Synthesis of functionalized trans-A2B2-porphyrins using donor-acceptor cyclopropane-derived dipyrromethanes

Article abstract of DOI:10.1002/adsc.201300141

meso-Substituted trans-A₂B₂-porphyrins bearing specific patterns of substituents are crucial building blocks in porphyrin-based biomimetic systems and molecular materials and can be used for the construction of well-defined porphyrin-based architectures. A new stepwise and rational synthesis of functionalized trans-A₂B₂-porphyrins is reported in which for the first time donor-acceptor-substituted cyclopropane precursors (d-a cyclopropanes) are exploited. The three presented d-a cyclopropanes are readily accessible in a multi-gram scale and serve as aldehyde equivalents in the reaction with an excess of pyrrole to afford the corresponding dipyrromethanes (DPMs). The three DPMs were synthesized in yields of 60-74%. They are stable in purified form in the absence of light and air and were subsequently condensed with a wide range of aliphatic and aromatic aldehydes bearing electron-donating or electron-withdrawing substituents followed by oxidation to form the corresponding trans-A₂B ₂-porphyrins. Fourteen functionalized porphyrins were synthesized in yields of 14-31%, indicating the broad scope of the synthetic procedure. The possibility to introduce key functional groups is emphasized, which enables subsequent modification of these porphyrins with moieties inducing biological activity. Modification of the tetrapyrroles may occur by addition to one of the porphyrin peripheral double bonds, the use of substituents of the aryl groups or via the methoxycarbonyl group at two of the meso-substituents. Three examples of porphyrins were converted into the corresponding 7,8-dihydroxychlorins by osmium-mediated dihydroxylation and one of the resulting chlorins was subjected to saponification to give a highly polar chlorin dicarboxylic acid. A 4-bromophenyl-substituted d-a cyclopropane was prepared by rhodium-catalyzed cyclopropanation and then transformed into a DPM which was subsequently condensed to a porphyrin. Its Zn complex allowed a Heck reaction to afford the functionalized bis(alkenyl)-substituted trans-A₂B₂-Zn- porphyrin. Copyright

Full text of DOI:10.1002/adsc.201300141

FULL PAPERS
DOI: 10.1002/adsc.201300141
Synthesis of Functionalized trans-A B -Porphyrins Using Donor–
2
2
Acceptor Cyclopropane-Derived Dipyrromethanes
a,b
a,c
a,
M. Hassan Beyzavi, Carolin Nietzold, Hans-Ulrich Reissig, *
a,b,
and Arno Wiehe *
Institut fꢀr Chemie und Biochemie, Freie Universitꢁt Berlin, Takustr. 3, 14195 Berlin, Germany
a
Fax : (+49)-30-838-55367; e-mail: hans.reissig@chemie.fu-berlin.de (homepage:
http://www.bcp.fu-berlin.de/chemie/oc/reissig)
biolitec research GmbH, Otto-Schott-Str. 15, 07745 Jena, Germany
b
E-mail: arno.wiehe@biolitec.de (homepage: http://www.biolitec.de)
Current address: Federal Institute for Materials Research and Testing, (BAM), Unter den Eichen 44–46, 12203 Berlin,
c
Germany
Received: February 14, 2013; Published online: April 30, 2013
th
Dedicated to Professor Dr. Harry Kurreck on occasion of his 80 birthday.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300141.
Abstract: meso-Substituted trans-A B -porphyrins key functional groups is emphasized, which enables
2
2
bearing specific patterns of substituents are crucial subsequent modification of these porphyrins with
building blocks in porphyrin-based biomimetic sys- moieties inducing biological activity. Modification of
tems and molecular materials and can be used for the tetrapyrroles may occur by addition to one of the
the construction of well-defined porphyrin-based ar- porphyrin peripheral double bonds, the use of sub-
chitectures. A new stepwise and rational synthesis of stituents of the aryl groups or via the methoxycar-
functionalized trans-A B -porphyrins is reported in bonyl group at two of the meso-substituents. Three
2
2
which for the first time donor–acceptor-substituted examples of porphyrins were converted into the cor-
cyclopropane precursors (d–a cyclopropanes) are ex- responding 7,8-dihydroxychlorins by osmium-mediat-
ploited. The three presented d–a cyclopropanes are ed dihydroxylation and one of the resulting chlorins
readily accessible in a multi-gram scale and serve as was subjected to saponification to give a highly polar
aldehyde equivalents in the reaction with an excess chlorin dicarboxylic acid. A 4-bromophenyl-substi-
of pyrrole to afford the corresponding dipyrrome- tuted d–a cyclopropane was prepared by rhodium-
thanes (DPMs). The three DPMs were synthesized catalyzed cyclopropanation and then transformed
in yields of 60–74%. They are stable in purified form into a DPM which was subsequently condensed to
in the absence of light and air and were subsequently a porphyrin. Its Zn complex allowed a Heck reaction
condensed with a wide range of aliphatic and aro- to afford the functionalized bis ACHUTNGRENNUG( alkenyl)-substituted
matic aldehydes bearing electron-donating or elec- trans-A B -Zn-porphyrin.
2
2
tron-withdrawing substituents followed by oxidation
to form the corresponding trans-A B -porphyrins.
2
2
Fourteen functionalized porphyrins were synthesized Keywords: cross-coupling; cyclopropanes; dihydroxy-
in yields of 14–31%, indicating the broad scope of lation; dipyrromethanes (dipyrranes); macrocycles;
the synthetic procedure. The possibility to introduce porphyrinoids; tetrapyrroles
Introduction
systems is closely dependent upon the availability of
suitable porphyrin building blocks. A trans-porphyrin
meso-Substituted trans-A B -porphyrins bearing dis- provides a substitution pattern that can be used for
2
2
tinct patterns of functional groups are valuable key the construction of porphyrin-based systems with
components found in a wide range of model systems a well-defined linear structure. Recent applications of
[
1,2]
[3]
in biomimetic and material chemistry.
The level of trans-A B -porphyrins include enzyme models, ma-
2 2
[4]
architectural complexity that can be achieved in such terials with non-linear optical properties, charge sep-
Adv. Synth. Catal. 2013, 355, 1409 – 1422
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M. Hassan Beyzavi et al.
FULL PAPERS
[
5]
aration devices that mimic photosynthesis, multipor-
phyrin arrays for light harvesting applications and
[7]
[
6]
dye-sensitized solar cells (DSSC), chiral sensors,
[
8]
[9]
chiral catalysts, optoelectronic devices, amplified
[
10]
two-photon absorption,
small molecules, liquid crystals, and bilayer lipid
membrane spanning arrays.
synthetic receptors for
[11]
[12]
[
13]
Efficient synthetic methods for preparing specifical-
ly functionalized trans-A B -porphyrins are essential
2
2
for the construction of materials and devices men-
tioned above. Often reported protocols are not com-
patible with key functional groups or the yields of pu-
rified porphyrins are very low. They may also result in
metalloporphyrins which require harsh conditions for
demetallation. Although trans-A B -porphyrins can in
2
2
principle quite easily be obtained by condensation of
pyrrole and two different aldehydes, this approach is
in practice still limited because this ꢃmixedꢄ condensa-
tion usually results in a statistical mixture of six por-
phyrins and consequently difficulties arise in separa-
tion and identification of products. Alternatively, por-
phyrins with a specific substitution pattern can also be
[
14]
prepared more rational by a step-by-step protocol.
However, more simple condensation reactions have
the advantage of a faster access to porphyrin struc-
tures. Therefore, due to their easy availability DPM
(
dipyrrane) derivatives play a key role in the synthesis
of regiospecifically pure trans-A B -porphyrins by
2
2
pre-designating the orientation of meso-substituents.
trans-A B -(metallo)porphyrins could be obtained
2
2
from three described pathways via [2+2]-type build-
Scheme 1. Three possible [2+2]building block approaches
for the synthesis of trans-A B -(metallo)porphyrins of type
[
15]
ing block approaches (Scheme 1). (i) The acid-cata-
lyzed self-condensation of an AB-substituted DPM-
monocarbinol 1 which in its scope is limited with
regard to functional groups tolerance. The reason is
2
2
4
.
that the mentioned monocarbinol derivatives are pre- the result of an acid-catalyzed fragmentation followed
pared by treatment of a meso-substituted DPM with by an altered recombination of meso-substituents.
not easily available pyridyl thioesters and reactive However, Linsday et al. have shown optimized condi-
Grignard reagents to yield the corresponding 1-acyldi- tions which diminish or even suppress the ever-pres-
[
20]
pyrromethane which then requires the subsequent re- ent possibility of scrambling.
duction step using NaBH4. (ii) Reaction of 1-acyldi-
[
16]
pyrromethane 2 with PdX or MgBr under reflux
2
2
conditions to give the palladium(II)- or magnesiu- Results and Discussion
[
17,18]
m(II)-porphyrins 4, respectively;
again, the 1-
acyldipyrromethanes are prepared by treatment of As a part of an ongoing project directed towards the
a meso-substituted DPM with pyridyl thioesters and synthesis of functionalized pyrrole-based macrocycles
[
21]
reactive Grignard reagents, which limits the scope of using d–a cyclopropanes as precursors, we planned
functional group tolerance. In addition, the primary to design trans-A B -porphyrin systems employing
2
2
products are metalloporphyrins from which the metal sterically less hindered cyclopropane-derived DPMs.
may sometimes not easily be removed. (iii) Acid-cata- They should allow the synthesis of novel functional-
lyzed condensation reaction of a meso-substituted ized porphyrins that are not readily accessible via the
[
19]
DPM 3 with an aldehyde; in contrast to the former known alternative strategies.
mentioned pathways, in this approach there is a wider
meso- or 5-substituted DPMs can simply be ob-
functional group tolerance. In practice, similar as in tained in multi-gram scales by the condensation of an
acid-catalyzed reactions involving polypyrromethanes, excess of pyrrole and the desired aldehyde and, for
the acid catalysis conditions required for this conden- some examples, even more efficient synthetic proto-
[
22]
sation introduce the possibility of scrambling which is cols have also been reported. DPMs are important
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Synthesis of Functionalized trans-A B -Porphyrins
2
2
precursors for the synthesis of meso-substituted por- and provide high versatility of the respective products
[
24]
phyrins, corroles, expanded and reduced porphyrins after ring cleavage. Compounds such as methyl 2-
and related compounds such as dipyrrins, calixpyr- siloxycyclopropanecarboxylates 5 serve as 1,3-zwitter-
Hence, we ionic synthons 6 and – in the presence of protic sol-
AHCTUNGTRENNUNG
[
23]
roles (porphyrinogens) and chlorins.
considered approach (iii) (vide supra and Scheme 1) vents, mild acids or fluoride ions – in situ generate
to be also feasible for the synthesis trans-A B -por- products of type 7 carrying two carbonyl functionali-
2
2
[
25]
phyrin systems based on d–a cyclopropane-derived ties in 1,4 distance (Scheme 2).
DPMs. We selected the easily available cyclopropanes 5
[26]
Cyclopropane derivatives vicinally substituted by as starting materials since in situ formed aldehydes 7
donor and acceptor groups are particularly suitable should be suitable in the condensation step with pyr-
[
27]
for synthetic applications, since the electronic effects role.
The introduced methoxycarbonyl group
of the substituents activate the strained compound should smoothly enable subsequent transformations.
For the synthesis of DPMs 8a and 8b, d–a cyclopro-
panes 5a and 5b were treated with an excess of pyr-
role in the presence of a catalytic amount of trifluoro-
[
19a]
acetic acid (TFA) (10 mol%).
After performing
the work up, the stable DPMs 8a and 8b were ob-
tained in 74 and 65% yields, respectively (Scheme 3).
Performing the two reaction steps in one pot (ring
opening of the cyclopropane and condensation with
excess pyrrole) and purifying only at the final step re-
Scheme 2. The d–a cyclopropanes 5 serving as 1,3-zwitter- duces the experimental effort and allows a good over-
[
28]
ionic synthons 6 and leading to 1,4-dicarbonyl compounds 7. all yield. We have also prepared the sterically more
congested DPM 8c from d–a cyclopropane 5c by the
same method and utilized it recently for the synthesis
of functionalized, meso-hydrogenated, oxidation-re-
[
21]
sistant calix[4]- and calix[6]phyrins. The three alde-
hydes 7a–c incorporated into DPMs 8a–c are fairly
elusive species and hard to prepare by alternative
methods.
With multi-gram amounts of DPMs 8a and 8b in
hand, we planned to react these compounds with dif-
ferent aldehydes in acid-catalyzed condensations to
form calixpyrroles followed by oxidation to give the
corresponding functionalized trans-A B -porphyrin
Scheme 3. Condensation of d–a cyclopropanes 5a–c with an
excess of pyrrole in a solvent-free condensation reaction systems (Scheme 4). Therefore, as a test reaction,
leading to functionalized DPMs 8a–c. DPM 8a was condensed with benzaldehyde in a 1:1
2
2
Scheme 4. Acid-catalyzed condensation of d–a cyclopropane-derived DPMs 8a and 8b with aldehydes (1:1 ratio) forming
functionalized trans-A B -porphyrins 11a–e and 12a–h via calixpyrrole intermediates 9a–e and 10a–h.
2
2
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Table 1. TFA-catalyzed (20 mol%) condensation of DPMs
To the best of our knowledge, this is the first report
in which d–a cyclopropane-derived DPMs are utilized
in the synthesis of porphyrin systems. By this method
meso-substituted alkyl chains carrying a terminal
functional group could easily be incorporated into the
porphyrin periphery. Following these promising re-
sults, we tested the generality and functional group
tolerance of this procedure for the synthesis of other
trans-A B -porphyrins. Therefore, we examined the
5a and 5b with different aldehydes (1:1 ratio, 2 mmol scale,
room temperature, CH Cl ) to functionalized trans-A B -
2
2
2
2
porphyrins 11 and 12.
[a]
Entry DPM Aldehyde
Product Time
Yield
[%]
[b]
[c]
[
h]
1
2
8a
8a
11a
11b
16
15
19
14
2
2
reaction of a range of substituted aromatic and ali-
phatic aldehydes with DPMs 8a or 8b in a 1:1 ratio
under the conditions used for the synthesis of 11a to
obtain the corresponding trans-A B -porphyrins 11a–
3
4
8a
8a
11c
11d
18
17
21
16
2
2
e and 12a–h, some of which are functionalized at all
four meso-bridges (Table 1).
As shown in Table 1, steric and electronic variations
of the aldehydes bearing electron-donating or elec-
tron-withdrawing substituents did not change the effi-
cacy of the reaction and resulted in the formation of
the desired functionalized trans-A B -porphyrins 11a–
5
8a
11e
16
14
2
2
6
7
8b
8b
12a
12b
22
18
26
24
e and 12a–h in acceptable yields (14–31%). For exam-
ple, several key functional groups such as acetoxy,
methoxy, methoxycarbonyl and acetamido are tolerat-
ed under the fairly mild reaction conditions (Table 1,
entries 2, 3 and 7–9). In addition, other substituents
such as pentafluorophenyl (allowing a variety of fur-
ther functionalizations such as nucleophilic aromatic
8
9
1
8b
8b
8b
12c
12d
12e
18
18
18
22
29
31
[
31]
substitutions)
or benzyloxyphenyl and alkyl sub-
stituents were also readily introduced into the porphy-
rin skeleton (Table 1, entries 4, 5 and 10–13). Since
chiral DPM 8b was used as a racemate, each of the
products 12a–h (entries 6–13) was obtained as a 1:1
mixture of diastereomers. To examine the feasibility
of this method on a larger preparative scale, the
model reaction leading to 11a was also performed on
a 15 mmol scale. The transformation proceeded simi-
larly to the small-scale experiment and provided the
desired porphyrin in 15% yield after 22 h (Table 1,
entry 14).
0
1
1
1
2
8b
8b
12f
12g
18
18
15
20
1
1
3
4
8b
8a
12h
11a
17
22
18
15
In addition, the effect of TFA loading was investi-
gated for the model reaction (DPM 8a with benzalde-
hyde in a 1:1 ratio). There is an ascending trend
[
d]
(
1
Figure 1), that is, increasing the acid loading from
0 mol% to 100 mol% leads to an increase of the
[
[
[
[
a]
Dipyrromethane.
Time for condensation step.
Yield of purified product.
yield of the product 11a from 15% to 34%. Using
b]
c]
a stoichiometric amount of acid catalyst also the A B-
3
d]
type by-product 5-(2-methoxycarbonylethyl)-10,15,20-
triphenylporphyrin resulting from scrambling (vide
supra) could be isolated in 2% yield (see Supporting
The reaction was performed on a 15 mmol scale.
ratio at room temperature in the presence of a catalyt- Information). In general, however, the DPMs 8a and
ic amount of TFA (20 mol%) in dichloromethane 8b seem to be remarkably resistant to scrambling.
[
29]
(
DCM) as described for other DPM condensations
These results suggest that in cases where interference
to furnish the corresponding calixpyrrole 9a. After of the acid catalyst with functional groups is not an
subsequent oxidation with 2,3-dichloro-5,6-dicyano-p- issue, a higher loading of acid catalyst can be applied
[
30]
benzoquinone (DDQ), the purple crystalline prod- to achieve even better yields than those in Table 1. In
uct 11a was isolated after column chromatography in a separate experiment under the same conditions as
19% yield.
described for the model reaction, the addition of TFA
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Synthesis of Functionalized trans-A B -Porphyrins
2
2
Figure 1. Effect of TFA loading on the yield of trans-A B
2
2
porphyrin 11a.
(
20 mol%) was performed gradually during 8 h using
syringe pump and a slightly improved yield of product
was observed (23%).
Scheme 6. Transformations of 12e by selective O-debenzyla-
The possibility to introduce and vary functional tion using TFA/PMB and subsequent saponification of 14 to
groups of the porphyrins should be emphasized here. furnish trans-A
They offer the option of a variety of additional trans-
B -porphyrin dicarboxylic acid 15.
2
2
formations and enable the connection of these func-
tionalized macrocycles to other interesting com- ize the presented trans-A B -porphyrins at their meso-
2
2
pounds. As an example, diester 12a was subjected to residues.
alkaline hydrolysis using potassium hydroxide in A manipulation of the porphyrinic chromophore
a mixture of THF/MeOH (3:2) as solvent to give the leading to an increase of the extinction coefficient
polar porphyrindicarboxylic acid 13 (d.r. 1:1) in 81% (loge) or to a red-shift of the longest absorption
yield (Scheme 5).
wavelength (lmax) is interesting as the resulting por-
[33]
In a second example, compound 12e underwent phyrinoids are useful for a number of applications.
a selective O-debenzylation using TFA and pentame- In order to accomplish such a modification, porphyr-
thylbenzene (PMB) as benzyl cation scavenger to give ins 11a–c were converted into the corresponding 7,8-
[
34]
porphyrin 14 with two free phenolic hydroxy groups dihydroxychlorins by the well-known OsO -mediat-
4
in quantitative yield (Scheme 6). This selective O-de- ed dihydroxylation of one of the porphyrin peripheral
[
35]
benzylation method is orthogonal to the reactivity of double bonds.
The initially formed osmate esters
[
32]
[36]
the methoxycarbonyl groups. In the following step, were reduced using sodium bisulfite.
As a result
1
4 was subjected to alkaline hydrolysis of the diester compounds 16a–c were obtained with 63, 62 and 59%
which furnished the polar bis(3-hydroxylphenyl)-sub- yields, respectively (Scheme 7). Product 16b was fur-
stituted porphyrindicarboxylic acid 15 in 85% yield, ther subjected to alkaline hydrolysis resulting in si-
exemplifying the possibility to selectively functional- multaneous hydrolysis of the alkyl ester as well as the
acetoxyphenyl substituents yielding the highly polar
compound 17. These chlorins exhibit typical differen-
ces in their absorption spectra compared to the por-
phyrins.
As an illustration for the absorption properties of
these compounds the UV/Vis spectra of 11a and 16a
are shown in Figure 2. Chlorin 16a shows a splitting
of the Soret band (lmax =407.5 and lmax =423) com-
pared to 11a (lmax =416.5). In addition, the longest
absorption wavelength of 16a at lmax =647.5 nm has
À1
À1
a higher extinction coefficient [loge (Lmol cm )=
.34] compared to that of 11a, l =650.5 nm [loge
4
max
À1
À1
(
Lmol cm )=3.55].
In order to prepare a more complex trans-A B -por-
2
2
[
37]
phyrin, the novel d–a cyclopropane 22
carrying
a para-bromophenyl group adjacent to the ethoxycar-
Scheme 5. Saponification of 12a to trans-A B -porphyrindi- bonyl functionality was prepared from the corre-
2
2
[
38]
carboxylic acid 13.
sponding diazo compound 20
and silyl enol ether
Adv. Synth. Catal. 2013, 355, 1409 – 1422
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M. Hassan Beyzavi et al.
FULL PAPERS
diazabicyclo
ACHTUNGTRENNUNG
diazoacetate 20 underwent Rh AHCNUTGTRENNUNG
2
4
[
39]
propanation of trimethylsilyl enol ether 21 to furnish
d–a cyclopropane 22 in 57% yield (Scheme 8). This
compound was then treated with an excess of pyrrole
in the presence of TFA (10 mol%). After work up, the
stable DPM 23 was obtained in 60% yield. Acid-cata-
lyzed condensation of DPM 23 with benzaldehyde as
a model substrate afforded trans-A B -porphyrin 24 as
2
2
1
:1 mixture of diastereomers in 21% yield.
Porphyrin 24 was subsequently metallated using
[
40]
zinc acetate to mask the inner core. The resulting
bis(4-bromophenyl)-functionalized trans-A B -Zn-por-
2
2
phyrin 25 was coupled with butyl acrylate by a Heck
[
41]
reaction in moderate yield.
only the (E,E)-isomer of the highly functionalized bis-
(alkenyl)-substituted trans-A B -Zn-porphyrin 26. The
This process provided
AHCTUNGTRENNUNG
2
2
multi-step synthesis of 26 illustrates the option of late
stage functionalizations at d–a cyclopropane-derived
moieties. Employing different aldehydes and olefins,
this approach could certainly be used to prepare a va-
riety of complex porphyrin systems. Other cross-cou-
pling reactions such as the Negishi, Suzuki, Stille or
Sonogashira reaction could further increase the diver-
sity of specifically substituted and functionalized por-
phyrins available by this approach.
Conclusions
Scheme 7. OsO -mediated dihydroxylations of 11a–c to 7,8-
dihydroxychlorins 16a–c followed by saponification of 16b
4
to dihydroxylated trans-A B -chlorindicarboxylic acid 17.
The field of tetrapyrrole chemistry is constantly ex-
panding but the synthesis of porphyrins bearing dis-
tinct functionalized meso-substituents still presents
a number of challenges. Simple and straightforward
synthetic approaches are required. We have presented
herein the first examples of applications of d–a cyclo-
propanes as precursors for the synthesis of functional-
ized porphyrin systems. These were utilized in acid-
catalyzed porphyrin condensation reactions with
a series of aromatic and aliphatic aldehydes affording
an efficient and highly flexible entry and direct access
to novel A B -porphyrins bearing functional groups in
2
2
2
2
strongly defined trans-substitution patterns. Porphyr-
ins carrying two different functional groups in their
meso positions were thus easily obtained. As exam-
ples for further modifications, selected porphyrin
products were converted into the corresponding 7,8-
dihydroxychlorins via the osmium-mediated dihydrox-
ylation as well as a selective O-debenzylation reac-
tion. In addition, through a multi-step synthesis,
a highly functionalized bis ACHTGNUTRNEUNG( alkenyl) trans-A B -Zn-
Figure 2. UV/Vis spectra of porphyrin 11a (solid line) and
2 2
7
,8-dihydroxychlorin 16a (dashed line) recorded in CH Cl
porphyrin was prepared using a Heck-type reaction.
This variety of modifications renders the d–a cyclopro-
pane-derived dipyrromethanes and their correspond-
2
2
À6
(
room temperature, 7.66ꢅ10 M).
2
1. Precursor 20 was obtained by reaction of ethyl 2- ing porphyrins as valuable tools for the synthesis of
(
4-bromophenyl)acetate (18) with 4-acetamidobenze- advanced tetrapyrrole systems for material sciences,
nesulfonyl azide (19) in the presence of 1,8- optoelectronics or biomedical applications.
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Synthesis of Functionalized trans-A B -Porphyrins
2
2
Scheme 8. Multi-step synthesis of functionalized trans-A B -Zn-porphyrin 26 by Rh ACHTNUGTRNEUNG( OAc) -catalyzed synthesis of d–a cyclo-
2 4
2
2
propane 22 conversion into DPM 23 and porphyrin 24 followed by metallation to 25 and Heck-reaction to bis
stituted trans-A B -Zn-porphyrin 26.
ACHTUNGTRENNU(GN alkenyl)-sub-
2
2
solution. Integrals are in accordance with assignments; cou-
Experimental Section
1
3
pling constants are given in Hz. All C NMR spectra are
proton decoupled. Multiplicity is indicated as follows: s (sin-
glet), d (doublet), t (triplet), m (multiplet), dd (doublet of
doublets), td (triplet of doublets), q (quartet), br. s (broad
singlet). For detailed peak assignments, 2D spectra were
General Remarks
Reactions were generally performed under argon in oven-
dried flasks. Reagents were added with syringes. Solvents
were dried by using standard procedures. Dichloromethane
1
1
1
13
1
13
measured ( H- H COSY, H- C HMQC, and H- C
HMBC). IR spectra were measured with a Jasco FT/IR-4100
spectrometer equipped with an attenuated total reflectance
(ATR) attachment (PIKE MIRacle). The UV/Vis spectra
were measured with a SPECORD S300 VIS UV/Vis spec-
trometer (Analytik Jena, Jena, Germany) with DCM as the
solvent and quartz cuvettes of 1 cm path length. HR-MS
analyses were performed with an Agilent 6210 ESI-TOF in-
strument (Agilent Technologies, Santa Clara, CA, USA).
(
DCM) was distilled and stored over molecular sieves (4ꢆ)
under an atmosphere of argon. Other reagents were pur-
chased and were used as received without further purifica-
tion unless otherwise stated. Products were purified by chro-
matography on silica gel (40–63 mm, Fluka, No. 60752, con-
taining 0.1% Ca) and detection was carried out with
a CAMAG variable UV detector (l=254/366 nm). Yields
refer to chromatographically purified products, unless other-
wise stated. Reactions were monitored by thin layer chro-
matography (TLC) analysis. NMR spectra were recorded
with Bruker (AC 250, AC 500, AVIII 700) and JOEL
À1
The solvent flow rate was adjusted to 4 mLmin and the
spray voltage was 4 kV. The drying gas flow rate was 15 psi
(1 bar). All other parameters were adjusted for maximum
+
(
Eclipse 500) instruments. Chemical shifts are reported rela-
abundance of the respective [M+H] ions (ESI-TOF=elec-
1
tive to tetramethylsilane (TMS, H: d=0.00 ppm), CHCl3
trospray ionization/time of flight). Elemental analyses were
carried out in CHN mode with a Vario EL instrument (Ele-
1
13
(
H: d=7.26 ppm), and CDCl ( C: d=77.0 ppm) in CDCl
3
3
Adv. Synth. Catal. 2013, 355, 1409 – 1422
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1415

M. Hassan Beyzavi et al.
FULL PAPERS
mentar Analysensysteme GmbH). Melting points were mea- General Procedure for the Synthesis of trans-A B -
2
2
sured with a Reichert Thermovar apparatus and are uncor-
rected. Methyl 3-(trimethylsiloxy)-1-cyclopropanecarboxy-
Porphyrin Derivatives 11a–e and 12a–h
[26]
A standard reaction was performed in a 1-L, three-necked,
round-bottom flask fitted with a septum port, bubble coun-
ter, and a gas inlet port with argon flow. 5-(3-Methoxy-3-ox-
opropyl)-dipyrromethane (8a) (465 mg, 2.00 mmol) or 5-(3-
late (5a), methyl 2-methyl-3-(trimethylsiloxy)-1-cyclopro-
[26]
panecarboxylate (5b) and ethyl 1-(4-bromophenyl)-2-(tri-
[37]
methylsiloxy)cyclopropane-1-carboxy-late (22)
were pre-
pared according to known procedures and their
spectroscopic data were compared with those reported in
the literature see the Supporting Information for the
methoxy-1-methyl-3-oxopropyl)-dipyrromethane
(8b)
(
493 mg, 2.00 mmol) and the appropriate aldehyde
1
(2.00 mmol) were dissolved in dry DCM (500 mL). The re-
sulting solution was degassed by bubbling with an argon
flow for 10 min, and TFA (30 mL, 0.40 mmol) was added by
a syringe with vigorous stirring. The reaction mixture was
stirred under argon in the dark at room temperature for the
specified time as indicated for each individual experiment in
Table 1. After the indicated time, the calixpyrrole intermedi-
ate was subjected to oxidation for 2 h by the addition of
DDQ (690 mg, 3.00 mmol), followed by neutralization of
H NMR spectrum of 22).
Synthesis of 5-(3-Methoxy-3-oxopropyl)dipyrro-
methane (8a)
The reaction was performed in a 250-mL, three-necked,
round-bottom flask fitted with a septum port, a bubble
counter, and a gas inlet port. A solution of methyl 3-(trime-
thylsiloxy)-1-cyclopropanecarboxylate
.21 mmol) and pyrrole (25 mL, 362 mmol) was degassed by
bubbling with argon for 10 min, then TFA (0.05 mL,
.72 mmol) was added. The solution was stirred for 1.5 h at
(5a)
(1.36 g,
7
TFA with NEt (500 mL, 3.60 mmol). The reaction mixture
3
was filtered through a sintered glass Bꢀchner funnel loaded
with silica gel and eluted with a mixture of DCM/EtOAc
(ratio depending on product, see individual procedures) to
afford the crude product. After concentration of the filtrate
under reduced pressure, the residue was dissolved in a mini-
mum volume of solvent and applied to gravity silica gel
column chromatography with DCM/hexanes ACHUTNGRNEGUN( /EtOAc) (ratio
depending on product, see individual procedures) for further
purification. Recrystallization of the product gave the de-
0
room temperature, and the progress of the reaction was
monitored by TLC analysis. The TLC plates were developed
in a solvent mixture of DCM/hexanes/NEt (85:14:1) and
3
the bands were visualized by exposure of the air-dried TLC
plate to bromine vapor on which the unreacted pyrrole
looks dark grey and dipyrromethane 8a looks pink when di-
luted and dark red when concentrated. Then, the reaction
mixture was diluted with DCM (200 mL) and washed with
aqueous NaOH (0.1N, 20 mL), followed by washing with
water (3ꢅ200 mL) and was then dried with anhydrous
Na SO . The solvent was removed under reduced pressure
sired pure comound. The main products as trans-A B -por-
phyrin 11 and 12 were obtained in yields between 14–31%
(see Table 1).
2 2
2
4
and then the unreacted pyrrole was removed by a rotary
evaporator (10 mbar, 608C). The resulting dark viscous oil
was dissolved in a minimal quantity of the eluent (DCM/
5
,15-Diphenyl-10,20-bis(3-methoxy-3-oxopropyl)-
porphyrin (11a)
According to the general procedure 5-(3-methoxy-3-oxo-
propyl)-dipyrromethane (8a) (465 mg, 2.00 mmol) and ben-
zaldehyde (20 mL, 2.00 mmol) were reacted in dry DCM
hexanes/NEt (85:14:1)) and was purified by silica column
3
chromatography using DCM/hexanes/NEt3 (85:14:1) as
eluent. Any remaining pyrrole elutes first, followed slowly
(
1
500 mL) using TFA (30 mL, 0.40 mmol) as catalyst. After
6 h the calixpyrrole intermediate was subjected to oxida-
by the dipyrromethane 8a (R 0.43) and followed later by
F
tailing materials. Colorless oil; yield: 1.24 g (5.34 mmol,
4%). IR (ATR): umax =3375 (NÀH), 3100 (CÀH pyrrole),
tion for 2 h by addition of DDQ (690 mg, 3.00 mmol), fol-
lowed by neutralization of TFA with NEt3 (500 mL,
7
2
(
1
(
955 (CÀH), 2875 (CH ), 1725 (C=O), 1560 (NÀH), 1435
3
CH ), 1370 (CH ), 1325 (CÀN), 1215 (CÀO), 1155 (CÀO),
3
.60 mmol). The reaction mixture was filtered and eluted
2
3
115 (CÀN), 1095 (CÀH pyrrole), 1025 (CÀH pyrrole), 885
with a mixture of DCM/EtOAc (95:5) to afford the crude
products. After concentration of the filtrate under reduced
pressure, the residue was dissolved in a minimum volume of
solvent and applied to gravity silica gel column chromatog-
raphy with DCM/hexanes (80:20) for further purification
and trans-A B -porphyrin 11a was obtained as the main
product. Recrystallization from a DCM/MeOH mixture
gave the pure product as purple crystals; yield: 121 mg,
À1
1
CÀH pyrrole), 790 (CÀH), 720 (CÀH) cm ; H NMR
(
500 MHz, CDCl ): d=2.22–2.28 (m, 2H, CHCH ), 2.29–
3
2
2
7
6
7
.35 (m, 2H, CH CO), 3.64 (s, 3H, OCH ), 4.01 (t, J=
2
3
.6 Hz, 1H, meso-H), 6.05–6.08 (m, 2H, pyrrole-H), 6.12–
.15 (m, 2H, pyrrole-H), 6.60–6.63 (m, 2H, pyrrole-H),
2
2
1
3
.82 ppm (br. s, 2H, 2 ꢅ NH); C NMR (126 MHz, CDCl ):
3
d=29.7 (CHCH ), 32.0 (CH CO), 37.0 (meso-C), 51.7
2
2
1
(
0.19 mmol, 19%); mp 2578C. H NMR (500 MHz, CDCl ):
(
OCH ), 105.9 (pyrrole-C), 108.2 (pyrrole-C), 117.5 (pyr-
3
3
d=À2.74 (br. s, 2H, 2ꢅNH), 3.51–3.54 (m, 4H, 2ꢅ
role-C), 132.5 (pyrrole-C), 174.0 ppm (C=O); HR-MS (ESI-
+
CH CH CO), 3.77 (s, 6H, 2ꢅOCH ), 5.32–5.36 (m, 4H, 2ꢅ
TOF): m/z=233.1278, calcd. for C H N O [M+H] :
2
2
3
1
3
17
2
2
CH CH CO), 7.76–7.84 (m, 6H, Ar), 8.19–8.21 (m, 4H, Ar),
2
33.1290; m/z=255.1109, calcd. for C H N NaO [M+
2
2
1
3
16
2
2
+
8
4
3
.90 (d, J=4.8 Hz, 4H, ß-pyrrole-H), 9.46 ppm (d, J=
.8 Hz, 4H, ß-pyrrole-H); C NMR (126 MHz, CDCl ): d=
0.5 (2ꢅCH CH CO), 41.9 (2ꢅCH CH CO), 52.0 (2ꢅ
Na] : 255.1109; m/z=271.0836, calcd. for C H KN O [M
+
1
3
16
2
2
13
+
K] : 271.0849; elemental anal. calcd. (%) for C H N O
3
1
3
16
2
2
(
1
232.1): C 67.22, H 6.94, N 12.06; found: C 66.55, H 6.69, N
1.81.
2
2
2
2
OCH ), 117.0 (Ar), 119.6 (Ar), 126.73 (Ar), 127.67 (Ar),
3
1
27.9 (Ar), 132.3 (Ar), 134.6 (Ar), 142.4 (Ar), 173.2 (2ꢅC=
O); HR-MS (ESI-TOF): m/z=635.2661, calcd. for
+
C H N O [M+H] : 635.2658; m/z=657.2488, calcd. for
4
0
35
4
4
+
C H N NaO [M+Na] : 657.7258; m/z=673.2217, calcd.
4
0
34
4
4
1416
asc.wiley-vch.de
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1409 – 1422

Synthesis of Functionalized trans-A B -Porphyrins
2
2
+
for C H KN O [M+K] : 673.2217; UV/Vis (CH Cl ): l
max
[
[
was washed with hexanes, after that, the residue was taken
up in a minimum volume of solvent and applied to silica gel
column chromatography for further purification using
DCM/MeOH (9:1) as the eluent. Recrystallization of the
isolated fraction from a DCM/hexanes mixture afforded the
pure product 14. Purple crystals; yield: 240 mg (0.35 mmol,
40
34
4
4
À1
2
2
À1
log e (Lmol cm )]=416.5 [5.27], 516.0 [4.20], 550.0
3.73], 594.5 [3.52], 650.5 nm [3.38].
5
,15-Diphenyl-10,20-bis(2-carboxy-1-methylethyl)-
porphyrin (13)
1
quantitative); mp 2908C (decomp.); 1:1 dr. H NMR
(
500 MHz, acetone-d ): d=À2.50 (s, 2H, 2ꢅNH), 2.39 (d,
6
5
,15-Diphenyl-10,20-bis(3-methoxy-1-methyl-3-oxopropyl)-
porphyrin (12a) (40 mg, 0.06 mmol) was dissolved in THF
15 mL). Then a solution of potassium hydroxide (270 mg,
.81 mmol) dissolved in hot methanol (10 mL) and three
drops of water were added, and the mixture was stirred for
2 h at room temperature. The evolution of the reaction was
J=7.4 Hz, 6H, 2ꢅCHCH ), 3.83–3.85 (m, 4H, 2ꢅCHCH ),
3
2
6
7
4
4
.01–6.09 (m, 2H, 2ꢅCHCH ), 7.33–7.35 (m, 2H, Ar), 7.60–
2
(
4
.63 (m, 2H, Ar), 7.67–7.70 (m, 4H, Ar), 8.90 (d, J=4.9 Hz,
H, ß-pyrrole-H), 8.91 (br. s, 2H, 2ꢅOH), 9.69 (d, J=
1
3
.9 Hz, 4H, ß-pyrrole-H); C NMR (126 MHz, acetone-d ):
6
2
d=26.60 (CHCH ), 26.61 (CHCH ), 36.5 (2ꢅCHCH ), 46.08
(
1
1
1
3
3
2
monitored by TLC. After 22 h the solvents of the mixture
were evaporated using a rotary evaporator. The residue was
dissolved in 100 mL of EtOAc, transferred to a 500 mL sep-
aratory funnel and to the organic phase was added water
CH CO), 46.10 (CH CO), 50.9 (2ꢅCO CH ), 115.0 (Ar),
2 2 2 3
19.1 (Ar), 121.9 (Ar), 123.1 (Ar), 126.2 (Ar), 127.6 (Ar),
28.5 (Ar), 129.2 (Ar), 132.0 (Ar), 144.2 (Ar), 155.8 (Ar),
72.6 (2ꢅC=O); HR-MS (ESI-TOF): m/z=695.2877, calcd.
(
100 mL) and the solution was neutralized by adding 25%
hydrochloric acid. The organic phase was washed with water
3ꢅ100 mL) (one spatula of NH Cl was added into this mix-
+
for C H N O [M+H] : 695.2870; UV/Vis (acetone): l
4
2
39
4
6
À1
max
À1
[
log e (Lmol cm )]=415.5 [5.47], 514.0 [4.18], 547.0
(
4
[
3.76], 593.5 [3.67], 649.0 nm [3.49].
ture for a better phase separation), and dried with anhy-
drous Na SO . The drying agent was removed and the or-
2
4
ganic phase was evaporated to dryness. The residue was dis-
solved in a minimum volume of DCM/MeOH (90:10) and
applied to gravity silica gel column chromatography with
DCM/MeOH (90:10) for further purification. Recrystalliza-
tion of 13 from a DCM/MeOH mixture gave the desired
5
,15-Bis(2-carboxy-1-methylethyl)-10,20-bis(3-
hydroxyphenyl)-porphyrin (15)
5
,15-Bis(3-hydroxyphenyl)-10,20-bis(3-methoxy-1-methyl-3-
oxopropyl)-porphyrin (14) (100 mg, 0.14 mmol) was dis-
solved in THF (15 mL). To this solution were added a solu-
tion of potassium hydroxide (270 mg, 4.81 mmol) dissolved
in hot methanol (10 mL) and three drops of water, and the
solution was stirred for 24 h at room temperature. The evo-
lution of the reaction was monitored by TLC. Once no fur-
ther progress of the reaction was detectable (after 24 h), the
solvents in the reaction mixture were evaporated using
a rotary evaporator. Then, the residue was dissolved in
EtOAc (100 mL) and was transferred into a 500 mL separa-
tory funnel and to the organic phase water was added
pure product as purple crystals; yield: 31 mg (0.05 mmol,
1
8
1%); mp >3008C; 1:1 dr. H NMR (500 MHz, DMSO-d ):
6
d=À2.70 (s, 2H, 2ꢅNH), 2.36 (d, J=7.2 Hz, 6H, 2ꢅ
CHCH ), 3.69–3.81 (m, 4H, 2ꢅCHCH ), 5.90–5.98 (m, 2H,
3
2
2
8
9
ꢅCHCH ), 7.81–7.85 (m, 4H, Ar), 7.85–7.89 (m, 2H, Ar),
2
.17–8.21 (m, 4H, Ar), 8.75 (d, J=5.0 Hz, 4H, ß-pyrrole-H),
.75 (d, J=5.0 Hz, 4H, ß-pyrrole-H), 12.14 (br. s, 2H, 2ꢅ
13
CO H); C NMR (126 MHz, CDCl ): d=27.75 (CHCH ),
2
3
3
2
7.77 (CHCH ), 36.7 (2ꢅCHCH ), 46.8 (2 ꢅ CH CO), 100.0
3
2
2
(
(
(
Ar), 104.5 (Ar), 108.6 (Ar), 114.3 (Ar), 119.2 (Ar), 124.1
Ar), 127.3 (Ar), 128.6 (Ar), 132.4 (Ar), 134.5 (Ar), 138.6
(
100 mL) and the solution was neutralized by adding 25%
Ar), 142.8 (Ar), 148.5 (Ar), 174.1 (2ꢅC=O); HR-MS (ESI-
hydrochloric acid. After neutralization, the organic phase
was washed with water (3ꢅ100 mL) (one spatula of NH Cl
was added into this mixture for a better phase separation),
and dried with anhydrous Na SO . The drying agent was re-
moved and the organic phase was evaporated to dryness.
The residue was dissolved in a minimum volume of DCM/
MeOH (70:30) and applied to gravity silica gel column chro-
matography with DCM/MeOH (70:30) for further purifica-
tion. Recrystallization of the product 15 from a DCM/
MeOH mixture gave the desired pure crystalline form of the
+
TOF): m/z=635.2609, calcd. for C H N O [M+H] :
4
0
35
4
4
4
6
35.2658; UV/Vis spectrum in CH Cl : lmax [log
2 2
À1
À1
e (Lmol cm )]=417.0 [4.86], 515.5 [3.82], 549.0 [3.66],
93.5 [3.63], 650.5 nm [3.60].
2
4
5
5
,15-Bis(3-hydroxyphenyl)-10,20-bis(3-methoxy-1-
methyl-3-oxopropyl)-porphyrin (14)
5,15-Bis(3-benzyloxyphenyl)-10,20-bis(2-methoxycarbonyl-1-
methylethyl)-porphyrin (12e) (305 mg, 0.35 mmol) was dis-
solved in trifluoroacetic acid (6 mL). To the resulting green
product as purple crystals; yield: 82 mg (0.12 mmol, 85%);
1
mp >3008C; 1:1 dr. H NMR (700 MHz, DMSO-d ): d=
6
solution
was
added
pentamethylbenzene
(206 mg,
À2.72 (br. s, 2H, 2ꢅNH), 2.37 (d, J=7.2 Hz, 6H, 2ꢅ
1.39 mmol). The reaction mixture was stirred at room tem-
CHCH ), 3.71–3.75 (m, 2H, 2ꢅCHCHHCO), 3.78–3.81 (m,
3
perature overnight. After this time, the reaction mixture was
transferred to a separatory funnel and crushed ice was
added, followed by EtOAc (200 mL) and water (150 mL).
NaOH (20%) was added to attain a pH of 5–6 in the aque-
ous phase, the color of the organic phase changing from
green to purple. The phases were separated and the organic
phase was then washed with water (4ꢅ200 mL) until neutral
pH was reached. The organic phase was dried with anhy-
drous Na SO . The drying agent was removed and the or-
2H, 2ꢅCHCHHCO), 5.91–5.96 (m, 2H, 2ꢅCHCH ), 7.26–
7.28 (m, 2H, Ar), 7.54–7.61 (m, 6H, Ar), 8.61 (br. s, 2H, 2ꢅ
2
C H OH), 8.83 (d, J=4.8 Hz, 4H, ß-pyrrole-H), 9.74 (d, J=
6
4
4.9 Hz, 4H, ß-pyrrole-H), 9.89 (br. s, 2H, 2ꢅCO H);
2
1
3
C NMR (176 MHz, DMSO-d ): d=27.60 (CHCH ), 27.62
6
3
(CHCH ), 36.6 (2ꢅCHCH ), 46.71 (CH CO), 46.73
3
2
2
(CH CO), 110.0 (Ar), 115.5 (Ar), 119.2 (Ar), 122.2 (Ar),
2
123.9 (Ar), 126.1 (Ar), 128.1 (Ar), 129.4 (Ar), 132.3 (Ar),
143.8 (Ar), 146.7 (Ar), 156.1 (Ar), 174.0 (2ꢅC=O); HR-MS
2
4
+
ganic phase was evaporated to dryness. The remaining solid
(ESI-TOF): m/z=667.2559, calcd. for C H N O [M+H] :
4
0
35
4
6
Adv. Synth. Catal. 2013, 355, 1409 – 1422
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1417

M. Hassan Beyzavi et al.
FULL PAPERS
À1
À1
6
4
67.2557; UV/Vis (MeOH): lmax [log e (Lmol cm )]=
1H, Ar), 8.02–8.05 (m, 1H, Ar), 8.06–8.09 (m, 2H, Ar), 8.32
(d, J=4.9 Hz, 1H, ß-pyrrole-H), 8.52 (d, J=4.5 Hz, 1H, ß-
pyrrole-H), 8.71 (d, J=4.9 Hz, 1H, ß-pyrrole-H), 9.02 (d,
J=5.0 Hz, 1H, ß-pyrrole-H), 9.08 (d, J=4.6 Hz, 1H, ß-pyr-
17.0 [5.19], 514.5 [3.97], 552.5 [3.73], 594.0 [3.58], 648.0 nm
[3.27].
1
3
role-H), 9.22 (d, J=5.0 Hz, 1H, ß-pyrrole-H); C NMR
5
,15-Diphenyl-10,20-bis(3-methoxy-3-oxopropyl)-7,8-
(126 MHz,
CDCl ):
d=28.8
(CH CH CO),
30.2
3
2
2
cis-dihydroxychlorin (16a)
(CH CH CO), 39.9 (CH
2
2
2
CH CO), 41.2 (CH
2
CH
2
CO), 51.86
2
(
(
(
(
(
(
(
OCH ), 51.94 (OCH ), 73.3 (CHOH), 74.2 (CHOH), 120.0
3
3
CAUTION: OsO is highly poisonous, even at low exposure
4
Ar), 121.3 (Ar), 122.6 (Ar), 124.6 (Ar), 125.0 (Ar), 126.8
Ar), 127.80 (Ar), 127.89 (Ar), 128.2 (Ar), 128.4 (Ar), 128.9
Ar), 129.4 (Ar), 132.3 (Ar), 133.7 (Ar), 134.0 (Ar), 134.8
Ar), 135.5 (Ar), 140.1 (Ar), 140.8 (Ar), 141.5 (Ar), 142.1
Ar), 152.3 (Ar), 153.2 (Ar), 160.5 (Ar), 162.9 (Ar), 173.2
levels, and must be handled with appropriate precautions.
OsO4 also stains the human cornea, which can lead to
blindness if proper safety precautions are not observed.
Under standard reaction conditions, in a 250-mL, three-
necked, round-bottom flask equipped with a gas inlet port
with argon flow and a stir bar, 5,15-diphenyl-10,20-bis(3-me-
thoxy-3-oxopropyl)-porphyrin (11a) (520 mg, 0.82 mmol)
C=O), 174.1 (C=O); HR-MS (ESI-TOF): m/z669.2688,
+
calcd. for C H N O [M+H] : 669.2713, m/z=691.2506,
calcd. for C H N NaO [M+Na] : 691.2513, m/z=
4
0
37
4
6
+
4
0
36
4
6
(
this amount was calculated from the commercially available
+
7
07.2239, calcd. for C H KN O [M+K] : 707.2272; UV/
40 36 4 6
250 mg OsO packed in a glass ampoule) was dissolved in
À1
À1
4
Vis (CH Cl ): l [log e (Lmol cm )]=407.5 [5.16],
2
2
max
dry DCM (30 mL) and freshly distilled pyridine (15 mL).
Then, the argon flow was temporarily closed and the am-
poule containing 1.2 equivalents of OsO4 (250 mg,
4
6
23.0shldr [5.09], 521.5 [4.10], 548.0 [4.12], 594.0 [3.71],
47.5 nm [4.26].
0.98 mmol) was opened by snapping off the glass top at the
neck using glass ampoule cracker and was immediately
along with the glass ampoule residues transferred into the
reaction mixture (caution: use gloves, eye protection, and
fume hood). Using an argon balloon, the flask was stop-
pered under argon atmosphere, shielded from light with alu-
minum foil, and the contents stirred at ambient temperature.
The evolution of the reaction was monitored by TLC. Once
no further progress of the reaction was detectable (after
5
7
,15-Bis(2-carboxyethyl)-10,20-bis(3-hydroxyphenyl)-
,8-cis-dihydroxychlorin (17)
5,15-Bis(3-acetoxyphenyl)-10,20-bis(3-methoxy-3-oxoprop-
yl)-7,8-cis-dihydroxychlorin (16b) (140 mg, 0.178 mmol) was
dissolved in THF (20 mL). To this solution was added a solu-
tion of potassium hydroxide (400 mg, 7.13 mmol) dissolved
in hot methanol (10 mL), and the solution was stirred for
12 h at room temperature. The evolution of the reaction was
monitored by TLC. Once no further progress of the reaction
was detectable (after 12 h), the solvents in the reaction mix-
ture were evaporated using a rotary evaporator. Then, the
residue was dissolved in 200 mL EtOAc, then transferred
into a 1 L separatory funnel and to the organic phase water
was added (200 mL) and the solution was neutralized by
adding 25% hydrochloric acid. After neutralization, the or-
ganic phase was washed with water (3ꢅ200 mL) (one spatu-
2
2 h) a saturated MeOH/H O (1:1) solution of NaHSO
2
3
(
50 mL) was added to the crude reaction mixture. The flask
was stoppered and wrapped in aluminum foil, and the bi-
phasic solution was vigorously stirred at ambient tempera-
ture for 24 h. Then, the mixture was filtered through a short
plug of diatomaceous earth (Celite) and washed with
MeOH and then the solvent in the filtrate was minimized
using a rotary evaporator. Then, the residue was transferred
into a 250 mL separatory funnel and EtOAc was added. The
organic phase (EtOAc) was washed with water (3ꢅ200 mL)
la of NH Cl was added into this mixture for a better phase
4
(
one spatula of NH Cl was added into this mixture for
separation), and dried with anhydrous Na SO . The drying
4
2
4
a better phase separation), and dried with anhydrous
Na SO . Then, the organic fraction was evaporated to dry-
agent was removed and the organic phase was evaporated
to dryness. The residue was dissolved in a minimum volume
of DCM/EtAOc/MeOH (70:25:5) and applied to gravity
silica gel column chromatography with DCM/EtAOc/MeOH
(70:25:5) for further purification. After the recovery of
a small amount of the low polarity starting material 16b
(4%) as the second major fraction the dihydroxychlorin di-
carboxylic acid 17 was obtained. Recrystallization of the
product 17 from a DCM/MeOH mixture gave the desired
pure crystalline form of the product as dark reddish-brown
2
4
ness. A gentle stream of argon for 30 min ensured that the
crude material was thoroughly dried. The residue was dis-
solved in a minimum volume of DCM/EtAOc (80:20) and
applied to gravity silica gel column chromatography with
DCM/EtAOc (80:20) for further purification. After the re-
covery of a small amount of the low polarity starting materi-
al 11a (14%) (purple in color), as the second major fraction
dihydroxychlorin 16a (red in color on TLC plate) was ob-
tained. Recrystallization of the product from a DCM/
MeOH mixture gave the desired pure crystalline form of the
crystals; yield: 79 mg (0.118 mmol, 66%); mp >3008C.
1
H NMR (500 MHz, CDCl ): d=3.20–3.25 (m, 3H, 2ꢅ
3
product aseddish-brown crystals; yield: 346 mg (0.52 mmol,
CHHCO, CHHCO), 3.40–3.45 (m, 1H, CHHCO), 4.47–4.75
(m, 4H, 2ꢅCH CH CO), 6.12–6.14 and 6.22–6.23 (2ꢅm,
1
6
3%); mp 2618C; H NMR (500 MHz, CDCl ): d=À1.91
3
2
2
(
br. s, 1H, NH), À1.74 (br. s, 1H, NH), 2.81 (br. s, 1H,
1H, CHOH), 6.38–6.43 and 6.49–6.52 (2ꢅm, 1H, CHOH),
7.12–7.16 (m, 1H, Ar), 7.20–7.22 (m, 1H, Ar), 7.31–7.56 (m,
6H, Ar), 8.30–8.32 (m, 1H, ß-pyrrole-H), 8.37–8.41 (m, 1H,
ß-pyrrole-H), 8.68–8.70 (m, 1H, ß-pyrrole-H), 8.86–8.92 (m,
1H, ß-pyrrole-H), 8.98–9.04 (m, 1H, ß-pyrrole-H), 9.13–
CHOH), 3.24–3.32 (m, 1H, CH CHHCO), 3.39 (t, J=
2
8
.3 Hz, 2H, CH CHHCO, CH CHHCO), 3.43–3.51 (m, 1H,
2
2
CH CHHCO), 3.73 (s, 3H, OCH ), 3.74 (s, 3H, OCH ), 4.29
2
3
3
(
br. s, 1H, CHOH), 4.65–4.73 (m, 1H, CHHCH CO), 4.87–
2
1
3
4
.94 (m, 1H, CHHCH CO), 5.02–5.09 (m, 2H, CHHCH CO,
9.19 ppm (m, 1H, ß-pyrrole-H);
C NMR (126 MHz,
2
2
CHHCH CO), 6.31 (d, J=7.2 Hz, 1H, CHOH), 6.57 (d, J=
CDCl ): d=28.5 (CmesoCH ), 31.4 (CmesoCH ), 39.6
2
3
2
2
7.3 Hz, 1H, CHOH), 7.69–7.78 (m, 6H, Ar), 7.92–7.95 (m,
(CmesoCH CH ), 40.9 (C CH CH ), 72.9 (CHOH), 73.0
2 2 meso 2 2
1418
asc.wiley-vch.de
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1409 – 1422

Synthesis of Functionalized trans-A B -Porphyrins
2
2
(
CHOH), 100.0 (Ar), 111.1 (Ar), 113.6 (Ar), 114.4 (Ar), 5,15-Bis[2-(4-bromophenyl)-3-ethoxy-3-oxopropyl]-
1
1
1
1
1
1
14.7 (Ar), 119.2 (Ar), 119.5 (Ar), 121.1 (Ar), 121.5 (Ar),
21.8 (Ar), 123.9 (Ar), 124.4 (Ar), 125.1 (Ar), 126.1 (Ar),
27.5 (Ar), 127.8 (Ar), 128.0 (Ar), 128.8 (Ar), 132.2 (Ar),
34.4 (Ar), 135.3 (Ar), 140.3 (Ar), 142.9 (Ar), 143.1 (Ar),
44.4 (Ar), 150.5 (Ar), 155.8 (Ar), 156.0 (Ar), 156.3 (Ar),
1
0,20-diphenylporphyrin (24)
The reaction was performed according to the general proce-
dure. 5-[2-(4-Bromophenyl)-3-ethoxy-3-oxopropyl]-dipyrro-
methane (23) (803 mg, 2.00 mmol) and benzaldehyde
(
20 mL, 2.00 mmol) were dissolved in dry DCM (500 mL).
62.0 (Ar), 164.1 (Ar), 174.9 (C=O), 175.9 (C=O); HR-MS
+
The resulting solution was degassed by bubbling with an
argon flow for 10 min, and TFA (30 mL, 0.40 mmol) was
added by syringe with vigorous stirring. The reaction mix-
ture was stirred under argon in the dark at room tempera-
ture for 16 h. Then, the calixpyrrole intermediate was sub-
jected to oxidation for 2 h by the addition of DDQ (690 mg,
(
ESI-TOF): m/z=673.2319, calcd. for C H N O [M+H] :
3
8
33
4
8
6
73.2298; m/z=695.2126, calcd. for C H N NaO [M+
38 32 4 8
+
Na] : 695.2118; m/z=711.1854, calcd. for C H KN O
3
8
32
4
8
+
[M+K] :
711.1857;
UV/Vis
(MeOH):
lmax
[log
À1
À1
e (Lmol cm )]=406.5 [5.14], 420.5
5
[5.08], 519.0 [4.08],
Shldr
46.0 [4.08], 595.0 [3.78], 647.5 nm [4.21].
3
.00 mmol), followed by neutralization of TFA with NEt3
(
500 mL, 3.60 mmol). The reaction mixture was filtered
through a sintered glass Bꢀchner funnel loaded with silica
gel and eluted with a mixture of DCM/EtOAc (90:10) to
afford the crude products. After concentration of the filtrate
under reduced pressure, the residue was dissolved in a mini-
mum volume of solvent and applied to gravity silica gel
column chromatography with DCM/EtOAc (98:2) for fur-
ther purification and trans-A B -porphyrin 24 as the main
Synthesis of 5-[2-(4-Bromophenyl)-3-ethoxy-3-oxo-
propyl]dipyrromethane (23)
A solution of ethyl 1-(4-bromophenyl)-2-(trimethylsiloxy)cy-
clopropane-1-carboxylate (22) (2.58 g, 7.21 mmol) and pyr-
role (25 mL, 362 mmol) was degassed by bubbling with
argon for 10 min, then TFA (0.05 mL, 0.72 mmol) was
added. The solution was stirred for 3 h at room temperature,
and the progress of reaction was monitored by TLC analysis.
The TLC plates were developed in a solvent mixture of
2
2
product was obtained. Recrystallization of the product from
a DCM/MeOH mixture gave the desired pure crystalline
form of the product as purple crystals; yield: 205 mg
1
DCM/EtOAc/NEt (95:4:1) and the bands were visualized
(0.21 mmol, 21%); mp 2448C; 1:1 dr. H NMR (500 MHz,
3
by exposure of the air-dried TLC plate to bromine vapor as
described for 8a. Then, the reaction mixture was diluted
with DCM (200 mL) and washed with aqueous NaOH
CDCl ): d=À2.81 (br. s, 2H, 2ꢅNH), 0.88 (t, J=7.2 Hz,
3
6H, 2ꢅCH ), 3.89–4.02 (m, 4H, 2ꢅCH CH ), 4.72 (t, J=
3
2
3
7.0 Hz, 2H, 2ꢅCH), 5.24–5.28 (m, 2H, 2ꢅCHHCH), 5.82
(dd, J=14.8, 7.5 Hz, 2H, 2ꢅCHHCH), 7.19 (d, J=8.1 Hz,
4H, 2ꢅAr [meta to Br]), 7.32 (d, J=8.3 Hz, 4H, 2ꢅAr
[ortho to Br]), 7.74–7.82 (m, 6H, 2ꢅAr), 8.15–8.18 (m, 4H,
2ꢅAr), 8.00–8.81 (m, 4H, ß-pyrrole-H), 9.26–9.27 (m, 4H,
(
0.1N, 20 mL), followed by washing with water (3ꢅ200 mL)
and was then dried with anhydrous Na SO . The solvent was
2
4
removed under reduced pressure and then the unreacted
pyrrole was removed by a rotary evaporator (10 mbar,
1
3
608C). The resulting dark viscous oil was dissolved in a mini-
ß-pyrrole-H); C NMR (126 MHz, CDCl ): d=13.9 (2ꢅ
3
mal quantity of the eluent (DCM/EtOAc/NEt (95:4:1)) and
CH ), 39.1 (2ꢅCH CH), 58.6 (2ꢅCH), 61.2 (2ꢅCH CH ),
3
3
2
2
3
was purified by silica column chromatography using DCM/
EtOAc/NEt3 (95:4:1) as eluent. Any remaining pyrrole
elutes first, followed slowly by the dipyrromethane 23 (RF
115.3 (Ar), 119.7 (Ar), 121.6 (Ar), 126.7 (Ar), 127.8 (Ar),
129.9 (Ar), 131.9 (Ar), 134.6 (Ar), 138.2 (Ar), 142.4 (Ar),
173.4 ppm (2ꢅC=O); HR-MS (ESI-TOF): m/z=971.1822,
+
0
.57) and followed later by tailing materials; colorless oil;
calcd. for C H Br N O [M+H] : 971.1808; UV/Vis
5
4
45
2
4
4
À1
À1
yield: 1.79 g (4.47 mmol, 62%). IR (ATR): umax =3375 (NÀ (CH Cl ): l
[log e (Lmol cm )]=418.5 [5.38], 517.5
2
2
max
H), 3095 (CÀH pyrrole), 2975 (CÀH), 2895 (CH ), 1715 (C= [4.16], 551.0 [4.47], 595.0 [3.40], 651.0 nm [3.25].
3
O), 1560 (NÀH), 1485 (CH ), 1440 (NÀH pyrrole), 1370
2
(
1
(
CH ), 1340 (CÀN), 1175 (CÀO), 1150 (CÀO), 1115 (CÀN),
3
AHCTUNGTRENNUNG
095 (CÀH pyrrole), 1025 (CÀH pyrrole), 1010 (Ar-Br), 790
1
À1
1
CÀH), 720 cm (CÀH); H NMR (500 MHz, CDCl ): d=
3
1
.17 (t, J=7.1 Hz, 3H, CH CH ), 2.36–2.41 (m, 1H,
A standard reaction was performed using a 100-mL, round-
bottom flask in which 5,15-bis[2-(4-bromophenyl)-3-ethoxy-
2
3
CHCHHCHCO), 2.62–2.68 (m, 1H, CHCHHCHCO), 3.48
t, J=7.6 Hz, 1H, CHCO), 3.81 (dd, J=9.0, 6.7 Hz, 1H,
meso-H), 4.00–4.12 (m, 2H, CH CH ), 6.01–6.03 (m, 1H,
(
3-oxopropyl]-10,20-diphenylporphyrin
(24)
(98 mg,
0.10 mmol) was dissolved in DCM/MeOH (4:1; 25 mL).
Then, zinc acetate dihydrate (133 mg, 0.60 mmol) was pre-
dissolved in MeOH (5 mL) and was added to the reaction
mixture at room temperature. The evolution of the reaction
was monitored by TLC. Once no further progress of the re-
action was detectable (after 2 h), the solvents were evapo-
rated using a rotary evaporator and to the crude reaction
mixture was added DCM (100 mL) and then the reaction
mixture was washed with water (3ꢅ150 mL) and dried with
anhydrous Na SO . The organic phase was finally evaporat-
2
3
pyrrole-H), 6.05–6.07 (m, 1H, pyrrole-H), 6.12–6.15 (m, 2H,
pyrrole-H), 6.58–6.59 (m, 1H, pyrrole-H), 6.63–6.64 (m, 1H,
pyrrole-H), 7.12–7.14 (m, 2H, Ar), 7.42–7.45 (m, 2H, Ar),
1
3
7
.69 (br s, 1H, NH), 7.74 ppm (br. s, 1H, NH); C NMR
(
126 MHz, CDCl ): d=14.2 (CH CH ), 35.4 (5-meso-C),
3
2
3
3
7.7 (CHCH CH), 48.7 (CHCO), 61.2 (CH CH ), 105.4 (pyr-
2
2
3
role-C), 106.5 (pyrrole-C), 108.2 (pyrrole-C), 108.3 (pyrrole-
C), 117.5 (pyrrole-C), 117.8 (pyrrole-C), 121.4 (Ar), 130.0
(
(
Ar), 131.7 (Ar), 131.9 (Ar), 132.6 (Ar), 137.8 (Ar), 173.4
2
4
C=O); HR-MS (ESI-TOF): m/z=401.0844, calcd. for
ed to dryness by rotary evaporation. The residue was dis-
solved in a minimum volume of DCM/EtAOc (90:10) and
applied to gravity silica gel column chromatography with
DCM/EtAOc (90:10) for further purification. The product
25 was obtained and recrystallization of the product from
+
C H BrN O [M+H] : 401.0865; m/z=423.0671, calcd. for
C H BrN NaO [M+Na] : 423.0684; elemental anal. calcd.
20
22
2
2
+
20
21
2
2
(
%) for C H BrN O (400.1): C 59.86, H 5.27, N 6.98;
20 21 2 2
found: C 58.97, H 5.01, N 6.61.
Adv. Synth. Catal. 2013, 355, 1409 – 1422
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1419

M. Hassan Beyzavi et al.
FULL PAPERS
a DCM/MeOH mixture gave the desired pure crystalline
CH CH CH ),
19.3
(2ꢅCH CH CH ),
30.8
(2ꢅ
2
2
3
2
2
3
form of the product as reddish-pink crystals; yield: 104 mg,
CH CH CH ), 39.5 (2ꢅCH CH), 59.2 (2ꢅCH CH), 61.2 (2ꢅ
2
2
3
2
2
1
010 mmol, quantitative); mp 1608C; 1:1 dr. H NMR
CO CH CH ), 64.5 (2ꢅCO CH CH ), 116.28 (CHCHCO ),
2
2
3
2
2
2
2
(
(
(
7
[
500 MHz, CDCl ): d=0.80–0.83 (m, 6H, 2ꢅCH ), 3.82–3.93
116.31
(CHCHCO ),
118.24
(CHCHCO ),
118.26
3
3
2
2
m, 4H, 2ꢅCH CH ), 4.66 (t, J=7.1 Hz, 2H, 2ꢅCH), 5.13
(CHCHCO ), 120.5 (Ar), 126.59 (Ph), 126.62 (Ph), 126.65
2
3
2
dd, J=13.9, 6.7 Hz, 2H, 2ꢅCHHCH), 5.66 (dd, J=14.9,
.7 Hz, 2H, 2ꢅCHHCH), 7.15 (d, J=8.3 Hz, 4H, 2ꢅAr
meta to Br]), 7.33 (dd, J=8.4, 1.9 Hz, 4H, 2ꢅAr [ortho to
(Ph), 127.6 (Ph), 128.44 (Ar*), 128.46 (Ar*), 128.8 (Ar*),
129.2 (Ar*), 132.6 (Ar), 133.70 (Ar), 133.73 (Ar), 134.47
(Ar), 134.53 (Ar), 134.57 (Ar), 141.58 (Ar), 141.60
(Ar),142.8 (Ar), 144.1 (Ar), 149.7 (Ar), 150.4 (Ar), 167.2
Br]), 7.76–7.84 (m, 6H, Ar), 8.12–8.15 (m, 4H, Ar), 8.83 (d,
J=4.7 Hz, 4H, ß-pyrrole-H), 9.20–9.24 (m, 4H, ß-pyrrole-
(2ꢅCHCHC=O), 173.5 (2ꢅCH CHC=O), *=carbons in
2
13
H); C NMR (126 MHz, CDCl ): d=13.70 (CH ), 13.72
1,4-disubstituted phenyls; HR-MS (ESI-TOF): m/z=
3
3
+
(
CH ), 39.2 (2ꢅCH CH), 58.6 (2ꢅCH), 61.0 (2ꢅCH CH ),
1129.4078, calcd. for C H N O Zn [M+H] : 1129.4094;
3
2
2
3
68 65
4
8
À1
À1
100.0 (Ar), 116.0 (Ar-Br), 120.4 (Ar), 121.5 (Ar), 126.53
UV/Vis (CH Cl ): l
[log e (Lmol cm )]=421.0 [5.52],
2
2
max
(
(
Ar-Br), 126.57 (Ar-Br), 126.61 (Ar-Br), 127.5 (Ar), 128.9
Ar-Br), 129.8 (Ar), 131.7 (Ar), 132.4 (Ar), 134.4 (Ar),
552.0 nm [4.24].
1
34.50 (Ar), 134.58 (Ar), 138.2 (Ar), 142.7 (Ar-Br), 149.5
Supporting Information
(
Ar), 150.1 (Ar), 173.3 (2ꢅC=O); HR-MS (ESI-TOF): m/
+
Preparation and characterization data of compounds 8b,
z=1033.0917, calcd. for C H Br N O Zn [M+H] :
5
4
43
2
4
4
1
À1
À1
11b–e, 12a–h, 16b, 16c and 20; copies of the H NMR spec-
1033.0943; UV/Vis (CH Cl ): l
[log e (Lmol cm )]=
2
2
max
1
13
trum of compound 22; H and C NMR spectra of com-
4
20.0 [5.16], 552.0 [4.33], 589.0 nm [3.70].
pounds 8a, 8b, 11b–e, 12a–h, and 13–26; copies of the COSY
1
1
1
13
1
13
H- H, HMQC H- C and HMBC H- C correlated NMR
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
{5,15-Bis[(E)-2-(4-(3-butoxy-3-oxoprop-1-en-1-yl)-
spectra of compound 11a as the parent compound are avail-
able as Supporting Information.
phenyl)-3-ethoxy-3-oxopropyl]-10,20-diphenyl-
porphyrinato}zinc(II) (26)
A standard reaction was performed in a 100-L, three-
necked, round-bottom flask fitted with a septum port,
bubble counter, and a gas inlet port with argon flow. Zn-por-
phyrin 25 (104 mg, 0.10 mmol) was dissolved in dry DMF
Acknowledgements
Financial support for this project by the European Union
and the Freie Universitꢀt Berlin is gratefully acknowledged
(
15 mL) under argon atmosphere in a Schlenk flask and was
transferred to the flask. To the resulting solution were
added palladium acetate (3.4 mg, 0.015 mmol, 15 mol-%),
triphenylphosphine (15.7 mg, 0.06 mmol), NaOAc (16.4 mg,
(
Ph.D. scholarships to M.H.B.). The authors thank Dr. R.
Zimmer for helpful discussions during the preparation of the
manuscript.
0.20 mmol) and butyl acrylate (574 mL, 4.00 mmol). The
temperature was raised to 1208C for 17 h. The evolution of
the reaction was monitored by TLC using DCM/EtAOc
(
80:20) as eluent. Then, the solvent was evaporated using References
a rotary evaporator and to the crude reaction mixture was
added DCM (100 mL) and then the reaction mixture was
washed with water (3ꢅ150 mL) and dried with anhydrous
Na SO . The organic phase was finally evaporated to dry-
ness by rotary evaporation. The residue was dissolved in
a minimum volume of DCM/EtAOc (80:20) and applied to
gravity silica gel column chromatography with DCM/EtAOc
[1] J. S. Lindsey, in: Metalloporphyrin-Catalyzed Oxida-
tions, (Eds.: F. Montanari, L. Casella), Kluwer Aca-
demic Publishers, The Netherlands, 1994, pp 49–86.
[2] J. S. Lindsey, in: The Porphyrin Handbook, vol. 1,
(Eds.: K. M. Kadish, K. Smith, R. Guilard), Academic
Press, San Diego, CA 1999, pp 45–118.
2
4
(
80:20) for further purification. The product 26 was obtained
[3] a) H. Volz, M. Holzbecher, Angew. Chem. 1997, 109,
1510–1513; Angew. Chem. Int. Ed. Engl. 1997, 36,
1442–1445; b) H.-A. Wagenknecht, C. Claude, W.-D.
Woggon, Helv. Chim. Acta 1998, 81, 1506–1520.
[4] a) M. Yeung, A. C. H. Ng, M. G. B. Drew, E. Vorpagel,
E. M. Breitung, R. J. McMahon, D. K. P. Ng, J. Org.
Chem. 1998, 63, 7143–7150; b) F. M. Qureshi, S. J.
Martin, X. Long, D. D. C. Bradley, F. Z. Henari, W. J.
Blau, E. C. Smith, C. H. Wang, A. K. Kar, H. L. Ander-
son, Chem. Phys. 1998, 231, 87–94; c) I. M. Blake, H. L.
Anderson, D. Beljonne, J.-L. Brꢇdas, W. Clegg, J. Am.
Chem. Soc. 1998, 120, 10764–10765; d) M. O. Senge, M.
Fazekas, M. Pintea, M. Zawadzka, W. J. Blau, Eur. J.
Org. Chem. 2011, 5797–5816.
and recrystallization of the product from a DCM/MeOH
mixture gave the desired pure crystalline form of the prod-
uct. purple crystals, yield: 41 mg (0.036 mmol, 36%); mp
1
1
358C; 1:1 dr. H NMR (500 MHz, CDCl ): d=0.78–0.83
3
(m, 6H, 2ꢅCOCH CH ), 0.94–0.97 (m, 6H, 2ꢅ
2 3
CH CH CH ), 1.38–1.46 (m, 4H, 2ꢅCH CH CH ), 1.63–1.69
(
COCH CH ), 4.12–4.16 (m, 4H, 2ꢅCO CH CH ), 4.78 (t,
J=7.0 Hz, 2H, 2ꢅCH CH), 5.31 (dd, J=14.9, 6.0 Hz, 2H,
2
6
1
7
1
2
2
3
2
2
3
m, 4H, 2ꢅCH CH CH ), 3.84–3.95 (m, 4H, 2ꢅ
2 2 3
2
3
2
2
2
2
ꢅCHHCH), 5.83 (dd, J=14.7, 7.7 Hz, 2H, 2ꢅCHHCH),
.30 (d, J=16.0 Hz, 1H, CHCHCO ), 6.31 (d, J=16.0 Hz,
2
H, CHCHCO ), 7.33–7.35 (m, 8H, 2ꢅCHC H CHCHCO),
2
6
4
.53 (d, J=16.0 Hz, 1H, CHCHCO ), 7.54 (d, J=16.0 Hz,
2
H, CHCHCO ), 7.72–7.80 (m, 6H, Ar), 8.11–8.15 (m, 4H,
[5] a) M. R. Wasielewski, Chem. Rev. 1992, 92, 435–461;
b) D. Gust, T. A. Moore, A. L. Moore, Acc. Chem. Res.
1993, 26, 198–205; c) H. Kurreck, M. Huber, Angew.
Chem. 1995, 107, 929–947; Angew. Chem. Int. Ed. Engl.
2
Ar), 8.87 (d, J=4.7 Hz, 4H, ß-pyrrole-H), 9.32–9.37 (m, 4H,
ß-pyrrole-H);
13
C NMR (126 MHz, CDCl ): d=13.80
3
(CO CH CH ),
13.82
(CO CH CH ),
13.85
(2ꢅ
2
2
3
2
2
3
1420
asc.wiley-vch.de
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1409 – 1422

Synthesis of Functionalized trans-A B -Porphyrins
2
2
1
995, 34, 849–866; d) A. Osuka, S. Marumo, N. Mataga,
Commun. 2004, 69, 1126–1136; d) J. K. Laha, S. Dhana-
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A. D. Bhise, M. Taniguchi, J. S. Lindsey, J. Org. Chem.
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