δ 1.99 (s, 6H), 2.24 (s,
3H), 4.47 (s, 2H), 7.62−7.65 (m, 3H), 7.79−7.80 (m, 2H), 7.96−7.97
10372
dx.doi.org/10.1021/ic3015354 | Inorg. Chem. 2012, 51, 10366−10374