Common origin, common fate: Regular porphyrin and N-confused porphyrin yield an identical tetrapyrrolic degradation product

Article abstract of DOI:10.1021/jo201489z

The formation of an identical linear tetrapyrrole observed in the course of photooxidation of meso-tetraarylpor-phyrin and its N-confused isomer can be explained as a result of 1,2- and 1,3-dioxygen addition, respectively, as substantiated by DFT calculations.

Full text of DOI:10.1021/jo201489z

Article
pubs.acs.org/joc
Common Origin, Common Fate: Regular Porphyrin and N-Confused
Porphyrin Yield an Identical Tetrapyrrolic Degradation Product
Jacek Wojaczynski, Marta Popiel, Ludmiła Szterenberg, and Lechosław Latos-Grazynski*
́
́
̇
Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50 383 Wrocław, Poland
S
* Supporting Information
ABSTRACT: The formation of an identical linear tetrapyrrole
observed in the course of photooxidation of meso-tetraarylpor-
phyrin and its N-confused isomer can be explained as a result of
1,2- and 1,3-dioxygen addition, respectively, as substantiated by
DFT calculations.
INTRODUCTION
Scheme 1
■
Since the discovery in 1994 that the acid-catalyzed Rothemund
condensation of pyrrole and aryl aldehyde yields both regular
tetraarylporphyrin (1, Chart 1) and its N-confused isomer 2,1 the
Chart 1
degradation products, from which a linear N-confused
tetrapyrrole could be isolated. Upon metalation with palladium-
(II), this compound converts into an N-confused biliverdin
analogue that can act as a binucleating ligand with two types
of coordination surroundings: (NNNO) and (CNOO).13 In
this contribution, we concentrate on further exploration of
photooxidation products, which led to the identification of
the unexpected but mechanistically very significant tetrapyr-
rolic compound 5a, typically formed in the course of TPP2−
degradation. Thus, we have shown that both 1,2-dioxygen
addition (common) and 1,3-dioxygen addition (unprece-
dented for porphyrinoids) are of importance in N-confused
porphyrin cleavage.
chemistry of the latter macrocycle has developed considerably.2 In
particular, the specific reactivity of the 3-carbon of N-confused pyrrole
has been exemplified by the formation of 3-oxo-2-aza-21-carbachlorin
derivatives 3, containing a lactam functionality,3 synthesis of a 3,3′-
linked dimer,4 substitution with pyrrole,5 and fusion of pyrrole rings
preceded by halogenation of 21- and 3-carbon atoms.6
The oxidative degradation of tetrapyrrolic macrocycles was
extensively investigated in the context of heme and chlorophyll
catabolism.7 The studies on mechanisms of dioxygen and/or
light-driven ring-opening reactions of porphyrins and their
complexes are also of special importance because they are
widely used as oxidation catalysts and photosensitizers.8,9
Photooxidation of zinc, magnesium, cadmium, and thallium(I)
complexes of tetraphenylporphyrin as well as the porphyrin
dianion (TPP2−, 4) was previously examined; the final product 5
bearing an −OR substituent in the 15-position results from
dioxygen attack on the Cmeso−Cα bond, followed by the addition
of water or alcohol (Scheme 1).10 As proved by isotope labeling
studies, both carbonyl oxygen atoms are derived from a single
molecule of O2.10b,c An analogous mechanism of ring-opening,
based on 1,2-cycloaddition of dioxygen, was suggested for other
tetrapyrroles, such as octaethylporphyrin,11 and corroles.12
Recently, we have shown that photooxidation of the dianion
of N-confused tetraphenylporphyrin led to a mixture of
RESULTS AND DISCUSSION
■
Degradation of NCTPP2−. N-confused tetraphenylpor-
phyrin dianion (NCTPP2−, 6) was photooxidized under
standard conditions as described previously.13 Originally, after
chromatographic purification, 5a was present in the fraction
containing its N-confused analog 7a (the amount of 5a was
1
estimated from H NMR spectrum as 20−30% of 7a) and
was treated as an impurity, which could be removed by
recrystallization. The effective chromatographic separation of
the two tetrapyrroles required their conversion into hydroxy-
lated analogues 5b and 7b, which exhibited more distinct Rf
values (Scheme 2).14
Received: July 21, 2011
Published: October 26, 2011
© 2011 American Chemical Society
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resonances because of the deuteration of the particular carbon
atom. This observation served as an additional proof that
compound 5a was not formed from trace TPP2− (which would
not be regioselectively pyrrole-deuterated under the conditions
used for preparation of 21-D-2). The newly observed
degradation product must then originate from dianion of N-
confused porphyrin and is formed by an attachment of oxygen
atoms to the 3- and 5-positions (1,3-cycloaddition) instead of
the expected breaking of the C4−C5 bond. Therefore, a
mechanism different from those previously proposed for the
degradation of tetrapyrrolic macrocycles should be responsible
for the observed phenomenon.10−12 One should remember, however,
that the formation of compound 7 requires 1,2-cycloaddition to the
C10−C11 bond. Thus, two different mechanisms operating in one
molecule could be detected.
Scheme 2
In a control experiment, photooxidation of TPP dianion was
performed under identical conditions. No traces of degradation
product coming from dioxygen attachment to 3,5-carbons
could be detected. Apparently, the presence of inverted
pyrrole in dianion 3 seems to be a prerequisite of this kind of
reactivity.
DFT Studies. DFT calculations were performed to
substantiate the formation of unexpected degradation products.
We limited the theoretical analysis to the reaction pathways
leading from 6 to the identified tetrapyrrolic compounds. The
proposed mechanism included the previous observations
concerning the origin of carbonyl oxygen atoms.10b,c
The starting NCTPP2− contained no traces of the TPP2−
dianion as carefully proved by the H NMR spectrum. Thus,
1
compound 5a was formed from the oxidation of N-confused
porphyrin dianion 6. However, to establish the undeniable origin
of product 5a and to give insight into the reaction mechanism, a
selectively deuterated substrate, 21,22,24-D3-2, was prepared
(1H NMR revealed ca. 80% deuteration of 21-C),1a and the
corresponding dianion 21-D-6 was subjected to a photo-
oxidation procedure under the conditions used previously for
6. The tetrapyrrolic degradation products were then converted
into −OH derivatives (23-D-7b and 3-D-5b, Chart 2) and
Thus, two main paths resulting from dioxygen attack on
C5 (path A) or C10 (path B) of dianion 6 were considered.
The analysis of calculated electron density distribution and
the coefficients of frontier molecular orbitals of starting
NCTPP2− dianion showed no significant difference among
meso positions that would be responsible for any kind of
regioselectivity.
Chart 2
For a comparison, a degradation of TPP2− (4, path C) was
also analyzed. For each path, five dianionic structures were
optimized (IA−VA, IB−VB, and IC−VC, respectively) as well
as starting dianions (6 and 4) and dioxygen molecule. The
subsequent reaction steps included the following:
1) Dioxygen attack on the porphyrin dianion and its addition
to a meso carbon, yielding a zwitterionic structure I. The
attempted calculations assuming the addition to Cα failed
or eventually led to form I.
separated. Under the conditions of their preparation, the
deuterium label was not exchanged as demonstrated by mass
spectrometry.15 The examination of 1H NMR spectra allowed us
to establish the fate of N-confused pyrrole. In particular, the
analysis of the 6−7 ppm region of compound 3-D-5b (Figure 1)
2) Ring closure by forming an O−Cα (structure II) or
O−Cβ bond (form III). Typically, a 4-membered (1,2-
dioxetane) ring formation was considered a key step in
the reaction of different olefins with singlet dioxygen.16
However, a 5-membered (1,2-dioxolane) ring closure
was also assumed in some oxygenation reactions,17 and
products containing this structural feature were isolated
from reactions of unsaturated compounds with dioxy-
gen.18 Here, to explain the observed unusual degradation
pathway, we postulate the structure of type III, which has
not been previously discussed for the tetrapyrrolic
substrates.
3) Breaking of O−O and Cα−Cmeso bonds, leading to
linear primary degradation ring-opened products IV
(from II) and V (from III), which are converted to the
observed final products, 5 or 7, by addition of alcohol
or water. These compounds were not included in
DFT calculations. All structures of type I−V are
isomeric, which makes possible the comparison of their
energies.
Figure 1. Parts of 1H NMR spectra of 5b (lower trace) and deuterated
3-D-5b obtained from 21-D-2. Resonance assignments taken
from ref 10d.
showed that a signal attributed to the 3-position exhibited a
lowered intensity as compared to the rest of the pyrrolic
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Scheme 3
Scheme 4
The three reaction paths are shown in Schemes 3−5. For
structure I, two resonance structures differing by the bond and
charge arrangement in the key pyrrole fragment are shown.
Steps leading to products that are in fact observed (5 and 7) are
indicated by frames.
The DFT optimized structures are shown in the Supporting
Information, and the representative intermediates IIB and IIIA
are presented in Figure 2. For structures of type I, the distances
from terminal oxygen to Cα and Cβ are comparable (in the
range of 2.61−2.72 Å), and no preference for ring-closing
direction is visible. The interruption of delocalization path in all
structures results in a partial alternation of bond lengths.
Oxygen−oxygen bond length in dianions I−III (1.49−1.55 Å)
is comparable with the one observed in X-ray structures of
peroxides, including cyclic ones.19,20
1,2-Dioxetane rings in structures II exhibit a typical,
nonplanar (puckered) conformation.19 For example, dihedral
angles between two halves of 4-membered ring in IIB are in the
range of 11−16.5°. For structures III, a half-chair conformation
was found for 5-membered 1,2-dioxalane ring.20 In IIIB, the
angle between C(10)−C(11)−C(12) plane and the mean
plane of C(10)−O−O−C(12) fragment equals 35°.
Compounds IVB and VB are characterized by different
configurations of Cmeso−Cα bonds as compared to the rest of
open structures (Figures 2 and 5S−7S in the Supporting
Information). In all cases, structures of type II or III with the
broken O−O and C−C bonds were used as starting points for
the calculations. In fact, the stereochemistry of these
degradation products remains unknown because (if they are
formed) they are readily converted to compounds 5 or 7, in
which the 15-carbon atom has a sp3 hybridization. The question
of configuration becomes less important if we only compare the
energy of structures belonging to one of the proposed degrada-
tion paths.
The relative energies calculated for the considered structures
are given in Table 1. The energy diagrams for the three paths
are shown in Figures 3−5.
When path A is taken into account, the formation of 5-
membered 1,2-dioxolane ring should be preferred over 4-
membered one (the energy of IIIA is 16.9 kcal/mol lower than
IIA). The ring-opened product VA has also a considerably
lower energy (by 12.9 kcal/mol) than IVA containing an N-
confused pyrrole (its formation was not detected in our
experiments).
In track B, IIIB is also more stable than IIB, but the energy
difference is much smaller (3.7 kcal/mol). In the case of TPP2−
degradation (path C), the energies of IIC and IIIC are
practically identical. In both cases, form IV exhibits lower
energy than V by ca. 6 kcal/mol. Again, only compounds 7
(formed from IVB) and 5 (resulting from the conversion of
IVC) were isolated in our experiments. Certainly, it does not
mean that other forms cannot be produced from the reaction
with dioxygen, as some tetrapyrrolic products can be further
converted to smaller ones (like tripyrrinone formed by the
elimination of N-confused pyrrole).13,21
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a
Scheme 5
Table 1. DFT Calculated Energies (kcal/mol)
path A
path B
path C
6 + O2
IA
0.0
−21.2
6 + O2
IB
0.0
−21.0
4 + O2
IC
0.0
−20.7
IIA
−15.7
IIB
−20.7
IIC
−25.3
IIIA
IVA
VA
−32.6
−122.1
−135.0
IIIB
IVB
VB
−24.4
−119.7
−113.5
IIIC
IVC
VC
−25.7
−141.8
−136.3
a
In each case, the energies were related to the substrates.
Figure 3. Energy diagram for path A.
Figure 4. Energy diagram for path B.
Figure 2. DFT calculated structures IIB (left) and IIIA (right), shown
above the expansions of the key bipyrrolic fragments.
CONCLUSION
■
The experimental study on the photooxidation of N-confused
porphyrin dianion revealed two different mechanisms operating
in one molecule. Apart from 1,2-dioxygen addition, which is
common for tetrapyrrolic macrocycles, the rare 1,3-addition was
also observed. DFT calculations used to analyze the degradation
process show that the proposed reaction pathway, including the
formation of 5-membered dioxolane ring, is reasonable and can
Figure 5. Energy diagram for path C.
be used to explain the formation of unexpected degradation
product 5. This new example of a specific reactivity of the 3-
position of NCTPP2− at the same time creates an interesting
link between the chemistries of the two porphyrin isomers.
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NH), 11.60 ppm (bs, 1H, NH); 13C NMR (150 MHz, CDCl3) δ 74.4
(C15), 110.6 (C17), 120.3 (C5), 120.4 (C18), 122.0 (C23), 125.0 (C2),
126.5 (C7), 126.6 (Cortho or Cmeta), 127.8 (Cpara), 127.9 (Cortho or
EXPERIMENTAL SECTION
■
1
All H NMR (600 MHz) and 13C NMR (150 MHz) measurements
were performed using a spectrometer equipped with a broadband
inverse gradient probehead. The data were collected at 300 K, with the
chemical shift referenced to a residual solvent signal (CDCl3, δ (1H) =
7.26 ppm, δ (13C) = 77.16 ppm). Mass spectra were measured using
the electrospray technique.
C
meta), 128.1 (Cortho or Cmeta), 128.2 (2 × Cortho or Cmeta), 128.3 (C13),
129.0 (Cortho or Cmeta), 129.4 (Cpara), 129.5 (Cpara), 130.4 (C16 or C19),
131.2 (Cortho or Cmeta), 131.3 (Cortho or Cmeta), 131.7 (Cpara), 134.0
(C11 or C14), 134.1 (Cipso), 135.5 (C8), 136.3 (Cipso), 137.1 (Cipso),
137.5 (C3), 138.3 (Cipso), 139.9 (C4), 142.1 (C11 or C14), 144.7 (C16
or C19), 145.8 (C10), 150.5 (C6 or C9), 166.3 (C6 or C9), 172.3 (C1),
185.0 ppm (Cortho at C20); HRMS (ESI) m/z 647.24431 ([M−OH]+),
calculated for C44H31N4O2 ([M − OH]+) m/z 647.24463.
DFT calculations were performed with the Gaussian 03 program.22
Starting geometries were taken from molecular mechanics calculations.
Geometry optimizations were carried out within unconstrained C1
symmetry. Becke’s three-parameter exchange functional23 with the
gradient-corrected correlation formula of Lee, Yang, and Parr
(B3LYP)24 was used with the 6-31G** basis set. The structures
were found to have converged to a minimum on the potential energy
surface; the resulting zero-point vibrational energies were included in
the calculation of relative energies. The Cartesian coordinates for the
calculated structures are given in the Supporting Information.
The preparation of N-confused tetraphenylporphyrin followed the
described procedure.25 The photooxidation of the respective dianion
was performed as described previously.13 To a solution of 2-aza-
21-carba-5,10,15,20-tetraphenylporphyrin (100 mg, 0.16 mmol) in
200 mL of dry tetrahydrofuran, 0.23 g (4.3 mmol) of sodium methoxide
in 2 mL of dry methanol was added. A stream of air was slowly bubbled
through the resulting green solution, which was irradiated using 60 W
tungsten lamp. No filters were applied, and the light source was
located ca. 3 cm from the 500 mL round-bottom flask containing
the reaction mixture. After 1 h, the resulting brown solution was
diluted with dichloromethane (100 mL) and washed with water (3 ×
150 mL). The organic phase was dried with MgSO4 and evaporated
to dryness, and the solid residue was chromatographed on a basic
alumina column (activity III). The chromatographic separation of
degradation products on basic alumina column (activity III) led to four
major fractions, containing the unreacted substrate (38 mg),
tripyrrinone dimethyl acetal (12 mg, 21%), tripyrrinone (16 mg,
30%), and a purple fraction that was identified as a mixture of 7a
(17 mg, 25%) and 5a (4 mg, 6%). The dichloromethane solution of
these tetrapyrroles was then shaken with 1 M aqueous HCl, washed
three times with water, dried, and evaporated. The resulting mixture of
compounds 7b and 5b was separated on a silica column. Dichloro-
methane containing 0.5% methanol eluted compound 5b. Its spectral
characteristics were in agreement with literature data.10d Increasing the
methanol content to 2% yielded a fraction containing 7b.
The selective deuteration of NCTPPH2 (2) was performed
according to the described procedure,1a yielding 80% isotope labeling
at C-21. Photooxidation of the respective deuterated dianion, 21-D-6,
performed as described above for 6, and further conversion with HCl
led to isolation of tetrapyrrolic products 3-D-5b and 23-D-7b with
spectral characteristics identical to that found for 5b and 7b,
respectively, with exceptions due to selective deuteration.
1
3-D-5b: H NMR (600 MHz, CDCl3) δ 6.15−6.18 (m, 3H, H2,
H13, H17), 6.30 (d, 1H, J = 4.4 Hz, H7), 6.33 s, 1H, 15-OH), 6.46 (d,
1H, J = 4.1 Hz, H12), 6.76 (d, 1H, J = 4.6 Hz, H), 6.82 (dd, J1 = 3.5 Hz,
J2 = 2.5 Hz), 6.85 (d, 0.2 H, residual H3), 7.33−7.55 (m, 18H, Ph),
7.86 (d, 2H, J = 7.1 Hz, o-H at C20), 9.87 (s, 1H, NH), 10.82 (bs, 1H,
NH), 12.46 ppm (bs, 1H, NH); HRMS (ESI) m/z 648.2496 ([M −
OH]+), calculated for C44H30DN4O2 ([M − OH]+, m/z 648.2509).
+
23-D-7b: 1H NMR (600 MHz, CDCl3) for c = 0.7 mM, δ 3.36 (bs,
1H, 15-OH), 6.05 (bs, H17), 6.22 (d, 1H, J = 5.5 Hz, H2), 6.27 (d, 1H,
J = 4.6 Hz, H7), 6.52 (s, 0.2H, residual H23), 6.72 (d, 1H, J = 4.6 Hz,
H8), 6.76 (bs, 1H, H18), 6.96 (d, 1H, J = 6.0 Hz, H3), 7.11 (s, 1H, H13),
7.25−7.33 (m, 4H, Ph), 7.39−7.46 (m, 13H, Ph), 7.52 (t, 1H, J = 7.3
Hz, p-H at C20), 7.82 (d, 2H, J = 7.3 Hz, o-H at C20), 9.86 (s, 1H, NH,
H24), 10.09 (bs, 1H, NH), 11.58 ppm (bs, 1H, NH); HRMS (ESI) m/
z 648.2491 ([M−OH]+), calculated for C44H30DN4O2+ ([M − OH]+,
m/z 648.2509).
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR and 13C NMR spectra of compounds 5b and 7b, DFT
optimized structures IA−VA, IB−VB and IC−VC, and
Cartesian coordinates all structures. This material is available
free of charge via the Internet at http://pubs.acs.org.
For 5b: 13C NMR (150 MHz, CDCl3) δ 75.0 (C15), 109.9 (C17),
111.8 (C13), 119.8 (C18), 121.3 (C5), 124.4 (C2), 125.2 (C12), 126.0
(C7), 127.0 (Cortho or Cmeta), 127.8 (Cortho or Cmeta), 128.18 (Cortho or
AUTHOR INFORMATION
■
Corresponding Author
C
meta), 128.24 (Cortho or Cmeta), 128.3 (Cpara), 128.6 (Cortho or Cmeta),
*Fax: (+)48 71 328 23 48. E-mail: llg@wchuwr.pl.
128.7 (Cpara), 128.9 (Cortho or Cmeta), 129.1 (Cpara), 130.4 (C16 or C19),
131.0 (Cortho or Cmeta), 131.4 (Cortho or Cmeta), 131.7 (Cpara), 132.1
(C11 or C14), 134.7 (C8), 136.2 (Cipso), 137.2 (Cipso), 137.8 (C3), 138.5
(Cipso), 139.4 (C4), 142.4 (C10), 142.7 (Cipso), 143.5 (C16 or C19),
149.7 (2 × Cα; C6 or C9, C11 or C14), 164.8 (C6 or C9), 173.3 (C1),
184.6 ppm (Cortho at C20).
ACKNOWLEDGMENTS
■
Financial support from the Ministry of Science and Higher
Education (Grant No. N N204 021939) is kindly acknowledged.
DFT calculations were carried out at the Supercomputer Center
1
For 7b: UV−vis λmax (log ε) 321 (4.08), 535 (3.91) nm. The H
NMR spectrum was found to be concentration-dependent, apparently
of Poznan
́.
1
due to partial dimerization: H NMR (600 MHz, CDCl3) for c =
5 mM, δ 4.22 (bs, 1H, 15-OH), 5.96 (dd, 1H, J1 = 3.7 Hz, J2 = 2.7 Hz,
H17), 6.20 (d, 1H, J = 5.7 Hz, H2), 6.26 (d, 1H, J = 4.6 Hz, H7), 6.51
(d, 1H, J = 1.3 Hz, H23), 6.71 (d, 1H, J = 4.6 Hz, H8), 6.73 (dd, 1H,
J1 = 3.7 Hz, J2 = 2.6 Hz, H18), 6.94 (d, 1H, J = 5.7 Hz, H3), 7.05 (d, 1H,
J = 1.3 Hz, H13), 7.25−7.33 (m, 4H, Ph), 7.39−7.46 (m, 13H, Ph), 7.52
(t, 1H, J = 7.5 Hz, p-H at C20), 7.77 (d, 2H, J = 7.1 Hz, o-H at C20),
10.08 (bs, 1H, NH), 10.45 (s, 1H, NH, H24), 11.68 ppm (bs, 1H,
NH); for c = 0.7 mM, δ 3.36 (bs, 1H, 15-OH), 6.05 (dd, 1H, J1 = 3.7
Hz, J2 = 2.6 Hz, H17), 6.22 (d, 1H, J = 5.7 Hz, H2), 6.27 (d, 1H, J = 4.6
Hz, H7), 6.52 (d, 1H, J = 1.3 Hz, H23), 6.72 (d, 1H, J = 4.5 Hz, H8),
6.76 (dd, 1H, J1 = 3.7 Hz, J2 = 2.6 Hz, H18), 6.96 (d, 1H, J = 5.7 Hz,
H3), 7.11 (d, 1H, J = 1.3 Hz, H13), 7.25−7.33 (m, 4H, Ph), 7.39−7.46
(m, 13H, Ph), 7.52 (tt, 1H, J1 = 7.4 Hz, J2 = 1.3 Hz, p-H at C20), 7.82
(d, 2H, J = 7.0 Hz, o-H at C20), 9.87 (s, 1H, NH, H24), 10.09 (bs, 1H,
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