European Journal of Organic Chemistry
10.1002/ejoc.202001165
FULL PAPER
Vis (CH
m/z calcd. for C47
2
Cl
2
): λmax (log ε) = 378(4.65), 661(4.15); HRMS (MALDI-TOF)
Technical University of Munich – Institute for Advanced Study
through a Hans Fischer Senior Fellowship.
+
H38IN
2
O
2
[M+H] 789.1978; found 789.1953.
Compound 26: Synthesized via General Procedure 1 from dipyrrole 25
200 mg, 0.345 mmol), C HF O (68 mg, 0.345 mmol), TFA (26 μL, 0.345
mmol), and DDQ (240 mg, 1.06 mmol) in 200 mL CH Cl . The crude
material was purified by alumina column chromatography (Brockmann
Keywords:
Expanded
porphyrins
•
Non-aromatic
•
(
7
5
2
2
Porphyrinoids • Photosensitizer • Homoporphyrins
Grade I). Yield
CH Cl /CH
=
41 mg, 16%. m.p. = 212 °C;
R
f
=
0.4 (SiO
2
,
[
1]
a) A. Osuka, S. Saito, Chem. Commun. 2011, 47, 4330−4339; b) M.
Toganoh, H. Furuta, Chem. Commun. 2012, 48, 937−954; c) J. L.
Sessler, Z. Gross, H. Furuta, Chem. Rev. 2017, 117, 2201−2202; d) J.
L. Sessler, S. J. Weghorn, Expanded, Contracted and Isomeric
Porphyrins, Pergamon, New York, 1997.
1
2
2
3
OH, 4:1 v/v); H NMR (400 MHz, CDCl
3
): δ = 7.44 (d, J = 7.5
Hz, 2H), 7.17 (d, J = 8.7 Hz, 4H), 6.97 (t, J = 7.6 Hz, 4H), 6.88 (t, J = 6.5
Hz, 6H), 6.72 (d, J = 7.9 Hz, 2H), 6.39 (d, J = 5.1 Hz, 2H), 3.84 (s, 6H),
2
1
1
.05 (s, 6H) ppm; 13C NMR (101 MHz, CDCl
3
): δ = 159.8, 159.5, 148.5,
48.3, 144.5, 140.1, 135.5, 134.8, 134.0, 133.8, 131.8, 130.1, 126.8,
26.3, 126.0, 55.3, 21.0 ppm; 19F NMR (377 MHz, CDCl
): δ = -137.17
[
2]
3]
a) R. Misra, T. K Chandrashekar, Acc. Chem. Res. 2008, 41, 265-279;
b) T. Tanaka, A. Osuka, Chem. Rev. 2017, 117, 2584–2640.
3
(
dd, J = 24.9, 8.2 Hz), -138.58 (dd, J = 24.9, 8.4 Hz), -155.24 (t, J = 20.9
Hz), -161.98 – -162.37 (m) ppm; UV-Vis (CH Cl ): max (log ε)
86(4.39), 633(4.24); HRMS (MALDI-TOF) m/z calcd. for C47
[
a) H. Rath, J. Sankar, V. PrabhuRaja, T. K. Chandrashekar, A. Nag, D.
Goswami, J. Am. Chem. Soc. 2005, 127, 11608−11609; b) J. F.
Arambula, C. Preihs, D. Borthwick, D. Magda, J. L. Sessler, Anticancer
Agents Med. Chem. 2011, 11, 222−232; c) Z. Zhang, D. S. Kim, C.-Y.
Lin, H. Zhang, A. D. Lammer, V. M. Lynch, I. Popov, O. Š. Miljanić, E. V.
Anslyn, J. L. Sessler, J. Am. Chem. Soc. 2015, 137, 7769−7774.
R. Grigg, J. Chem. Soc. C 1971, 3664−3668.
2
2
λ
=
3
33 5 2 2
H F N O
+
[
M+H] 753.2540; found 753.1715.
Compound 27: Synthesized via General Procedure 1 from dipyrrole 25
200 mg, 0.345 mmol), C15 10O (72 mg, 0.345 mmol), TFA (26 μL, 0.345
mmol) and DDQ (240 mg, 1.06 mmol) in 200 mL CH Cl . The crude
(
H
[4]
[5]
2
2
a) H. J. Callot, T. Tschamber, Tetrahedron Lett. 1974, 3155−3158; b) H.
J. Callot, T. Tschamber, E. Schaeffer, Tetrahedron Lett. 1975,
2919−2922; c) B. Chevrier, R. Weiss, J. Am. Chem. Soc. 1975, 97,
1416–1421.
material was purified by alumina column chromatography (Brockmann
Grade I). Yield = 34 mg, 13%. m.p. = 192 °C; R
NMR (400 MHz, CDCl
1
f
= 0.60 (SiO
2
, CH
2
Cl
2
); H
3
): δ = 8.53 (s, 1H), 8.26 (d, J = 8.6 Hz, 1H), 8.06
(
7
3
(
1
d, J = 8.4 Hz, 2H), 7.95 (d, J = 8.8 Hz, 1H), 7.51 – 7.39 (m, 4H), 7.38 –
[6]
[7]
a) E. Ganapathi, W.-Z. Lee, M. Ravikanth, J. Org. Chem. 2014, 79,
9603−9612; b) K. G. Thorat, G. Chowdhary, P. Isar, M. Ravikanth, Eur.
J. Org Chem. 2018, 5389−5396; c) E. Ganapathi, S. Kuilya, T.
Chatterjee, M. Ravikanth, Eur. J. .Org. Chem. 2016, 282−290.
a) K. S. Anju, M. Das, B. Adinarayana, C. H. Suresh, A. Srinivasan,
Angew. Chem. Int. Ed. 2017, 56, 15667−15671; b) B. Adinarayana, M.
Das, C. H. Suresh, A. Srinivasan, Chem. Eur. J. 2019, 25, 4683−4687.
a) M. Stępień, L. Latos-Grażyński, Acc. Chem. Res. 2005, 38, 88–98;
b) T. D. Lash, Org. Biomol. Chem. 2015, 13, 7846−8082; c) D. I.
AbuSalim, M. L. Merfeld, T. D. Lash J. Org. Chem. 2013, 78, 10360–
.30 (m, 1H), 7.11 (d, J = 25.5 Hz, 5H), 6.98 (s, 2H), 6.80 (d, J = 8.3 Hz,
H), 6.74 (s, 1H), 6.63 (d, J = 4.3 Hz, 2H), 5.82 (d, J = 3.7 Hz, 2H), 3.79
s, 6H), 2.10 (s, 6H). ppm; 13C NMR (101 MHz, CDCl
3
): δ = 159.4, 144.5,
33.9, 133.6, 131.8, 130.1, 128.9, 126.0, 125.8, 125.6, 113.0, 55.2, 21.1
ppm; UV-Vis (CH
(
2
Cl
2
):
λ
max (log ε) = 394(4.53), 641(4.22); HRMS
+
MALDI-TOF) m/z calcd. for C55
H N O
43 2 2
[M] 763.3325; found 763.3291.
[8]
Compound 28: Synthesized via General Procedure 1 from dipyrrole 25
200 mg, 0.345 mmol), C IO (80 mg, 0.345 mmol), TFA (26 μL, 0.345
mmol), and DDQ (240 mg, 1.06 mmol) in 200 mL CH Cl . The crude
material was purified by alumina column chromatography (Brockmann
Grade I). Yield = 29 mg, 11%. m.p. = 186 °C; R = 0.60 (SiO
CH Cl /CH OH, 99:1, v/v; 1H NMR (400 MHz, CDCl ): δ = 7.78 (d, J =
(
7 5
H
10368; d) S. C. Fosu, G. M. Ferrence, T. D. Lash J. Org. Chem. 2014,
2
2
79, 11061–11074.
[
[
9]
T. D. Lash, S. T. Chaney, D. T. Richter, J. Org. Chem. 1998, 63,
076−9088.
f
2
,
9
2
2
3
3
10] a) M. Stępień, L. Latos-Grażyński, Chem. Eur. J. 2001, 7, 5113– 5117;
b) M. Stępień, L. Latos-Grażyński, J. Am. Chem. Soc. 2002, 124,
3838–3839.
8
6
5
1
1
5
.0 Hz, 2H), 7.53 (dd, J = 19.9, 8.9 Hz, 1H), 7.45 (s, 1H), 7.26 – 7.16 (m,
H), 7.10 – 6.96 (m, 4H), 6.94 – 6.82 (m, 7H), 6.75 (s, 2H), 6.58 (d, J =
.1 Hz, 2H), 3.86 (s, 6H), 2.04 (s, 6H); 13C NMR (101 MHz, CDCl
3
): δ =
[
11] a) B. Szyszko, A. Białońska, L. Szterenberg, L. Latos-Grażyński Angew.
Chem. Int. Ed. 2015, 54, 4932−4936; b) B. Adinarayana, A. P. Thomas,
C. H. Suresh, A. Srinivasan, Angew. Chem. Int. Ed. 2015, 54, 10478–
10482.
59.63, 148.89, 144.51, 137.45, 137.13, 136.85, 135.75, 134.71, 133.95,
32.78, 132.40, 131.71, 130.14, 128.47, 125.83, 113.88, 113.57, 113.18,
5.32, 20.92. ppm; UV-Vis (CH
2
Cl
2
): λmax (log ε) = 388(4.43), 641(4.22);
[M]+ 789.1978; found
HRMS (MALDI-TOF) m/z calcd. for C47
7
2 2
H38IN O
[
12] S. Callaghan, M. O. Senge, Photochem. Photobiol. Sci. 2018, 17,
89.1957.
1490–1514.
[
13] Q. Zhao, Y. Wang, Y. Xu, Y. Yan, J. Huang, Sci. Rep. 2016, 6, 31339.
14] a) C. J. Medforth, M. O. Senge, K. M. Smith, L. D. Sparks, J. A.
Shelnutt J. Am. Chem. Soc. 1992, 114, 9859–9869; b) M. O. Senge
Chem. Commun. 2006, 243–256.
Supporting Information (see footnote on the first page of this article):
Spectroscopic data of all compounds, singlet oxygen production
measurements, and X-ray crystallographic data. CCDC 2025181 (for 19),
[
2
025182 (for 20) and 2025183 (for 27) contain the supplementary
[15] X.-F. Duan, J. Zeng, J.-W. Lü, Z.-B. Zhang, J. Org. Chem. 2006, 71,
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
9873–9876.
[
[
16] J. E. McMurry, M. P. Fleming J. Am. Chem. Soc. 1974, 96, 4708–4709.
17] a) J. M. Lim, Z. S. Yoon, J.-Y. Shin, K. S. Kim, M.-C. Yoon, D. Kim,
Chem. Commun. 2009, 261–273; b) R. E. Haddad, S. Gazeau, J.
Pécaut, J.-C. Marchon, C. J. Medforth, J. A. Shelnutt, J. Am. Chem.
Soc. 2003, 125, 1253–1268; c) S. Zakavi, N. G. Gharab, Polyhedron
Acknowledgements
2
007, 26, 2425–2432.
18] M. C. DeRosa, R. J. Crutchley, Coord. Chem. Rev. 2002, 233-234,
51–371.
This work was supported by grants from Science Foundation
Ireland (IvP 13/IA/1894), the Irish Research Council
[
3
(
GOIPD/2017/1395) and has received funding from the
[19] a) A. Harriman, B. G. Maiya, T. Murai, G. Hemmi, J. L. Sessler, T. E.
Mallouk J. Chem. Soc., Chem. Commun., 1989, 314–316; b) J.-H. Ha,
G. Y. Jung, M.-S. Kim, Y. H. Lee, K. Shin, Y.-R. Kim Bull. Korean Chem.
Soc. 2001, 22, 63–67.
European Union's Horizon 2020 research and innovation
programme under the Marie Skłodowska-Curie Grant
Agreement No. 764837. It was prepared with the support of the
[20] a) M. Korínek, R. Dědic, A. Molnár, A. Svoboda, J. Hála, J. Mol. Struct.
2005, 744, 727–731; b) H. Rosen, S. J. Klebanoff, J. Biol. Chem. 1977,
252, 4803–4810.
1
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