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Review
. 2017 Jun 15;22(6):994.
doi: 10.3390/molecules22060994.

Coumarin-Tetrapyrrolic Macrocycle Conjugates: Synthesis and Applications

Ana F R Cerqueira  1 , Vítor A S Almodôvar  2 , Maria G P M S Neves  3 , Augusto C Tomé  4
Affiliations
Review

Coumarin-Tetrapyrrolic Macrocycle Conjugates: Synthesis and Applications

Ana F R Cerqueira et al. Molecules. .

Abstract

This review covers the synthesis of coumarin-porphyrin, coumarin-phthalocyanine and coumarin-corrole conjugates and their potential applications. While coumarin-phthalocyanine conjugates were obtained almost exclusively by tetramerization of coumarin-functionalized phthalonitriles, coumarin-porphyrin and coumarin-corrole conjugates were prepared by complementary approaches: (a) direct synthesis of the tetrapyrrolic macrocycle using formylcoumarins and pyrrole or (b) by functionalization of the tetrapyrrolic macrocycle. In the last approach a range of reaction types were used, namely 1,3-dipolar cycloadditions, hetero-Diels-Alder, Sonogashira, alkylation or acylation reactions. This is clearly a more versatile approach, leading to a larger diversity of conjugates and allowing the access to conjugates bearing one to up to 16 coumarin units.

Keywords: corroles; coumarins; phthalocyanines; porphyrins.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Route to coumarin–porphyrin dyads [38,39].
Figure 1
Figure 1
Structures of coumarin conjugates obtained from natural porphyrins [43].
Scheme 2
Scheme 2
Synthesis of aryl-substituted coumarin–porphyrin dyads [44].
Scheme 3
Scheme 3
Synthesis of β-triazole bridged coumarin–Cu(II)porphyrin conjugates [46].
Scheme 4
Scheme 4
Synthesis of zinc(II) β-triazolylmethyl-bridged coumarin–porphyrin dyads [47].
Scheme 5
Scheme 5
Synthesis of zinc (II) meso-phenyl-triazole bridged coumarin–porphyrin dyads [48].
Figure 2
Figure 2
meso-(Coumarin-4-yl)porphyrins reported by Lin et al. [49].
Scheme 6
Scheme 6
Route to meso-tetrakis(4-chlorocoumarin-3-yl)porphyrins reported by Amaravathi et al. [52].
Scheme 7
Scheme 7
Route to coumarin–porphyrin conjugates reported by Fréchet and co-workers [53,54].
Scheme 8
Scheme 8
Synthesis of three porphyrin-core dendrimers with eight coumarin units [56].
Scheme 9
Scheme 9
Synthesis of porphyrin-core dendrimers bearing 12 coumarin units [57].
Scheme 10
Scheme 10
A coumarin–porphyrin dyad reported by Weiying Lin and co-workers [58].
Scheme 11
Scheme 11
Synthesis of a donor–acceptor system [60].
Scheme 12
Scheme 12
Synthesis of supramolecular porphyrin dendrimers with coumarin units [61].
Scheme 13
Scheme 13
Synthesis of an artificial photosynthetic reaction center [62].
Figure 3
Figure 3
Model compounds of artificial photosynthetic reaction centers [62].
Scheme 14
Scheme 14
Typical route to coumarin–phthalocyanine conjugates [63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91].
Scheme 15
Scheme 15
Synthesis of metal-free and metallophthalocyanines [64].
Scheme 16
Scheme 16
Synthesis of coumarin–phthalocyanine conjugates 61 [92,93,94,95,96,97,98,99,100,101,102,103,104].
Scheme 17
Scheme 17
Synthesis of coumarin–phthalocyanine conjugates [105].
Scheme 18
Scheme 18
Synthesis of axial coumarin-substituted titanium(IV) phthalocyanines [106].
Scheme 19
Scheme 19
Coumarin–corrole dyads obtained by the [2 + 1] approach [108].
Scheme 20
Scheme 20
Coumarin–corrole dyad obtained under copper-free Sonogashira conditions [108].
Figure 4
Figure 4
Coumarin–corrole dyads obtained under copper-free Sonogashira conditions [113].
Figure 5
Figure 5
Coumarin–corrole dyads obtained by the [2 + 1] strategy [113].
Scheme 21
Scheme 21
Synthesis of the dyad 82 [114].
Scheme 22
Scheme 22
Synthesis of coumarin–corrole conjugates via hetero-Diels–Alder reactions [39].
Figure 6
Figure 6
Solvatochromic effect of compound 84b. Reprinted with permission from ref. [39]. Copyright © 2013 Elsevier Ltd.
See this image and copyright information in PMC

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