Highly substituted 2,3,7,8,12,13,17,18-octaethylporphyrins with meso aryl residues

Article abstract of DOI:10.1016/j.tet.2010.03.008

Highly substituted porphyrin-bearing meso aryl groups are useful compounds for optical applications and for studies on the interrelationship between the substituent pattern, macrocycle conformation and physical properties. They serve as biomimetic models for the function of tetrapyrroles in nature and help to elucidate modulation of cofactor properties through conformational effects. Using a sequence of lithium organic substitution reactions the synthesis of novel free base 5,10-A₂- and 5,10-AB-2,3,7,8,12,13,17,18-octaethylporphyrins bearing donating groups such as -OMe and -NMe₂ on the aryl-substituent was achieved. Larger aromatic residues (1-naphthyl, 9-anthracenyl and 9-phenanthrenyl) could be introduced into the macrocycle system as well, and these systems were used for the preparation of highly substituted porphyrins with a mixed substituent pattern. Using phenanthrenyl derivatives, the complete series of meso phenanthrenyl substituted octaethylporphyrins was successfully synthesized and the palladium complexes were prepared for photophysical investigations. Structural studies clearly showed the influence of individual substituents on the conformation of the tetrapyrrole macrocycle and conformational analyses revealed the variation of the underlying distortion modes depending on the type and arrangement of the meso substituents.

Full text of DOI:10.1016/j.tet.2010.03.008

Tetrahedron 66 (2010) 3508–3524
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Highly substituted 2,3,7,8,12,13,17,18-octaethylporphyrins with meso aryl residues
*
Mathias O. Senge , Julia Richter, Ines Bischoff, Aoife Ryan
School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity College Dublin, Dublin 2, Ireland
a r t i c l e i n f o
a b s t r a c t
Article history:
Highly substituted porphyrin-bearing meso aryl groups are useful compounds for optical applications
and for studies on the interrelationship between the substituent pattern, macrocycle conformation and
physical properties. They serve as biomimetic models for the function of tetrapyrroles in nature and help
to elucidate modulation of cofactor properties through conformational effects. Using a sequence of
lithium organic substitution reactions the synthesis of novel free base 5,10-A2- and 5,10-AB-
2,3,7,8,12,13,17,18-octaethylporphyrins bearing donating groups such as –OMe and –NMe2 on the aryl-
substituent was achieved. Larger aromatic residues (1-naphthyl, 9-anthracenyl and 9-phenanthrenyl)
could be introduced into the macrocycle system as well, and these systems were used for the preparation
of highly substituted porphyrins with a mixed substituent pattern. Using phenanthrenyl derivatives, the
complete series of meso phenanthrenyl substituted octaethylporphyrins was successfully synthesized
and the palladium complexes were prepared for photophysical investigations. Structural studies clearly
showed the influence of individual substituents on the conformation of the tetrapyrrole macrocycle and
conformational analyses revealed the variation of the underlying distortion modes depending on the
type and arrangement of the meso substituents.
Received 8 December 2009
Received in revised form 15 February 2010
Accepted 1 March 2010
Available online 12 March 2010
Keywords:
Porphyrins
Conformational analysis
Highly Substituted porphyrins
Tetrapyrroles
Organolithium reagents
Nucleophilic substitution
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
R1
R
Unsymmetrically meso substituted porphyrins are of interest for
a wide range of potential applications including nonlinear optics
(NLO), photodynamic therapy (PDT), and sensor and device appli-
cations.1 Based on both condensation2 and C–C coupling reactions3
the array of methods suitable for these so-called ABCD-type por-
N
N
N
N
N
N
N
N
R2
R4
R
M
M
R
R
phyrins is continuously expanding for
b-unsubstituted porphyrins.
However, applying similar methods to
b
-substituted porphyrins,
R3
e.g., 2,3,7,8,12,13,17,18-octaethylporphyrin (H2OEP) 1 to yield sys-
tems of type 5, remains a challenge.
The controlled access to halogenated derivatives such as meso
mono- and dibromosubstituted OEP remains especially difficult,
and thus prevents the use of straightforward Heck– or Suzuki–type
coupling reactions.4 Indeed, many syntheses actually first construct
5
1 R = H, M = 2H
2 R = H, M = Ni(II)
3 R = H, M = Pd(II)
4 R = H, M = Pt(II)
a purely meso substituted porphyrin, followed by
and then subsequent C–C couplings to construct porphyrins with
both meso and
substituents.5
Due to their excellent solubility, well established photophysics
and the potential to fine-tune their physicochemical properties via
conformational control,6 OEP derivatives are of considerable in-
terest. Even more so, many potential technical applications use the
b-bromination
easily available Pd(II) (3) or Pt(II) complexes of OEP (4),7 or
p
-extended S4 symmetric porphyrins.8
b
Further optimization of these systems requires a fine–tuning of
the porphyrin properties via modification of either the b
8or meso
positions, and the latter requires the synthesis of multiply meso-
substituted OEP derivatives. Many approaches for symmetric meso-
substituted OEP-derivatives have been published, primarily in the
context of highly substituted porphyrins or the synthesis of ben-
zoporphyrins.6,9,10 Nevertheless, approaches to unsymmetric de-
rivatives primarily involved the use of mixed condensation with
necessary tedious chromatographic work-up.
* Corresponding author. E-mail address: sengem@tcd.ie.
0040-4020/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.03.008

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3509
A different approach developed by us involved the use of orga-
R1
M
nolithium reagents for the direct substitution of porphyrins.11,12 This
approach showed that it was feasible to introduce up to four dif-
ferent meso substituents at the meso positions into a porphyrin.
However, most of the developmental work for this reaction was
done with simple 5,15-disubstituted porphyrins and we here turn
our attention back to the functionalization of OEP derivatives.12,13
N
N
N
N
a, b, c, d
1 or 2
2. Results and discussion
R1
=
Ni(II)
M =
2H
sBu
2.1. meso Monosubstituted porphyrins
7, 11%
8, 48%
First we studied the reaction of OEP with various organolithium
reagents to yield meso monosubstituted porphyrins. In line with
earlier results,11a–c,14 OEP reacts only sluggishly with sterically
hindered reagents, such as sBuLi, while the alkenylporphyrin 8
could be prepared in acceptable yields (Scheme 1). However, pri-
marily we were interested in extending the scope of this reaction
for aryl residues. We had shown that PhLi reacts in quantitative
yield with H2OEP 1 and in good yield with the related NiII complex
2.11a,b Accordingly, we used various aryl lithium reagents for re-
action with H2OEP all of which gave the desired products, shown in
Scheme 1, in low to excellent yields. Reactions with aryl residues
carrying –OH, –OMe or –NMe2 groups typically gave the lowest
yields while no reaction was observed with lithiated anthracene
derivatives. In several reactions formation of multiply substituted
products was observed when using a large excess of RLi reagent.
Most of these reactions were performed and optimized for free
base OEP to allow for the later introduction of various metals
without any demetallation/metalation sequences. Overall, use of
15–20 equiv of the respective bromides and an excess of
30–40 equiv of BuLi for the generation of the lithiated species was
used. This allowed the preparation of various meso mono-
substituted porphyrins carrying functional groups suitable for
subsequent modification. For example, the 4-aminophenyl residues
could be introduced in both the free base and NiII complex in good
yields (13 and 24 in 72 and 59% yield, respectively). The yields
observed in these reactions are slightly lower when compared to
similar reactions with 5,15-disubstituted porphyrins without
(9, 100% 23, 68%)13
10, 20%
11, 83%
12, 72%
NH2
13, 72% 24, 59%
14, 17%
NMe2
15, 26%
OH
Br
16, 56% 25, 40%13
17, 64%
CF3
18, 4%
OMe
b
-substituents.11f,14 However, most of those reactions were per-
formed with the more reactive NiII complexes.
19, 46%
2.2. meso Disubstituted porphyrins
Next we turned our attention to the preparation of meso
disubstituted porphyrins. Initial reactions were performed with
free base 5-Ph-OEP 9. As shown in Scheme 2 this porphyrin reacted
readily with various ArLi reagents in good to excellent yields, in-
cluding the naphthyl-, anthryl- and phenanthryl derivatives. Again,
3-methoxyphenyllithium gave only very unsatisfactory yields.
As expected the 5,10-regioisomer is the only regioisomer
formed in these reactions. In distinction to earlier studies with alkyl
lithium reagents, in most cases no formation of the 5,15-
regioisomers was observed. This confirms our earlier assumptions
about the reaction mechanism.11c
20, 31%
21, 73-89%
22, 26%
However, in several cases, the formation of meso trisubstituted
porphyrins, i.e., products of a diarylation reactionwere observed. For
example, reaction of 9 with 9-anthracenyl lithium gave the products
33 and 34 in a 2:1 ratio. In the case of reaction of 11 with 9-phe-
nanthrenyl lithium the higher arylated species 40 was the main
product. Formation of these products is the result of the necessity to
use an excess of RLi reagents to drive the reaction. This is clearly
evidenced by reaction of 9 with 9-phenanthrenyl lithium. As shown
in Scheme 2, this reaction can be adjusted in such a way as to give
either the meso disubstituted product 35in almost quantitativeyield
or the meso trisubstituted product 36 in 33% yield by adjusting the
Scheme 1. Synthesis and yields of meso substituted 2,3,7,8,12,13,17,18-octaethylpor-
phyrins. (a) LiR1, THF, ꢀ40 to ꢀ80 ꢁC; (b) 1 h, rt; (c) H2O, 15 min; (d) DDQ, 1 h.
number of equivalents of reagents used. Likewise, reaction of 21
with 9-phenanthrenyl lithium resulted in formation of the meso di-
48, tri- 49, and tetrasubstituted 66 porphyrins. Similar multiple
arylation were observed for reactions of benzoporphyrins.11e,13
In order to further test the reactivity of OEP metal complexes we
prepared the palladium complexes15 of some of the meso mono-
substituted porphyrins. Pd(II)OEP 3 did not react with nBuLi or

3510
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
R1 R2
R1
NH
N
NH
N
NH
N
N
N
N
a, b, c, d
R2
R1
+
HN
HN
HN
R2
R1
=
R2
=
---
---
26, 45%
27, 46%
28, 4%
9
9
9
9
9
9
9
9
9
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
4-pentylphenyl
4-bromophenyl
3-methoxyphenyl
4-dimethylaminophenyl
4-ethynylphenyl
1-naphthyl
29, 3%
---
30, 79%
31, 61%
32, 48%
33, 16%
35, 92%
---
---
---
34, 7%
---
9-anthracenyl
9-phenanthrenyl
9-phenanthrenyl
36, 33%
---
37, 47%
38, 38%
39, 16%
41, 65%
42, 48%
43, 47%
44, 44%
45, 46%
47, 71%
48, 43%
11
11
11
12
17
19
19
19
21
21
---
4-pentylphenyl
4-pentylphenyl
4-pentylphenyl
4-pentylphenyl
9-anthracenyl
9-phenanthrenyl
40, 25%
---
---
---
4-ethynylphenyl
3-trifluoromethylphenyl
4-ethynylphenyl
---
4-dimethylaminophenyl
46, 14%
---
1-naphthyl
4-pentylphenyl
1-naphthyl
49, 25%
1-naphthyl
9-phenanthrenyl
4-dimethylaminophenyl
9-phenanthrenyl
1-naphthyl
9-phenanthrenyl
9-phenanthrenyl
Scheme 2. Synthesis and yields of meso di- and trisubstituted 2,3,7,8,12,13,17,18-octaethylporphyrins. (a) LiR2, THF, ꢀ40 to ꢀ80 ꢁC; (b) 1 h, rt; (c) H2O, 15 min; (d) DDQ, 1 h.
sBuLi. Reaction with PhLi gave a pink product in small amounts that
could not be isolated. The only example reported in the literature
was the reaction with an electrophile when Grigg et al. serendipi-
tously prepared (2,3,7,8,12,13,17,18-octaethyl-5-methylporphy-rina-
to)palladium from 3 by reaction with trifluoromethyl sulfonate.16
The meso monosubstituted Pd(II)OEP complexes showed an in-
creased reactivity toward RLi reagents (Scheme 3).
Reaction of Pd(II)(5-nBu-OEP) with nBuLi gave an inseparable
mixture of the 5,10- and 5,15-regioisomers in a 3:1 ratio and 82%
overall yield (not shown). Similar results were obtained with the
Pd(II) complex 51. Reaction with sBuLi gave an inseparable 1:1
mixture of the two regioisomers 57a and 57b (combined yield
approx. 11%). NMR spectroscopy indicated that 57a occurred as
a mixture of two atropoisomers. Reaction of 52 with nBuLi gave the
respective 5,10-regioisomer 58a based on NMR spectroscopy in
high yield. However, all attempts to purify the material failed. Re-
action of the same starting material 52 with naphthyl lithium was
a bit more promising and gave the desired 5,10-regioisomer 59a as
the sole product in good yield (61%).
R1
50, R1 = Ph
N
N
51, R1 = 9-phenanthrenyl
52, R1 = 1-naphthyl
53, R1 = 3-F3C-C6H4
54, R1 = 2-naphthyl
N
N
Pd
R1
N
N
N
N
a, b, c, d
R1
M
R1
R1
Pd
N
N
N
N
N
N
N
N
60 R1 = Ph, M = 2H
R2
+
Pd
61 R1 = 4-ethynylphenyl, M = Ni(II)
R2
a
b
In practical terms, the use of the Pd(II) complexes in substitution
reactions was a disappointment. While the reactions proceeded
reasonably well, in many cases the products could not be separated
chromatographically. Thus it appeared likely that use of free base
porphyrins in the substitution reactions followed by insertion of
Pd(II) is the better route to Pd(II) complexes of highly substituted
porphyrins. In addition, we prepared the metal complex 61 in 85%
yield via metalation of 41 for comparative analyses and coupling
experiments.
55, R1 = Ph, R2 = n-Bu (a 50%)
56, R1 = Ph, R2 = s-Bu (a+b: 37%)
57, R1 = 9-phenanthrenyl, R2 = s-Bu (a+b: 11%)
58, R1 = 1-naphthyl, R2 = n-Bu (a: >90%)
59, R1 = R2 = 1-naphthyl (a: 61%)
Scheme 3. Reactions of meso monosubstituted palladium porphyrins. (a) LiR2, THF,
ꢀ40 to ꢀ80 ꢁC; (b) 1 h, rt; (c) H2O, 15 min; (d) DDQ, 1 h.

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3511
2.3. meso Tri- and tetrasubstituted porphyrins
bands, which is an indication of increased macrocycle distor-
tion.18,22 Larger meso aryl residues typically gave larger red shifts,
presumably due to stronger peri interactions. A typical example is
the series of phenanthrenylporphyrins with 1–4 meso residues: 21,
48, 49, 66. The Soret and long wavelength Q absorption band for
these porphyrins are: 406, 426; 426, sh; 445, 665; and 493, 697 nm,
respectively, indicating a maximum bathochromic shift of almost
100 nm compared to H2OEP. Similar results were observed for the
related Pd(II) series: 51, 67, 68, 69. Here the relevant absorption
maxima are: 400, 550; 414, 562; 429, 575; and 443, 590 nm, re-
spectively. The meso 5,10-disubstituted OEPs with larger residues
often exhibited split Soret bands. Similar trends were found for the
Pd(II) complexes. Depending on higher polarity on un-
symmetrically substituted nonplanar porphyrins, a solvent de-
pendency of the absorption spectra has also been shown.23
The synthesis of meso tri- and tetrasubstituted porphyrins pro-
ceeded similarly to the syntheses for mono- or disubstitution. As
described above, meso trisubstituted OEPs were accessible to some
extent as side products of the disubstitution reaction. A more log-
ical approach is their synthesis through reaction of the di-
substituted porphyrins with another RLi sequence. For example,
reaction of 60 with 4-dimethylaminophenyl lithium gave the por-
phyrin 62 in 69% yield, while the meso tetrasubstituted porphyrin
66 could be prepared in 42% yield directly from 21. In contrast to
our earlier results with alkyl lithium reagents11a,b,17 no thermody-
namically and sterically controlled formation of porphodimethenes
was observed for the highly substituted phenanthrenylporphyrins.
Again, for spectroscopic analyses, several Pd(II) complexes (67–70)
were prepared through standard reactions.
2.5. Conformational and structural studies
2.4. Spectroscopic studies
In order to gain some insight into the structural and confor-
mational effects of the meso substitution, crystal structure analyses
were performed for several compounds. Based on earlier data,
H2OEP derivatives with one meso substituent were expected to
show evidence for localized Cm displacements at the substituted
position and in-plane distortion through core elongation.24,25
In line with these results compound 8 (Fig. 1) exhibits a rela-
tively flat macrocycle with an average deviation of the 24 macro-
cycle atoms from their least-squares plane of 0.04 Å (Table 1). The
local steric effect of the 5-meso substituent is evidenced by the
larger out-of-plane displacement of the substituted Cm atom
The NMR spectra of the porphyrins prepared here show typical
features for highly substituted porphyrins. These are
R1
N
N
N
N
R1
R3
M
compared to the others. Similar to other octa-b-meso-mono-
substituted free base porphyrins the compound shows in-plane
distortion through core elongation of the macrocycle. The double
bond character of the terminal C54–C55 bond is clearly indicated by
the bond length of 1.350(3) Å.
R2
62 R1 = Ph, R2 = 4-dimethylaminophenyl, R3 = H, M = 2H
63 R1 = Ph, R2 = 4-bromophenyl, R3 = H, M = 2H
64 R1 = Ph, R2 = 4-pentylphenyl, R3 = H, M = 2H
65 R1 = R2 = 1-naphthyl, R3 = H, M = 2H
66 R1 = R2 = R3 = 9-phenanthrenyl, M = 2H
67 R1 = 9-phenanthrenyl, R2 = R3 = H, M = Pd(II)
68 R1 = R2 = 9-phenanthrenyl, R3 = H, M = Pd(II)
69 R1 = R2 = R3 = 9-phenanthrenyl, M = Pd(II)
R1
N
N
N
N
R2
M
R1
70 R1 = 9-phenanthrenyl, R2 = Ph, M = Pd(II)
Figure 1. View of the molecular structure of 8 in the crystal. Hydrogen atoms and
disordered positions have been omitted for clarity; thermal ellipsoids are drawn for
50% occupancy.
notably upfield shifts of the signals with increasing degree of
substitution,9 NH signals shifted downfield with increasing sub-
stitution18 and in several cases a broadening of the 1H NMR proton
signals at rt was observed.10b,19 Porphyrins with larger aromatic
residues, e.g., the naphthyl and phenanthrenyl derivatives occurred
as mixtures of atropoisomers, due to hindered rotation of the aryl
substituents. Detailed NMR spectroscopic investigations20 were in
agreement with earlier reports.19,21
A similar situation is found in the structure of 12 (Fig. 2).
However, here the conformation is clearly nonplanar (Fig. 3) with
significant up and down out-of-plane displacements for all Cm
positions, i.e., ruf distortion. This is the result of closer crystal
packing. Both 8 and 12 form
p-stacked aggregates, with a closer
intermacrocycle separation in the latter. The triple bond on the
aryl ring is clearly indicated by a bond length of 1.181(5) Å for
C57–C58.
As expected, an increasing number of meso substituents is ac-
companied by increasing bathochromic shifts of the absorption

3512
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
Table 1
Selected structural and conformation parameters [Å]
Compd
8
12
16
55
M-N(21)
M-N(22)
M-N(23)
M-N(24)
M-Nav
4a
d
d
d
1.996(2)
2.008(2)
2.010(2)
2.011(2)
2.006(2)
2.006
0.016
0.286
0.369
0.545
d
d
d
d
d
d
d
d
d
d
d
d
2.074
0.337
0.04
0.04
0.10
0
2.023
0.356
0.132
0.22
0.24
0.24
0.31
0.08
2.069
0.296
0.141
0.22
0.26
0.20
0.30
0.13
Xb
D
D
24c
d
Cm
e
d
d
d
d
C5
e
e
e
C10
C15
C20
0.307
0.289
0.339
0.03
0.02
a
Core size, average vector length from the geometric center of the four nitrogen
atoms to the nitrogen atoms.
b
Core elongation parameter defined as the difference between the vector lengths
(jN21-N22jþjN23-N24j)/2-(jN22-N23jþjN21-N24j)/2.
c
Figure 4. View of the molecular structure of 16 in the crystal. Hydrogen atoms and
disordered positions have been omitted for clarity; thermal ellipsoids are drawn for
50% occupancy.
Average deviation of the 24 macrocycle atoms from their least-squares plane.
d
Average deviation of the Cm carbon atoms from the 4N-plane.
e
Average deviation of the Cm carbon atom from the 4N-plane.
Figure 2. View of the molecular structure of 12 in the crystal. Hydrogen atoms have
been omitted for clarity; thermal ellipsoids are drawn for 50% occupancy.
Figure 5. View of the molecular structure of 55 in the crystal. Hydrogen atoms have
been omitted for clarity; thermal ellipsoids are drawn for 50% occupancy.
1
0.5
Å
0
Figure 3. Side view of the molecular structure of 12 in the crystal. Hydrogen atoms
have been omitted for clarity.
-0.5
-1
As shown in Table 1 the conformation of 16 (Fig. 4) is similar to
that of 12. Both in-plane and Cm out-of-plane distortions are
present; which is typical for these ‘nonasubstituted’ porphyrins.26
The structure of the palladium(II) porphyrin 55 with two differ-
ent meso substituents is the first example of such a Pd(II) compound
(Fig. 5). The conformation of the porphyrin is clearly nonplanar,
which is best seen in the skeletal deviationplot (Fig. 6). As evidenced
by a normal structural decomposition (NSD) analysis27 (Fig. 7) the
main contributors to the conformation are the out-of-plane sad and
ruf distortion modes. Thus, a significant mixing of distortion modes
occurs in this type of compound. The average Pd–N bond length is
slightly shorter then those of the planar Pd(II)OEP28a or the ruffled
(5,10,15,20-tetraisopropylporphyrinato)palladium(II).28b
Figure 6. View of the skeletal deviations in 55. The sequence of meso carbon atoms is
C20, C5, C10, C15, C20 from left to right.
3. Experimental
3.1. General methods
1H NMR spectra were recorded on a Bruker DPX 400 (400 MHz
for 1H NMR) or a Bruker AV 600 instrument (600 MHz for 1H NMR;
100 MHz for 13C NMR). High resolution mass spectrometry was
carried out on Micromass/Waters Corp. USA liquid chromatography
time-of-flight spectrometer equipped with electrospray source.
Low resolution mass spectra were recorded on Micromass/Waters

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3513
1.5
1.3
1.1
0.9
0.7
0.5
0.3
0.1
-0.1
n-hexane/CH2Cl2, v/v, 1/1 to 1/2 and for complete elution with
CH2Cl2. For more polar meso di- and higher substituted products it
was filtered through aluminum oxide with CH2Cl2 and for complete
elution ethylacetate was added. The solvent was evaporated and the
crude product purified by column chromatography on silica gel
(elution with n-hexane/CH2Cl2, v/v, 4/1 to 2/1, and after elution of
yellow impurities addition of 20 mL acetone to 200 mL eluent for
elution of disubstituted products and addition of 20 mL ethylacetate
to 200 ml eluent or 5 mL of EtOH to 100 mL eluent for elution of tri-
and tetrasubstituted products). meso Monosubstituted compounds
were recrystallized from CH2Cl2/CH3OH. Fractions of meso di-
(brown-orange solution, purple solid), tri- or tetra-substituted
products (green-brown to green solutions, purple and green solids)
were, if necessary, purified or separated again by column chroma-
tography on aluminum oxide with n-hexane/CH2Cl2, v/v, from 7/1 to
2/1 to neat CH2Cl2 and by addition of acetone or ethylacetate to the
eluent (20–200 mL CH2Cl2) for complete elution or elution of the
tetrasubstituted product. Further purification by passing through
aluminum oxide also deprotonated the inner NH groups due to its
basic character, as indicated by a color change from clear green to
dirty brown-green and which is necessary for the palladium(II) in-
sertion. Compounds were precipitated from CH2Cl2/MeOH.
Out of Plane
0.5
0.4
0.3
0.2
0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
In Plane
Figure 7. NSD analysis of Pd(II) porphyrin 55. Top panel gives out-of-plane distortions,
lower panel in-plane distortions.
Corp. Quattro microÔ LC-MS/MS instrument. UV/vis measurements
were performed using a Shimadzu MultiSpec-1501 instrument.
Melting points were determined using a Stuart SMP10 melting
point apparatus and are uncorrected. Thin layer chromatography
(TLC) was performed on silica gel 60F254 (Merck) precoated alu-
minum sheets. Column chromatography was performed using
a forced flow of the indicated solvent system on Fluka silica gel 60
(230–400 mesh) or aluminum oxide. Diethylether and THF were
distilled from sodium/benzophenone under argon. n-Butyl lithium,
1-bromonaphthalene, 2-bromonaphthalene, 1,4-dibromobenzene,
and 3-bromobenzotrifluoride were purchased from Aldrich Chem.
Co., 1-bromo-4-pentylbenzene was supplied from Maybridge, 9-
bromophenanthrene, 3-bromoanisol, and 9-bromoanthracene
from Acros, and 4-bromo-dimethylanilin from Fluka. All named
chemicals were used without further purification. Other techniques
were as described earlier.1b
3.3.2. General procedure Bdpalladium(II) insertion. The respective
free base porphyrin was dissolved in chloroform (c]0.002 mol Lꢀ1
)
and two equivalents of palladium acetate in methanol
(c]0.015 mol Lꢀ1) was added. For sterically hindered porphyrins,
the free base in solution was passed through a short column of alox
to assure formation of the unprotonated form. The reaction mixture
was stirred under an air atmosphere for 4 h to two days at rt under
TLC monitoring (silica gel, n-hexane/CH2Cl2, v/v, 1/1). A color
change from brown-green to red or dark pink was observed. The
solvent was evaporated under reduced pressure and the red resi-
due dissolved in a small amount of CH2Cl2 and purified using col-
umn chromatography (silica gel, n-hexane/CH2Cl2, v/v, 4/1). For
further purification the compounds were precipitated from CH2Cl2
with n-hexane or methanol.
3.2. Starting materials
3.4. Syntheses
2,3,7,8,12,13,17,18-Octaethylporphyrin 1,29 and its nickel(II)
complex 2 were synthesized according to standard procedures. The
synthesis of the Pd(II) complex 50–52 will be given elsewhere.30
3.4.1. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-methylpropyl)
porphyrin
(7). General procedure A: H2OEP (150 mg, 0.28 mmol) was dis-
solved at rt in THF (50 mL) under an Ar atmosphere. Over 15 min of
sBuLi (3.2 mL, 4.2 mmol, 15 equiv, 1.3 M in cyclohexane) was added
slowly at ꢀ75 ꢁC. The reaction mixture turned from red to green
and stirring was continued for 30 min at ꢀ50 ꢁC followed by 25 min
at rt. The mixture was quenched with water (1 mL) and after 5 min
DDQ in dichloromethane was added. Stirring was continued for
10 min at ꢀ40 ꢁC and 20 min at rt. The crude mixture was filtered
through alumina eluting with n-hexane/CH2Cl2 (1:1, v/v) followed
by column chromatography on silica gel with n-hexane/CH2Cl2 (1:1,
v/v). First a yellow and brown fraction eluted, then, after addition of
2 mL ethanol to 200 mL of the eluent a red product fraction was
obtained to yield 19 mg (0.03 mmol,11%). Mp 278 ꢁC; Rf¼0.80 (SiO2,
n-hexane/CH2Cl2/MeOH, 3:3:1, v/v); 1H NMR (400 MHz, CDCl3,
3.3. General procedures
3.3.1. General procedure Adpreparation of meso mono-, di-, and tri-
substituted free base 2,3,7,8,12,13,17,18-octaethylporphyrins. For the
preparation of in situ generated organolithium reagents the corre-
sponding bromide (optimized equivalents) was dissolved in ether
(15 mL) and an excess of n-BuLi (optimized equivalents, 2.5 M in n-
hexane) was added during 5–10 min at 0 to ꢀ50 ꢁC depending on the
bromide under an argon atmosphere. The reaction mixture was
stirred for an hour at rt and the corresponding octaethylporphyrin
dissolved in 50 mL THF (rt to ꢀ50 ꢁC) was added at rt to ꢀ75 ꢁC.
Stirringwas continuedforone houror untilTLC monitoring indicated
the formation of the product (red and slightly more polar than OEP
for meso monosubstituted compounds; green-brown, polar spot for
di- and higher substituted octaethylporphyrins on silica gel, n-hex-
ane/CH2Cl2, v/v, 1/1). The reaction was quenched with 1–2 mL of
water at rt to ꢀ50 ꢁC (color change from brown-red to dark green for
meso monosubstituted compounds) and 5 min later a solution of
DDQ (150–300 mg) in 15-mL CH2Cl2 was added quickly for oxidation
at the same temperature (color change to dark red for meso mono-
substituted OEPs) and stirred for 15–30 min at rt. Monosubstituted
products were filtered through a frit with silica gel, eluting with
TMS):
d
¼10.08 (s, 2H, Hmeso), 9.74 (s, 1H, Hmeso), 5.11 (m, 1H, sBu–
CH), 4.03 (m, 16H, CH2), 2.62 (d, 3H, J¼7.64 Hz, sBu–CH3), 2.48 (m,
2H, sBu–CH2), 2.2 (m, 1H, CH), 1.95 (m, 18H, CH3), 1.81 (t, 3H,
J¼7.09 Hz, CH3), 0.51 (t, 3H, J¼7.28 Hz, sBu–CH3); ꢀ2.30 ppm (s, 2H,
NH); 13C NMR (100 MHz, CDCl3):
d¼13.7, 17.4, 17.8, 18.4, 19.7, 20.0,
22.4, 24.4, 29.7, 33.7, 40.1, 95.1, 96.6, 124.4, 140.0, 140.6, 140.7, 141.9,
142.1,144.4,145.7,146.1 ppm; MS (ESþ), m/z (%): 591 (100) [MþH]þ;
HRMS (ESþ) [C40H54N4]: calcd 591.4425, found 591.4425.
3.4.2. 2,3,7,8,12,13,17,18-Octaethyl-5-(5-pentenyl)-porphyrin
(8). For the synthesis of the organolithium reagent of 5-bromo-1-

3514
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
pentene (1.2 mL, 8 mmol) was treated with LitBu (9 mL,15 mmol) in
abs diethylether (30 mL) at ꢀ78 ꢁC and stirred for 10 min. A solu-
tion of 1 (100 mg, 0.19 mmol) in THF (50 mL) was cooled to ꢀ78 ꢁC
and added to the organolithium reagent over the course of 1 h.
Further conditions were as described for 11. Column chromato-
graphic workup on silica gel (dichloromethane/n-hexane, 1:1, v/v)
gave two red fractions. The first one was identified as starting
material (42%) and the second one yielded 54 mg (0.09 mmol, 48%)
of 8 as purple crystals after recrystallization from CH2Cl2/MeOH,
mp 262 ꢁC; Rf¼0.44 (dichloromethane, silica gel, 6ꢂ3 cm); 1H NMR
of the cold bath the mixture was stirred for 15 min under argon. A
solution of 2,3,7,8,12,13,17,18-octaethylporphyrin (150 mg,
1
0.29 mmol) in abs THF (60 mL) was cooled to ꢀ20 ꢁC and then
added under argon to the vigorously stirred reaction mixture. The
cold bath was removed and the mixture stirred for 60 min, followed
by addition of water (5 mL) in THF (5 ml). After stirring for an ad-
ditional 30 min 10–15 equiv of DDQ (ca. 0.06 M as a solution in THF)
were added. After 60 min the reaction mixture was filtered through
neutral alumina, washed with dichloromethane and concentrated
in vacuo. Column chromatographic work-up on alumina eluting
with dichloromethane/n-hexane (1:20, v/v) gave three fractions.
The starting material (10 mg, 7%) eluted first, followed by porphyrin
12 (128 mg, 0.2 mmol, 72%) and the disubstituted compound 41
(21 mg, 0.029 mmol, 10%). Compound 12 crystallized as purple
crystals from CH2Cl2/MeOH, mp 260 ꢁC; Rf¼0.42 (dichloromethane/
n-hexane¼1:10, v/v, alumina, 6ꢂ3 cm); 1H NMR (500 MHz, CDCl3,
(500 MHz, CDCl3, TMS):
d¼9.96 (s, 2H, 10,20-H), 9.73 (s, 1H, 15-H),
5.77 (m, 1H, CH2CH2CH2CH]CH2), 4.90, 4.98 (each m, 4H,
CH2CH2CH2CH]CH2, CH2CH2CH2CH]CH2), 3.97 (m, 16H,
8ꢂCH2CH3), 2.15 (m, 2H, CH2CH2CH2CH]CH2), 1.80 (m, 26H,
8ꢂCH2CH3, CH2CH2CH2CH]CH2), ꢀ2.96, ꢀ2.90 (each s (br), 2H,
NH),; MS (EI, 80 eV); m/z (%): 602 (100) [Mþ], 547 (21) [MþꢀC4H7],
533 (9) [MþꢀC5H9], 301 (6) [M2þ]; UV/vis (CH2Cl2) lmax (log
3
)¼406
SiMe4):
d
¼10.18 (s, 2H, Hmeso), 9.93 (s, 1H, Hmeso), 7.85, 8.20 (each d,
(5.19), 507 (4.03), 541 (3.62), 576 nm (3.58); HRMS [C41H54N4]:
calcd 602.4348, found 602.4385.
4H, J¼4.7, HPh), 3.95–4.15 (m, 12H, 6ꢂCH2CH3), 3.35 (s, 1H, C^CH),
2.75 (m, 4H, 2ꢂCH2CH3), 1.90 (m, 12H, 4ꢂCH2CH3), 1.85 (t, 6H,
3J¼7.5 Hz, 2ꢂCH2CH3), 1.15, (t, 6H, J¼7.5 Hz, CH2CH3), ꢀ3.20, ꢀ3.05
(s (br.), 2H, NH), ppm; MS (EI, 80 eV, 250 ꢁC), m/z (%): 634 (100)
[Mþ], 619 (3) [MþꢀCH3], 534 (14) [(MþH)þꢀC8H5], 317 (9) [M2þ];
3.4.3. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-methylphenyl)-porphyrin
(10). Porphyrin 1 (150 mg, 0.28 mmol) was reacted with 20 equiv
4-bromotoluene (0.957 g, 5.6 mmol) and 40 equiv of nBuLi
(4.48 mL, 11.8 mmol) according to general procedure A at ꢀ10 to
0 ꢁC. The purple title compound 10 (35 mg, 0.056 mmol, 20%) was
obtained after two column chromatographic purification steps on
silica gel (first with n-hexane/CH2Cl2, 2/1, v/v and a second time
with n-hexane/CH2Cl2, 4/1, v/v,). In addition, 23 mg of starting
material were recovered as a first fraction (0.042 mmol, 15%). Mp
UV/vis (CH2Cl2): lmax (log
3)¼405 (5.21), 504 (4.27), 539 (4.08), 573
(4.06), 625 nm (3.91); HRMS [C44H50N4]: calcd 634.4036, found
634.4032.
3.4.6. 5-(4-Aminophenyl)-2,3,7,8,12,13,17,18-octaethyl-porphyrin
(13). For preparation of the organolithium reagent 1 g p-bromoa-
niline (5 mmol) were dissolved in diethylether (15 mL) in a 250 ml
Schlenk tube. Within 1 h LinBu (6 mL, 2.5 M in n-hexane, 15 mmol)
were added dropwise at 0 ꢁC (Ar) to the reaction mixture. The cold
bath was removed and the yellow mixture stirred for 1 h at room
temperature. Porphyrin 1 (100 mg, 0.19 mmol) was dissolved in
THF (60 mL) and cooled to ꢀ40 ꢁC. The cold solution of the por-
phyrin was added under Ar to the organo-lithium reagent and
stirred for 1 h at room temperature. The cold bath was removed and
the mixture stirred for 60 min, followed by addition of 5 ml water
in 5 ml THF. After stirring for an additional 30 min 10–15 equiv of
DDQ (ca. 0.06 M as a solution in THF) were added. After 60 min the
reaction mixture was filtered through neutral alumina, washed
with dichloromethane, and concentrated in vacuo. Column chro-
matography on neutral alumina (Brockmann grade III) eluting with
n-hexane/dichloromethane (6:1, v/v) yielded three fractions. The
most polar one was identified as the main product 13 and gave
85 mg (0.14 mmol, 72%) of purple crystals after recrystallization
from dichloromethane/methanol. The two remaining fractions
were further purified with a second chromatography column
eluting with n-hexane/CH2Cl2 (9:1, v/v). The first fraction was
identified as starting material (w5%) 1 and the second fraction as
a minor fraction of 2,3,7,8,12,13,17,18-octaethyl-5-phenyl-porphyrin
9. Analytical data for 13: mp 259 ꢁC; Rf¼0.24 (n-hexane/dichloro-
methane, 4:1, v/v, alumina, 6ꢂ3 cm); 1H NMR (500 MHz, CDCl3,
220 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.23 (s, 2H, Hmeso), 9.98 (s,
1H, Hmeso), 8.14 (d, 2H, J¼8.8 Hz, HPh), 7.52 (d, 2H, J¼7.8 Hz, HPh),
4.12 (m, 12H, CH2CH3), 2.85 (q, 4H, J¼7.4 Hz, CH2CH3), 2.77 (s, 3H,
Ph–CH3), 1.98 (t, 12H, J¼6.6 Hz, CH2CH3), 1.88 (t, 6H, J¼7.6 Hz,
CH2CH3), 1.21 (t, 6H, J¼7.4 Hz, CH2CH3), ꢀ2.94 ppm (s, 2H, NH); 13
C
NMR (100 MHz, CDCl3):
d
¼11.4, 13.7, 14.1, 18.0, 18.4, 18.5, 19.1, 19.7,
19.8, 20.7, 20.8, 21.7, 22.6, 24.9, 25.2, 26.9, 29.0, 30.7, 31.6, 34.3, 34.6,
36.0, 41.3, 95.2, 96.6, 119.1, 133.2, 138.0, 138.9, 140.8, 141.8, 142.1,
142.6, 142.8, 143.7, 144.0, 145.6, 173.9 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼406 (5.09), 505 (3.95), 538 (3.67), 571 (3.66), 624 nm (3.16);
MS (ESþ), m/z (%): 625 (80) [MþH]þ; HRMS [C43H52N4]: calcd
625.4270, found 625.4272.
3.4.4. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-pentylphenyl)-porphyrin
(11). Porphyrin 1 (150 mg, 0.28 mmol) was reacted with 20 equiv
of 1-bromo-4-pentylbenzene (1 mL, 5.6 mmol) and 40 equiv of
nBuLi (4.48 mL, 11.2 mmol) at 0 ꢁC following general procedure A
and yielded purple crystals after precipitation (160 mg, 0.22 mmol,
82%). Mp 200 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.16 (s, 2H, meso-
H), 9.92 (s, 1H, meso-H), 8.10 (d, 2H, J¼7.8 Hz, HPh), 7.47 (d, 2H,
J¼7.8 Hz, HPh), 4.06 (m, 12H, CH2CH3), 2.98 (t, 2H, J¼7.35 Hz, pentyl-
CH2), 2.79 (m, 4H, CH2CH3), 1.91 (t, 12H, J¼7.7 Hz, CH2CH3), 1.85 (t,
6H, J¼7.7 Hz, CH2CH3),1.51 (m, 6H, pentyl-CH2),1.15 (t, 6H, J¼7.7 Hz,
CH2CH3), 1.04, (t, 3H, J¼7.3 Hz, pentyl-CH3), ꢀ3.02 (s, 1H, NH),
TMS):
d
¼10.19 (s, 2H, 10,20-H) 9.95 (s, 1H, 15-H), 7.95 (d, 2H,
ꢀ3.15 ppm (s, 1H, NH); 13C NMR (400 MHz, CDCl3):
d
¼14.2, 18.0,
3J¼3.8 Hz, HPh), 6.96 (d, 2H, 3J¼3.8 Hz, HPh), 4.08 (m, 12H,
6ꢂCH2CH3), 3.95 (s, 2H, phenyl–NH2), 2.94 (q, 4H, 3J¼7.4 Hz,
2ꢂCH2CH3), 1.95 (t, 12H, 3J¼7.5 Hz, 4ꢂCH2CH3), 1.89 (t, 6H,
3J¼7.4 Hz, 2ꢂCH2CH3), 1.19 (t, 6H, 3J¼7.3 Hz, 2ꢂCH2CH3), ꢀ3.05,
2.99 (each s, 2H, NH) ppm; MS (EI, 80 eV), m/z (%): 625 (100) [Mþ],
610 (6) [MþꢀCH3], 596 (4) [MþꢀC2H5], 313 (11) [M2þ]; UV/vis
18.4, 18.5, 19.8, 20.7, 22.7, 31.7, 31.5, 72.7, 80.5, 96.6, 153.6, 155.0,
184.9, 191.6 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼404 (5.12), 503
(4.99), 537 (4.69), 571 nm (4.64); MS (ESþ), m/z (%): 681 (13)
[MþH]þ; HRMS (ESþ) [C47H60N4]: calcd 681.4896, found 681.4871.
3.4.5. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-ethynyl-phenyl)porphyrin
(12). 1-Bromo-4-ethynylbenzene (0.5 g, 2.7 mmol) was dissolved
in abs diethylether (15 ml) in a 250 ml Schlenk tube. Butyl lithium
(2.2 ml of a 2.5 M solution in hexane, 5.5 mmol) was added drop-
wise over 30 min under argon at ꢀ70 ꢁC. The reaction mixture was
warmed to ꢀ40 ꢁC and THF (abs) was added dropwise until the aryl
lithium compound formed a light white suspension. After removal
(CH2Cl2þ1% NEt3): lmax (log )¼406 (5.45), 505 (4.39), 537 (4.07),
3
573 (3.99), 625 nm (3.49); HRMS [C42H51N5]: calcd 625.4144, found
625.4172.
3.4.7. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-dimethyl-amino-
phenyl)porphyrin (14). Free base 1 (150 mg, 0.28 mmol) was reac-
ted following general procedure
A
with 20 equiv of

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3515
4-dimethylaniline (1.12 g, 5.6 mmol) and 40 equiv of n-BuLi
(4.48 mL, 11.2 mmol) at ꢀ70 to ꢀ40 ꢁC to yield 33 mg of purple
crystals (0.050 mmol, 17%). Mp >300 ꢁC; Rf¼0.03 (CH2Cl2/n-hex-
ane, v/v, 2/1, silica gel, 3.5ꢂ6 cm), 0.62 (CH2Cl2/n-hexane/MeOH, v/
and 40 equiv of n-BuLi (4.48 mL, 11.2 mmol) according to general
procedure A at ꢀ30 ꢁC and yielded purple crystals (125 mg,
0.179 mmol, 64%). Mp 212 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.20
(s, 2H, Hmeso), 9.67 (s, 1H, Hmeso), 8.61 (s, 1H, HPh), 8.36 (d, 1H,
J¼7.5 Hz, HPh), 8.11 (d, 1H, J¼7.9 Hz, HPh), 7.81 (t, 1H, J¼7.6 Hz, HPh),
4.09 (m, 12H, CH2CH3), 2.81 (m, 2H, CH2CH3), 2.61 (m, 2H,
CH2CH3), 1.93 (t, 12H, J¼7.4 Hz, CH2CH3), 1.85 (t, 6H, J¼7.5 Hz,
CH2CH3), 1.15 (t, 6H, J¼7.4 Hz, CH2CH3), ꢀ3.02 (s, 1H, NH),
v, 3/3/1, silica gel, 3.5ꢂ6 cm); 1H NMR (400 MHz, CDCl3):
¼10.20
d
(s, 2H, Hmeso), 9.95 (s, 1H, Hmeso), 8.04 (d, 1H, J¼8.7 Hz, HPh), 7.49 (d,
1H, J¼9.0 Hz, HPh), 7.04 (d, 1H, J¼8.7 Hz, HPh), 6.83 (d, 1H, J¼8.8 Hz,
HPh), 4.09 (m, 12H, CH2CH3), 3.24 (s, 6H, N(CH3)2), 2.94 (m, 4H,
CH2CH3), 1.96 (t, 12H, J¼7.7 Hz, CH2CH3), 1.90 (t, 6H, J¼7.6 Hz,
CH2CH3), 1.20 ppm (t, 6H, J¼7.3 Hz, CH2CH3); 13C NMR (100 MHz,
ꢀ3.17 ppm (s, 1H, NH); 13C NMR (100 MHz, CDCl3):
¼17.7, 18.4,
d
18.50, 18.53, 19.7, 20.7, 95.7, 96.1, 116.5, 125.1, 127.0, 129.5, 136.5,
CDCl3):
d
¼18.1, 18.4, 19.7, 19.8, 20.8, 40.7, 40.9, 96.5, 110.4, 113.7,
141.1, 142.0, 142.3, 142.9, 144.5, 145.8 ppm; UV/vis (CH2Cl2): lmax
119.7, 126.5, 133.9, 140.7, 142.0, 143.0, 143.7, 145.5, 150.8, 162.8,
(log
3
)¼404 (6.68), 503 (5.44), 537 (4.93), 571 nm (4.76); MS (ESþ),
170.5 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼406 (5.26), 505 (4.33), 538
m/z (%): 679 (100%) {MþH]þ; HRMS [C43H49F3N4]: calcd 679.3988,
(3.97), 572 nm (3.97), 624 (1.25); MS (ESþ), m/z (%): 654 (100)
[MþH]þ; HRMS [C44H55N5]: calcd 654.4536, found 654.4537.
found 679.3958.
3.4.11. 2,3,7,8,12,13,17,18-Octaethyl-5-(3-methoxy-phenyl)porphyrin
(18). The free base 1 (150 mg, 0.28 mmol) was reacted with
10 equiv of 3-bromoanisol (0.523 g, 2.8 mmol) and 20 equiv of
n-BuLi (2.24 mL, 5,6 mmol) according to general procedure A at
ꢀ75 ꢁC. The mixture was stirred at rt and OEP was added after 1 h.
Workup after 24 h yielded purple crystals (7 mg, 0.011 mmol, 4%).
3.4.8. 2,3,7,8,12,13,17,18-Octaethyl-5-(3-hydroxy-phenyl)porphyrin
(15). The free base 1 (150 mg, 0.28 mmol) was reacted with
20 equiv of 3-bromophenol (0.968 g, 5.6 mmol) and 60 equiv of
nBuLi (6.72 mL, 16.8 mmol) at ꢀ70 to ꢀ40 ꢁC following general
procedure A. Column chromatography eluted first 33 mg
(0.061 mmol, 21%) of starting material and then a fraction that gave
red-purple crystals of the title compound after precipitation
(46 mg, 0.073 mmol, 26%). Mp >300 ꢁC; Rf¼0.65 (CH2Cl2/n-hexane/
MeOH, 3/3/1, v/v, 3.5ꢂ6 cm, silica gel); 1H NMR (400 MHz, CDCl3):
Mp 217 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.17 (s, 2H, Hmeso), 9.92
(s, 1H, Hmeso), 7.82 (d, 1H, J¼7.25 Hz, HPh), 7.77 (br s, 1H, HPh), 7.56 (t,
1H, J¼7.26 Hz, HPh), 7.36 (m, 1H, HPh); 4.07 (m, 12H, CH2), 3.96 (s,
3H, OCH3), 2.82 (m, 4H, CH2), 1.91 (m, 18H, CH3), 1.21 (m, 6H, CH3),
d
¼10.16 (s, 2H, Hmeso), 9.92 (s, 1H, Hmeso), 7.78, 7.59 (each m, each
ꢀ3.07 ppm (s, 2H, NH); 13C NMR (100 MHz, CDCl3):
¼18.0, 18.4,
d
1H, HPh), 7.49 (t, 1H, J¼7.95 Hz, HPh), 7.22 (m, 1H, HPh), 4.06 (m, 12H,
CH2CH3), 2.83 (q, 4H, J¼7.48 Hz, CH2CH3), 1.91 (t, 12H, J¼7.57 Hz,
CH2CH3), 1.85 (t, 6H, J¼7.57 Hz, CH2CH3), 1.18 ppm (t, 6H, J¼7.48 Hz,
19.7, 20.7, 55.4, 95.3, 96.6, 114.5, 118.6, 119.0, 126.5, 127.3, 140.9,
141.3, 141.8, 142.2, 142.7, 143.3, 144.2, 145.6, 157.6 ppm; UV/vis
(CH2Cl2): lmax (log
3
)¼405 (5.32), 503 (4.26), 537 (3.95), 571 (3.92),
CH2CH3); 13C NMR (100 MHz, CDCl3):
d¼21.2, 104.3, 105.4, 107.9,
623 nm (3.41); MS (ESþ), m/z (%): 641 (100%) {MþH]þ; HRMS
109.1, 114.1, 115.9, 151.7, 152.5, 155.5, 159.8, 162.4, 172.5, 176.9, 182.5,
183.9, 184.6, 188.1, 195.6, 199.3, 208.5, 212.2 ppm; UV/vis (CH2Cl2):
[C43H53N4O]: calcd 641.4219, found 641.4244.
lmax (log
3
)¼404 (5.03), 503 (4.02), 537 (3.79), 571 (3.76), 623 (3.45)
3.4.12. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-naphtyl)-porphyrin
(19). The free base 1 (150 mg, 0.28 mmol) was reacted with
31 equiv of 1-bromonaphthalene (1.2 mL, 8.68 mmol) and 40 equiv
of n-BuLi (4.48 mL, 11.2 mmol) according to general procedure A at
ꢀ30 ꢁC. The mixture was stirred at rt and OEP was added after 1 h at
ꢀ30 ꢁC. Workup after 24 h yielded purple crystals (91 mg,
nm; MS (ESþ), m/z (%): 627 (100) [MþH]þ; HRMS [C42H50N4O]:
calcd 627.4063, found 627.4036.
3.4.9. 5-(4-Bromophenyl)-2,3,7,8,12,13,17,18-octaethyl-porphyrin
(16). For preparation of p-bromophenyl lithium 1 g (4.24 mmol)
1,4-dibromobenzene were dissolved in 20 ml abs THF and cooled to
ꢀ80 ꢁC. After a course of 30 min LinBu (2.12 mL, 2 M solution,
4.24 mmol) was added to the cold solution. The cold bath was re-
moved and the reaction mixture stirred for 1 h. In the meantime
a solution of 1 (100 mg, 0.19 mmol) in THF (50 mL) was prepared
and cooled to 0 ꢁC. The solution of the porphyrin was added to the
organolithium reagent under argon and stirred for 30 min at room
temperature. Subsequent steps followed the procedure given for
12. The crude mixture was purified using silica gel (dichloro-
methane/n-hexane, 1:1, v/v) and gave two red fractions. The first
fraction contained starting material 1 (28%) and the second fraction
gave 73 mg (0.11 mmol, 56%) of purple crystals of 16 after re-
crystallization from CH2Cl2/n-hexane, mp 248 ꢁC; Rf¼0.37
(dichloromethane, silica gel, 6ꢂ3 cm); 1H NMR (500 MHz, CDCl3,
0.128 mmol, 46%). Mp 200 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.20
(s, 2H, Hmeso), 9.98 (s, 1H, Hmeso), 8.40 (d, 1H, J¼5.8 Hz, Hnaphthyl),
8.30 (d, 1H, J¼7.7 Hz, Hnaphthyl), 8.12 (d, 1H, J¼8.3 Hz, Hnaphthyl), 7.84
(t, 1H, J¼6.9 Hz, Hnaphthyl), 7.47 (m, 1H, Hnaphthyl), 7.01 (m, 2H,
Hnaphthyl), 4.12 (m, 8H, CH2), 3.97 (m, 4H, CH2), 2.64 (m, 2H, CH2),
2.29 (m, 2H, CH2), 1.95 (t, 12H, J¼7.8 Hz, CH3), 1.87 (t, 6H, J¼7.6 Hz,
CH3), 0.87 (t, 6H, J¼7.6 Hz, CH3), ꢀ2.79 ppm (s, 2H, NH); 13C NMR
(100 MHz, CDCl3):
124.3, 125.9, 127.7, 128.4, 128.8, 131.7, 132.6 ppm; UV/vis (CH2Cl2):
d
¼16.6, 18.4 m 19.7, 19.8, 20.7, 95.4, 96.6, 116.4,
lmax (log
3
)¼406 (4.13), 504 (4.02), 538 (3.84), 572 (3.85), 625 nm
(3.41); MS (ESþ), m/z (%): 661 (100%) {MþH]þ; HRMS [C46H52N4]:
calcd 661.4270, found 661.4265.
3.4.13. 2,3,7,8,12,13,17,18-Octaethyl-5-(2-naphthyl)-porphyrin
(20). Free base 1 (100 mg, 0.18 mmol) was reacted with 20 equiv
2-bromonaphthalene (0.7449 g, 3.6 mmol) and 60 equiv of n-BuLi
(4.5 mL, 10.8 mmol) at ꢀ50 ꢁC according to general procedure A to
yield purple crystals (45 mg, 0.055 mmol, 31%). Mp 198 ꢁC; 1H NMR
TMS):
d
¼10.10 (s, 2H, 10–20-H) 9.85 (s, 1H, 15-H), 8.01 (d, 2H,
3J¼4.3 Hz, HPh), 7.72 (d, 2H, 3J¼4.3 Hz, HPh), 3.98 (m, 12H,
6ꢂCH2CH3), 2.72 (m, 4H, 2ꢂCH2CH3), 1.80 (m, 18H, 6ꢂCH2CH3), 1.09
(m, 6H, 2ꢂCH2CH3,), ꢀ3.24, ꢀ3.11 (each s, br, 2H, NH) ppm; UV/vis
(CH2Cl2): lmax (log
3)¼424 (5.15), 520 (4.12), 592 nm (3.79); MS (EI,
(400 MHz, CDCl3):
d
¼10.22 (s, 2H, Hmeso), 9.98 (s, 1H, Hmeso), 8.72 (s,
80 eV), m/z (%): 690 (100) [C42H49N481Brþ], 688 (80)
[C42H49N479Brþ], 611 (21) [Mþꢀ81Br, Mþꢀ79Br], 591 (13)
[MþꢀC6H5Br], 534 (69) [MþꢀC5H9], 345 (10) [C42H49N481Br2þ], 344
(10) [C42H49N479Br2þ]; HRMS [C42H49N479Br]: calcd 688.3141, found
688.3168; HRMS [C42H49N481Br]: calcd 690.3120, found 690.3165.
1H, Hnaphthyl), 8.39 (d, 1H, J¼8.1 Hz, Hnaphthyl), 8.21 (d, 1H, J¼7.6 Hz,
Hnaphthyl), 8.16 (d, 1H, J¼8.1 Hz, Hnaphthyl), 8.04 (d, 1H, J¼7.2 Hz,
Hnaphthyl), 7.03 (m, 2H, Hnaphthyl), 4.12 (m, 8H, CH2CH3), 4.03 (m, 4H,
CH2CH3), 2.77 (m, 2H, CH2CH3), 2.57 (m, 2H, CH2CH3), 1.59 (t, 12H,
J¼7.6 Hz, CH2CH3), 1.86 (t, 6H, J¼7.5 Hz, CH2CH3), 1.08 (t, 6H,
J¼7.2 Hz, CH2CH3), ꢀ2.92 (s, 1H, NH), ꢀ3.09 ppm (s, 1H, NH); 13C
3.4.10. 2,3,7,8,12,13,17,18-Octaethyl-5-(3-trifluoromethyl-phenyl)-
porphyrin (17). The free base 1 (150 mg, 0.28 mmol) was reacted
with 20 equiv of 3-bromobenzotrifluoride (0.77 mL, 5.6 mmol)
NMR (100 MHz, CDCl3):
d¼17.7, 18.4, 18.5, 19.7, 19.8, 20.8, 95.3, 96.7,
118.7, 125.5, 126.4, 126.8, 131.6, 132.1, 133.1, 139.2, 140.9, 141.8, 142.2,
142.6, 142.7, 143.6, 144.2, 145.7 ppm; UV/vis (CH2Cl2): lmax

3516
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
(log
3
)¼406 (5.61), 505 (4.48), 538 (4.20), 572 (4.20), 624 nm (3.71);
procedure A using 40 equiv of 1-bromo-4-pentylbenzene (0.93 mL,
5.24 mmol) and 50 equiv of n-BuLi (2.62 mL, 6.55 mmol) at 0 ꢁC to
rt. Porphyrin 9 (80 mg, 0.131 mmol) in THF was added after 80 min
at ꢀ0 ꢁC. After 30 min at rt the mixture was cooled to ꢀ0 ꢁC and
quenched. Standard work-up yielded 46 mg (0.060 mmol, 45%) of
a purple solid of the title compound. Mp 110 ꢁC; 1H NMR (400 MHz,
MS (ESþ), m/z (%): 661 (100) [MþH]þ; HRMS [C46H52N4]: calcd
661.4270, found 661.4290.
3.4.14. 2,3,7,8,12,13,17,18-Octaethyl-5-(9-phenanthren-yl)porphyrin
(21). Free base 1 (150 mg, 0.28 mmol) was reacted at ꢀ20 ꢁC with
31 equiv 9-bromophenanthrene (2.23 g, 8.86 mmol) and 40 equiv
of n-BuLi (4.5 mL, 11.2 mmol, ꢀ30 ꢁC) according to general pro-
cedure A to yield purple crystals (147 mg, 0.207 mmol, 89%). Mp
>300 ꢁC; Rf¼0.86 (CH2Cl2/n-hexane/MeOH, v/v, 3/3/1, silica gel); 1H
CDCl3):
d¼9.68 (s, 2H, Hmeso), 8.37 (d, 2H, J¼7.02 Hz, HpentylPh), 8.25
(d, 2H, J¼7.78 Hz, HpentylPh), 7.80 (t, 1H, J¼7.40 Hz, para HPh), 7.72 (t,
2H, J¼7.42 Hz, meta HPh), 7.53 (t, 2H, J¼7.79 Hz, ortho HPh), 3.98 (m,
4H, CH2CH3), 3.79 (m, 4H, CH2CH3), 2.99 (t, 2H, J¼7.41 Hz, pentyl-
CH2), 2.73 (m, 4H, CH2CH3), 2.32 (m, 4H, CH2CH3), 1.86 (t, 6H,
J¼7.54 Hz, CH2CH3), 1.62 (t, 6H, J¼7.52 Hz, CH2CH3), 1.52 (m, 6H,
pentyl-CH2), 1.04 (t, 3H, J¼6.81 Hz, pentyl-CH3), 0.69 (m, 6H,
CH2CH3), 0.50 (m, 6H, CH2CH3), ꢀ2.70 ppm (s, 2H, NH); 13C NMR
NMR (400 MHz, CDCl3):
d¼10.20 (s, 2H, Hmeso), 9.98 (s, 1H, Hmeso),
9.04 (d, 1H, J¼8.56 Hz, Hphenanthrenyl), 9.00 (d, 1H, J¼7.54 Hz, Hphe-
nanthrenyl), 8.71 (m, 1H, Hphenanthrenyl), 8.08 (d, 1H, J¼7.89 Hz, Hphe-
nanthrenyl), 7.92 (t, 1H, J¼8.20 Hz, Hphenanthrenyl), 7.81 (t, 1H,
J¼7.27 Hz, Hphenanthrenyl), 7.65 (m, 1H, Hphenanthrenyl), 7.27 (m, 1H,
Hphenanthrenyl), 7.14 (m, 1H, Hphenanthrenyl), 4.13 (m, 8H, CH2), 3.96 (m,
4H, CH2), 2.79 (m, 2H, CH2), 2.36 (m, 2H, CH2), 1.94 (t, 12H,
J¼7.20 Hz, CH3), 1.82 (t, 6H, J¼7.61 Hz, CH3), 0.85 (t, 6H, J¼7.42 Hz,
CH3), ꢀ2.73 (s, 1H, NH), ꢀ3.00 ppm (s, 1H, NH); 13C NMR (100 MHz,
(100 MHz, CDCl3):
22.6, 31.2, 31.4, 35.9, 94.7, 94.8, 119.2, 119.5, 125.7, 126.6, 126.8,
d
¼14.0, 14.1, 17.3, 17.9, 18.1, 19.3, 19.5, 20.5, 22.5,
128.2, 135.1, 135.3, 138.7, 141.4, 143.1 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼425 (5.50), 521 (4.29), 592 nm (4.13); MS (ESþ), m/z (%): 556
(39), 757 (38) [Mþ]; HRMS [C53H64N4]: calcd 757.5209, found
757.5180.
CDCl3):
d
¼17.0, 18.6, 18.7, 20.0, 21.1, 21.3, 96.1, 97.1, 116.4, 123.4,
126.9, 127.8, 129.4, 131.2, 137.7, 141.8, 142.9, 143.0, 145.4 ppm; UV/
vis (CH2Cl2): lmax (log
3
)¼406 (5.13), 504 (4.13), 538 (3.86), 571
3.4.18. 5-(4-Bromophenyl)-2,3,7,8,12,13,17,18-octaethyl-10-phenyl-
porphyrin (27). The reaction was performed following the general
procedure A using 40 equiv of 1,4-dibromobenzene (1.236 g,
5.24 mmol) and 50 equiv of n-BuLi (2.6 mL, 6.55 mol) at ꢀ30 ꢁC to
rt. Porphyrin 9 (80 mg, 0.131 mmol) in THF was added after
100 min at ꢀ30 ꢁC and after stirring for 30 min at rt it was
quenched at ꢀ30 ꢁC with water. Work-up yielded 47 mg
(0.061 mmol, 46%) of the title compound as a purple solid. Mp
(3.83), 624 nm (3.52); MS (ESþ), m/z (%): 711 (49) [MþH]þ; HRMS
[C50H54N4]: calcd 711.4427, found 711.4426.
3.4.15. 5-Acenaphthyl-2,3,7,8,12,13,17,18-octaethylporphyrin
(22). Free base 1 (150 mg, 0.28 mmol) was reacted at ꢀ20 ꢁC with
31 equiv 1-bromoacenaphtene (2.021 g, 8.68 mmol) and 40 equiv of
n-BuLi (4.5 mL, 11.2 mmol, ꢀ60 ꢁC) according to general procedure
A to yield purple crystals (51 mg, 0.074 mmol, 26%). Mp 190 ꢁC; 1H
119 ꢁC; 1H NMR (500 MHz, CDCl3):
d
¼9.66, 9.65 (each s, each 1H,
NMR (400 MHz, CDCl3):
d¼10.21 (s, 2H, Hmeso), 9.98 (s, 1H, Hmeso),
Hmeso), 8.33 (m, 2H, H4-Br–Ph), 8.23 (d, 2H, J¼8.18 Hz, HPh), 7.86 (d,
2H, J¼8.16 Hz, H4-Br–Ph), 7.77 (t, 1H, J¼7.43 Hz, HPh), 7.69 (t, 2H,
J¼7.44 Hz, HPh), 3.95 (q, 4H, J¼7.45 Hz, CH2CH3), 3.82 (m, 4H,
CH2CH3), 2.71 (m, 4H, CH2CH3), 2.29 (m, 4H, CH2CH3), 1.84 (t, 6H,
J¼7.59 Hz, CH2CH3), 1.59 (t, 6H, J¼7.41 Hz, CH2CH3), 0.66 (t, 6H,
J¼7.26 Hz, CH2CH3), 0.47 (m, 6H, CH2CH3), ꢀ2.72 ppm (s, 2H, NH);
8.36 (d, 1H, J¼6.6 Hz, Hacenaphthyl), 7.64 (d, 1H, J¼6.8 Hz, Hacenaphthyl),
7.32 (d, 1H, J¼6.6 Hz, Hacenaphthyl), 7.05 (t, 1H, J¼8.4 Hz, Hacenaphthyl),
6.66 (d, 1H, J¼8.2 Hz, Hacenaphthyl), 4.12 (m, 8H, CH2), 3.99 (m, 4H,
CH2), 3.79 (m, 2H, CH2acenaphthyl), 3.72 (m, 2H, CH2acenaphthyl), 2.73
(m, 2H, CH2), 2.35 (m, 2H, CH2), 1.95 (t, 12H, J¼8.5 Hz, CH3), 1.85 (t,
6H, J¼7.5 Hz, CH3), 0.91 (t, 6H, J¼7.3 Hz, CH3), ꢀ2.8 (s, 1H, NH),
13C NMR (100 MHz, CDCl3):
22.4, 25.0, 26.7, 28.8, 30.7, 31.4, 34.3, 34.4, 94.8, 94.9, 117.3, 119.3,
122.7, 126.4, 128.1, 129.6, 135.0, 136.5, 140.0, 141.1 ppm; UV/vis
d
¼11.2, 13.9, 17.0, 17.8, 18.0, 20.2, 20.4,
ꢀ3.04 ppm (s,1H, NH); 13C NMR (100 MHz, CDCl3):
d¼17.1,18.4,18.5,
19.73, 19.78, 19.83, 20.8, 95.3, 96.5, 116.3, 117.8, 119.2, 123.0, 127.9,
133.1, 135.5, 138.3, 140.8, 141.8, 142.5, 144.4, 144.3, 145.3, 145.5,
(CH2Cl2): lmax (log
3
)¼425 (3.99), 521 (3.81), 592 nm (3.61); MS
146.8 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼407 (5.02), 505 (3.92), 538
(ESþ), m/z (%): 765.3538 (48) [Mþ]; HRMS [C48H53N4Br]: calcd
(3.66), 574 (3.64), 625 nm (3.26); MS (ESþ), m/z (%): 687 (42)
[MþH]þ; HRMS [C48H54N4]: calcd 687.4427, found 687.4450.
765.3532, found 765.3538.
3.4.19. 2,3,7,8,12,13,17,18-Octaethyl-5-(3-methoxy-phenyl)-10-phe-
nylporphyrin (28). The reaction was performed following general
procedure A using 40 equiv of 3-bromoanisol (0.66 mL, 5.24 mmol)
and 50 equiv of n-BuLi (2.62 mL, 6.55 mmol) at ꢀ60 ꢁC to rt. Free
base 9 (80 mg, 0.131 mmol) in 50 mL THF was added after 90 min at
ꢀ50 ꢁC. The reaction was kept at low temperature for 15 min and
then stirred for 35 min at rt. It was quenched at ꢀ20 ꢁC, followed by
standard work-up to yield 4 mg (0.0054 mmol, 4%) of the title
compound (first fraction) as a purple solid accompanied by 3% of 29
(second fraction). Data for 28: Mp 133 ꢁC; 1H NMR (500 MHz,
3.4.16. {5-(4-Aminophenyl)-2,3,7,8,12,13,17,18-octa-ethyl-
porphyrinato}nickel(II) (24). Preparation of the organo-lithium re-
agent and the general synthetic procedure was performed as
described for the free base. Use of 2 (100 mg, 0.17 mmol) and
chromatographic work-up with neutral alumina (Brockmann grade
III, n-hexane/dichloromethane, 4:1, v/v) yielded two fractions. The
first, red band was starting material 2 followed by a major second,
red fraction. After recrystallization from dichloromethane/metha-
nol 68 mg (59%, 0.10 mmol) of purple crystals were obtained. Mp
263 ꢁC. Rf¼0.35 (n-hexane/dichloromethane, 4:1, v/v, alumina,
CDCl3):
d¼9.63 (s, 2H, Hmeso), 8.31 (d, 2H, J¼6.63 Hz, HPh), 7.92 (d,
6ꢂ3 cm); 1H NMR (500 MHz, CDCl3, TMS):
d
¼0.83 (t, 6H, 3J¼7.3 Hz,
1H, J¼7.44 Hz, HMeO–Ph), 7.87 (m,1H, HMeO–Ph), 7.76 (t,1H, J¼7.41 Hz,
HPh), 7.67 (t, 2H, J¼7.50 Hz, HPh), 7.57 (t, 1H, J¼8.02 Hz, HMeO–Ph),
7.33–7.31 (m, 1H, HMeO–Ph), 3.95 (s, 3H, OCH3), 3.92 (q, 4H,
J¼7.40 Hz, CH2CH3), 3.81 (m, 4H, CH2CH3), 2.69–2.63 (m, 4H,
CH2CH3), 2.34–2.25 (m, 4H, CH2CH3), 1.80 (t, 6H, J¼7.59 Hz,
CH2CH3), 0.88 (m, 6H, CH2CH3), 0.70 (t, 3H, J¼7.38 Hz, CH2CH3), 0.62
(t, 3H, J¼7.38 Hz, CH2CH3), 0.51 (t, 3H, J¼7.01 Hz, CH2CH3), 0.44 (t,
3H, J¼6.93 Hz, CH2CH3), ꢀ2.74 ppm (s, 2H, NH); 13C NMR (100 MHz,
2ꢂCH2CH3), 1.60 (t, 6H, 3J¼7.3 Hz, 2ꢂCH2CH3), 1.69 (t, 12H,
3J¼7.4 Hz, 4ꢂCH2CH3), 2.67 (q, 4H, 3J¼7.4 Hz, 2ꢂCH2CH3), 3.67 (m,
4H, 2ꢂCH2CH3), 3.70 (m, 8H, 4ꢂCH2CH3), 6.79 (d, 2H, 3J¼4.0 Hz,
HPh), 7.62 (d, 2H, 3J¼4.0 Hz, HPh), 9.41 (s, 1H, 15-H), 9.46 ppm (s, 2H,
10,20-H); UV/vis (CH2Cl2): lmax (log
3
)¼403 (5.21), 525 (4.02),
559 nm (4.28); MS (EI, 80 eV), m/z (%): 681 (100) [Mþ], 666 (6)
[MþꢀCH3], 638 (4) [MþꢀC3H7], 341 (10) [M2þ]; HRMS
[C42H49N5Ni]: calcd 681.3341, found 681.3372.
CDCl3):
55.5, 60.4, 94.9, 114.3, 118.9, 119.2, 120.8, 126.6, 127.5, 128.2, 135.2,
141.3, 142.6 ppm; UV/vis (CH2Cl2): lmax (log
)¼425 (4.59), 448
(4.36), 521 (3.48), 592 (3.37), 636 nm (0.035); MS (ESþ), m/z (%):
d¼14.1,17.35,17.39,17.4,18.0,18.2,19.3,19.5, 20.5, 22.6, 29.6,
3.4.17. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-pentylphenyl)-10-phenyl-
porphyrin (26). The reaction was performed following general
3

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3517
730 (100) [MþH]þ; HRMS [C49H56N4O]: calcd 730.4849, found
3.3.1 using 40 equiv of 1-bromonaphthalene (0.71 mL, 5.24 mmol)
and 50 equiv of n-BuLi (2.62 ml, 6.55 mmol) at ꢀ40 ꢁC to rt. Free
base 9 (80 mg, 0.131 mmol) in 50 mL THF was added after 1 h at
ꢀ10 ꢁC. After 30 min at rt the reaction was quenched at rt to yield
46 mg (0.062 mmol, 47%) of a purple solid. Mp 155 ꢁC; 1H NMR
730.4867.
3.4.20. 2,3,7,8,12,13,17,18-Octaethyl-5,15-bis(3-methoxyphenyl)-10-
phenylporphyrin (29). The compound was isolated from the re-
action described in Section 3.4.19. Yield: 4 mg, (0.0048 mmol, 3%)
(500 MHz, CDCl3):
d¼9.69 (s, 1H, Hmeso), 9.67 (s, 1H, Hmeso), 8.42 (d,
of a green solid. Mp 168 ꢁC; 1H NMR (500 MHz, CDCl3):
d
¼9.38–
1H, J¼6.87 Hz, Hnaphthyl), 8.33 (d, 2H, J¼7.09 Hz, HPh), 8.29 (d, 1H,
J¼8.25 Hz, Hnaphthyl), 8.11 (d, 1H, J¼8.07 Hz, Hnaphthyl), 7.90 (t, 1H,
J¼9.37 Hz, HPh), 7.83 (d, 1H, J¼8.04 Hz, Hnaphthyl), 7.82–7.75 (m, 1H,
Hnaphthyl), 7.68 (t, 2H, J¼7.42 Hz, HPh),7.53 (d, 1H, J¼7.82 Hz,
Hnaphthyl), 7.22 (t, 1H, J¼7.62 Hz, Hnaphthyl), 3.97 (m, 4H, CH2CH3),
3.84 (m, 2H, CH2CH3), 3.74 (m, 2H, CH2CH3), 2.69 (br m, 2H,
CH2CH3), 2.42 (br m, 2H, CH2CH3), 2.39–2.24 (m, 4H, CH2CH3), 1.84
(t, 6H, J¼7.50 CH2CH3), 1.60 (t, 3H, J¼7.51 CH2CH3), 1.53 (t, 3H,
J¼7.43 CH2CH3), 0.67 (t, 3H, J¼7.36, CH2CH3), 0.46 (t, 3H, J¼7.41 Hz,
CH2CH3), 0.41 (t, 3H, J¼7.36 Hz, CH2CH3), 0.34 (t, 3H, J¼7.17 Hz,
CH2CH3), ꢀ2.60 ppm (s, 2H, NH); 13C NMR (100 MHz, CDCl3):
9.24 (br s, 1H, Hmeso), 8.60–8.40 (m, 2H, HPh), 8.05 (m, 2H, HMeO–Ph),
7.84 (m, 1H, HPh, 2H, HMeO–Ph), 7.68 (m, 2H, HPh), 7.50 (m, 2H, HMeO–Ph),
7.37 (m, 2H, HMeO–Ph), 4.1 (s, 6H, 2ꢂOCH3), 3.66 (m, 4H, CH2CH3),
2.73–2.67 (m, 12H, CH2CH3), 1.53 (m, 6H, CH2CH3), 0.68–0.2 (m,
18H, CH2CH3), ꢀ0.08 ppm (s, 2H, NH); 13C NMR (100 MHz, CDCl3):
d
¼15.3, 16.4, 18.1, 19.9, 55.9, 116.0, 121.0, 121.9, 29.1, 129.3, 130.8,
137.3, 139.2, 142.7 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼465 (5.23),
569 (3.56), 608 (3.86), 663 nm (4.01); MS (ESþ), m/z (%): 578 (29),
823 (22) [MþH]þ; HRMS [C56H62N4O2]: calcd 823.4951, found
823.4958.
d
¼16.6, 16.9, 17.3, 17.4, 18.0, 18.2, 19.2, 19.4, 19.5, 20.4, 20.5, 94.9,
3.4.21. 5-(4-Dimethylaminophenyl)-2,3,7,8,12,13,17,18-octaethyl-10-
phenylporphyrin (30). The reaction was performed following the
general procedure A using 40 equiv of 1-bromo-4-dimethylami-
nobenzene (1.048 g, 5.24 mmol) and 50 equiv of n-BuLi (2.62 mL,
6.55 mmol) at ꢀ45 ꢁC to rt. Free base 9 (80 mg, 0.131 mmol) in THF
was added after 1 h at ꢀ20 ꢁC and after 30 min stirring at rt the
reaction was quenched at the same temperature to yield 76 mg
(0.104 mmol, 79%) of a purple solid. Mp 151 ꢁC; 1H NMR (500 MHz,
95.0, 116.2, 118.9, 124.4, 125.8, 126.0, 126.6, 127.7, 128.1, 128.2, 128.9,
132.2, 133.4, 135.2, 137.1, 139.1, 141.3 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼425 (3.22), 520 (3.01), 592 (sh), 650 nm (sh); MS (ESþ), m/z
(%): 737 (32) [MþH]þ; HRMS [C52H56N4]: calcd 737.4583, found
737.4572.
3.4.24. 5-(9-Anthracenyl)-2,3,7,8,12,13,17,18-octaethyl-10-(4-phe-
nyl)porphyrin (33). The reaction was performed following the
procedure in Section 3.3.1 using 50 equiv of 9-bromoanthracene
(1.2403 g, 4.90 mmol) and 60 equiv of n-BuLi (2.35 mL, 5.88 mmol)
at ꢀ40 ꢁC to rt. Free base 9 (60 mg, 0.098 mmol) in 50 mL THF was
added after 80 min at ꢀ20 ꢁC, followed by stirring for 80 min at rt.
After quenching with water ꢀ0 ꢁC the reaction yieled 13 mg
(0.0165 mmol, 16%) of a purple solid of the title compound as the
first green-brown fraction and 7 mg of 34 as the second green
CDCl3):
d
¼9.61 (s, 1H, Hmeso), 9.60 (s, 1H, Hmeso), 8.33 (d, 2H,
J¼6.94 Hz, HPh), 8.12 (d, 2H, J¼8.54 Hz, HMe2N–Ph), 7.87 (d, 1H,
J¼9.04 Hz, HPh), 7.67 (t, 2H, J¼7.43 Hz, HPh), 7.03 (d, 2H, J¼8.60 Hz,
HMe2N–Ph), 3.92 (q, 4H, J¼7.50 Hz, CH2CH3), 3.81 (m, 4H, CH2CH3),
3.23 (s, 6H, N(CH3)2), 2.83 (m, 2H, CH2CH3), 2.69 (m, 2H, CH2CH3),
2.35 (m, 2H, CH2CH3), 2.23 (m, 2H, CH2CH3), 1.80 (t, 6H, J¼7.59 Hz,
CH2CH3), 1.63 (m, 6H, CH2CH3), 0.63 (m, 6H, CH2CH3), 0.42 (m, 6H,
CH2CH3), ꢀ2.64 ppm (br s, 2H, NH); 13C NMR (100 MHz, CDCl3):
fraction. Mp 110 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼9.70 (s, 1H,
d
¼13.9, 17.3, 17.8, 19.2, 19.5, 24.6, 31.5, 40.6, 40.7, 74.1, 74.2, 94.3,
Hmeso), 9.67 (s, 1H, Hmeso), 8.88 (s, 1H, Hanthracenyl), 8.30 (d, 2H,
J¼6.6 Hz, HPh), 8.21 (d, 2H, J¼8.6 Hz, Hanthracenyl), 7.73 (t, 1H,
J¼7.41 Hz, HPh), 7.61 (t, 2H, J¼7.43 Hz, HPh), 7.59 (m, 1H, Hanthracenyl),
7.47 (m, 3H, Hanthracenyl), 7.10 (m, 2H, Hanthracenyl), 3.96 (m, 4H,
CH2CH3), 3.83 (m, 2H, CH2CH3), 3.63 (m, 2H, CH2CH3), 2.66 (m, 2H,
CH2CH3), 2.11 (m, 2H, CH2CH3), 1.84 (m, 4H, CH2CH3), 1.59 (m, 6H,
CH2CH3), 1.45 (t, 3H, J¼7.52 Hz, CH2CH3), 0.89 (m, 3H, CH2CH3), 0.68
(t, 3H, J¼7.37 Hz, CH2CH3), 0.33 (t, 3H, J¼7.19 Hz, CH2CH3), 0.01 (m,
3H, CH2CH3), ꢀ0.08 (t, 3H, J¼7.30 Hz, CH2CH3), ꢀ2.50 ppm (br s, 2H,
94.6, 110.5, 112.5, 112.9, 125.2, 126.6, 126.9, 130.0, 130.5, 132.7,
135.3, 136.2, 150.1, 155.5 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼427
(4.40), 593 (3.27), 667 nm (3.30); MS (ESþ), m/z (%): 730.4867
(100) [MþH]þ; HRMS [C50H59N5]: calcd 730.4867, found
730.4849.
3.4.22. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-ethynyl-phenyl)-10-phe-
nylporphyrin (31). The organo-lithium reagent was prepared as
described in Section 3.4.5 for 12 using 1 g 1-bromo-4-ethy-
nylbenzene (5.4 mmol) and reacted with 100 mg 9 (0.19 mmol) in
40 ml THF at ꢀ20 ꢁC. Column chromatography on neutral alumina
eluting with dichloromethane/n-hexane (1:1, v/v) resolved first
a yellow fraction. The polarity of the solvent was slowly increased
and elution with neat dichloromethane gave a red fraction con-
taining starting material 9 (35%). Subsequent development of the
column with dichloromethane/methanol (99:1, v/v) eluted the
target compound and gave purple crystals after recrystallization
from CH2Cl2/CH3OH (82 mg, 0.12 mmol, 61%), mp 265 ꢁC; Rf¼0.25
(dichloromethane/n-hexane: 3:1, v/v, alumina, 6ꢂ3 cm); 1H NMR
NH); 13C NMR (100 MHz, CDCl3):
19.3,19.6, 20.5, 31.8, 94.9, 95.2, 113.8,125.3,126.5,127.1,127.9,128.0,
d
¼15.3, 15.9, 17.4, 18.0, 18.2, 19.2,
128.1, 128.6, 130.9, 135.2, 135.4 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼425 (4.54), 520 (3.50), 592 nm (sh, 3.92); MS (ESþ), m/z (%):
787 (20) {MþH]þ; HRMS [C56H58N4]: calcd 787.4740, found
787.4703.
3.4.25. 5,15-bis(9-Anthracenyl)-2,3,7,8,12,13,17,18-octa-ethyl-10-
phenylporphyrin (34). The compound was obtained from the re-
action described in Section 3.4.24 and was isolated as a green solid
(7 mg, 0.0072 mmol, 7%). NMR spectroscopy indicated the forma-
tion of atropoisomers due to hindered anthracenyl rotation. Mp
(500 MHz, CDCl3, TMS):
d
¼9.64, 9.65 (each s, 2H, 15–20-H) 8.27 (d,
4H, 3J¼4.3 Hz, HPh), 7.83 (d, 2H, 3J¼4.3 Hz, HPh), 7.77 (m, 1H, HPh),
7.67 (m, 2H, HPh), 3.91 (m, 4H, 2ꢂCH2CH3), 3.80 (m, 4H, 2ꢂCH2CH3),
3.37 (s, 1H, C^CH), 2.64–2.76 (m, 8H, 4ꢂCH2CH3), 1.79 (t, 6H,
3J¼7.3 Hz, 2ꢂCH2CH3), 1.57 (t, 6H, 3J¼7.3 Hz, 2ꢂCH2CH3), 1.11 (t,
12H, 3J¼7.5 Hz, 4ꢂCH2CH3), ꢀ2.82 (s, 2H, NH); UV/vis (CH2Cl2þ1%
145 ꢁC; 1H NMR (300 MHz, CDCl3):
d
¼9.52 (s, 1H, Hmeso), 8.90 (s, 2H,
Hanthracenyl), 8.35 (d, 2H, J¼6.58 Hz, HPh), 8.26 (d, 4H, J¼8.52 Hz,
Hanthracenyl), 7.69 (m, 1H, HPh), 7.62 (m, 2H, HPh, 4H, Hanthracenyl), 7.52
(m, 4H, Hanthracenyl), 7.21 (m, 4H, Hanthracenyl), 3.56 (m, 6H, CH2), 3.40
(m, 2H, CH2), 2.09–1.88 (m, 8H, CH2), 2.28–2.01 (m, 8H, CH2), 1.56 (t,
6H, J¼7.48 Hz, CH3), 0.25 (t, 6H, J¼7.10 Hz, CH3), 0.08 (t, 6H,
J¼7.30 Hz, CH3), ꢀ0.06 (t, 6H, J¼7.24 Hz, CH3), ꢀ0.25 ppm (s, 2H,
NEt3): lmax (log
3
)¼424 (5.15), 520 (4.12), 592 nm (3.79); MS (EI,
80 eV), m/z (%): 710 (100) [Mþ], 681 (4) [MþꢀC2H5], 355 (10) [M2þ];
HRMS [C50H54N4]: calcd 710.4348, found 710.4384.
NH); 13C NMR (100 MHz, CDCl3):
d
¼11.4, 14.1, 15.3, 19.3, 20.4, 20.6,
22.65, 22.69, 25.2, 26.9, 29.0, 29.6, 31.5, 31.9, 34.6, 41.3, 112.4, 125.3,
128.2, 128.4, 131.0, 135.3 ppm; UV/vis (CH2Cl2): lmax (log
)¼446
(4.59), 538 (3.59), 609 (3.42), 666 (3.31) nm; MS (ESþ), m/z 578 (80),
3.4.23. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-naphthyl)-10-phenyl-
porphyrin (32). The reaction was performed as described in Section
3

3518
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
963 (15) [MþH]þ; HRMS [C70H66N4]: calcd 963.5375, found
pentyl-CH2), 1.00 (t, 6H, J¼6.80 Hz, pentyl-CH3), 0.64 (t, 6H,
J¼7.35 Hz, CH2CH3), 0.45 (t, 6H, J¼6.75 Hz, CH2CH3), ꢀ2.71 ppm (s,
963.5366.
2H, NH); 13C NMR (100 MHz CDCl3):
d
¼14.2, 17.3, 18.0, 18.1, 19.5,
3.4.26. 2,3,7,8,12,13,17,18-Octaethyl-5-(9-phenanthre-nyl)-10-phe-
nylporphyrin (35). The reaction was performed using the general
procedure A using 34 equiv of 9-bromophenanthrene (1.708 g,
6.64 mmol) and 43 equiv of n-BuLi (3.37 mL, 8.425 mmol) at ꢀ30 ꢁC
to rt. Free base 9 (120 mg, 0.196 mmol) in 50 mLTHF was added after
1 h at rt. After 40 min at the same temperature the reaction was
quenched with water to yield 125 mg (0.181 mmol, 92%) of a purple
solid after work-up as the main fraction. When the reaction was
performed with 30 equiv of 9-bromoanthracene, 30 equiv of BuLi
and 150 mg of 9 gave 26 mg (0.032 mmol, 13%) of the title com-
pound as the second fraction, followed by 25 mg (0.025 mmol, 10%)
of the trisubstituted compound 36 accompanied by 22% recovered
starting material as the first fraction. Mp 168 ꢁC; 1H NMR (500 MHz,
19.6, 20.5, 22.6, 29.7, 31.3, 31.4, 35.9, 94.7, 119.4, 135.2, 138.7,
143.1 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼425 (5.17), 521 (4.00),
592 nm (3.78); MS (ESþ), m/z (%): 827 (100) [MþH]þ; HRMS
[C58H74N4]: calcd 827.5992, found 827.5952.
3.4.29. 5-(9-Anthracenyl)-2,3,7,8,12,13,17,18-octaethyl-10-(4-pentyl-
phenyl)porphyrin (38). The reaction was performed as described in
Section 3.3.1 using 60 equiv of 9-bromoanthracene (1.3668 g,
5.40 mmol) and 75 equiv of n-BuLi (2.7 mL, 6.75 mmol) at ꢀ30 ꢁC to
rt. The free base 11 (62 mg, 0.090 mmol) in THF was added after 1 h
at ꢀ10 ꢁC and the mixture was stirred for 4 h at rt. This was fol-
lowed by quenching with water ꢀ0 ꢁC to yield 30 mg (0.035 mmol,
38%) of the title compound as a purple solid. Mp 72 ꢁC; 1H NMR
CDCl3):
d¼9.69 (s, 1H, Hmeso), 9.67 (s, 1H, Hmeso), 9.00 (m 2H,
(400 MHz, CDCl3):
d¼9.70 (s, 1H, Hmeso), 9.68 (s, 1H, Hmeso), 8.90 (s,
Hphenanthrenyl), 8.66 (s,1H, Hphenanthrenyl), 8.33 (d, 2H, J¼6.09 Hz, HPh),
8.09 (d, 1H, J¼7.63 Hz, Hphenanthrenyl), 7.87 (t, 1H, J¼7.11 Hz,
Hphenanthrenyl), 7.65–7.80 (m, 2H, HPh; 3H, Hphenanthrenyl), 7.59 (d, 1H,
J¼7.95 Hz, HPh), 7.29 (t, 1H, J¼7.21 Hz, Hphenanthrenyl), 3.96 (m, 4H,
CH2CH3), 3.84 (m, 2H, CH2CH3), 3.70 (m, 2H, CH2CH3), 2.72–2.53 (m,
4H, CH2CH3), 2.27–2.09 (m, 4H, CH2CH3), 1.83 (t, 6H, J¼7.47 Hz,
CH2CH3), 1.59 (t, 6H, J¼7.47 Hz, CH2CH3), 0.67 (t, 3H, J¼7.33 Hz,
CH2CH3), 0.45 (t, J¼7.35 Hz, 3H, CH2CH3), 0.37 (t, 6H, J¼6.31 Hz,
CH2CH3), ꢀ2.58 ppm (s, 2H, NH); 13C NMR (100 MHz, CDCl3):
1H, Hanthracenyl), 8.25 (d, 2H, J¼8.1 Hz, HAr), 8.19 (d, 2H, J¼7.8 Hz,
HAr), 7.86 (m, 2H, Hanthracenyl), 7.51 (m, 5H, Hanthracenyl), 7.13 (m, 2H,
Hanthracenyl), 3.98 (m, 4H, CH2CH3), 3.85 (m, 2H, CH2CH3), 3.65 (m,
2H, CH2CH3), 2.93 (t, 2H, J¼7.41 Hz, pentyl-CH2), 2.70 (m, 2H,
CH2CH3), 2.16 (m, 2H, CH2CH3), 1.86 (m, 6H, CH2CH3, 2H, CH2CH3),
1.72 (m, 2H, CH2CH3), 1.60 (t, 3H, J¼7.55 Hz, CH2CH3), 1.47 (m, 6H,
pentyl-CH2; 3H, CH2CH3), 1.00 (m, 3H, CH2CH3), 0.71 (t, 3H,
J¼7.40 Hz, CH2CH3), 0.36 (t, 3H, J¼7.17 Hz, pentyl-CH3), 0.3 (t, 3H,
J¼7.39 Hz, CH2CH3), ꢀ0.07 (t, 3H, J¼7.34 Hz, CH2CH3), ꢀ2.48 (s, 2H,
d
¼16.4,16.7,17.3,18.0,18.2,19.2,19.3,19.4,19.5,19.8, 20.2, 20.6, 29.6,
NH); 13C NMR (100 MHz, CDCl3):
d
¼14.1, 15.2, 15.8, 17.3, 17.8, 18.1,
94.9, 95.1, 116.0, 118.9, 122.5, 122.9, 126.4, 126.6, 127.1, 127.2, 128.2,
129.1, 129.2, 129.4, 130.7, 130.9, 134.1, 135.2, 136.4, 137.3, 141.3 ppm;
19.3, 19.7, 20.3, 20.8, 22.5, 26.9, 29.0, 31.2, 31.6, 34.6, 35.9, 94.1, 95.1,
113.6, 125.4, 125.8, 126.7, 127.8, 128.0, 128.8, 130.9, 135.1, 135.6 ppm;
UV/vis (CH2Cl2): lmax (log
3
)¼430 (sh), 454 (4.76), 587 (3.63), 541
UV/vis (CH2Cl2): lmax (log
3
)¼425 (4.68), 520 (3.63), 592 (3.34),
(4.07), 638 nm (3.42); MS (ESþ), m/z (%): 681 (13) [MþH]þ.
644 nm (2.78); MS (ESþ), m/z (%): 857 (20) [MþH]þ, 578 (60);
HRMS [C61H68N4]: calcd 857.5522, found 857.5541.
3.4.27. 2,3,7,8,12,13,17,18-Octaethyl-5,15-bis(9-phenan-threnyl)-10-
phenylporphyrin (36). The title compound could be obtained from
the reaction described in Section 3.4.26. Alternatively, reaction of 9
with 24 equiv of 9-bromophenanthrene and 37 equiv. BuLi afforded
exclusively the title compound (39 mg, 0.0404 mmol, 33%).
3.4.30. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-pentylphenyl)-10-phenan-
threnyl-porphyrin (39). The reaction was performed as described in
Section 3.3.1 using 40 equiv of 1-bromophenanthrene (2.263 g,
8.80 mmol) and 40 equiv of n-BuLi (3.52 mL, 8.80 mmol) at ꢀ50 ꢁC
to rt. The porphyrin 11 (150 mg, 0.220 mmol) in 50 mL THF was
added after 90 min at ꢀ30 ꢁC. After stirring for 40 min at rt the
reaction mixture was quenched at ꢀ30 ꢁC to yield 32 mg
(0.037 mmol,16%) of purple crystals of 39 from MeOH/CH2Cl2 as the
first green-brown fraction, followed by a second, light green frac-
tion upon addition of EtOH that contained 40 (58 mg, 0.056 mmol,
Mp 148 ꢁC; 1H NMR (500 MHz, CDCl3):
d¼9.52 (s, 1H, Hmeso), 8.98
(m, 4H, Hphenanthrenyl), 8.68 (s, 1H, Hphenanthrenyl), 8.67 (s, 1H,
Hphenanthrenyl), 8.34–8.43 (m, 3H, HPh), 8.08 (d, 2H, J¼7.73 Hz,
Hphenanthrenyl), 7.85 (t, 2H, J¼7.54 Hz, Hphenanthrenyl), 7.76 (t,
2H, J¼7.35 Hz, HPh), 7.75–7.64 (m, 6H, Hphenanthrenyl), 7.36 (m, 2H,
Hphenanthrenyl), 3.67 (m, 4H, CH2CH3), 2.59 (m, 2H, CH2CH3), 2.37 (m,
2H, CH2CH3), 2.28–2.01 (m, 8H, CH2CH3), 1.52 (m, 6H, CH2CH3), 0.54
(t, 6H, J¼7.26 Hz, CH2CH3), 0.40 (t, 6H, J¼7.29, CH2CH3), 0.27 (m, 6H,
CH2CH3), ꢀ1.78 ppm (br s, 2H, NH); 13C NMR (100 MHz, CDCl3):
25%). Data for 39: mp 165 ꢁC; 1H NMR (400 MHz, CDCl3):
d¼9.71 (s,
1H, Hmeso), 9.70 (s, 1H, Hmeso), 9.01 (d, 1H, J¼8.48 Hz, Hphenanthrenyl),
9.00 (d, 1H, J¼8.40 Hz, Hphenanthrenyl), 8.70 (s, 1H, Hphenanthrenyl), 8.23
(d, 2H, J¼6.21 Hz, HAr), 8.12 (d, 1H, J¼7.68 Hz, Hphenanthrenyl), 7.89 (t,
1H, J¼7.65 Hz, Hphenanthrenyl), 7.80 (t, 1H, J¼7.46 Hz, Hphenanthrenyl),
7.72 (t, 1H, J¼7.51 Hz, Hphenanthrenyl), 7.63 (d, 1H, J¼8.21 Hz,
Hphenanthrenyl), 7.50 (d, 2H, J¼7.45 Hz, HAr), 7.32 (t, 1H, J¼7.71 Hz,
Hphenanthrenyl), 3.99 (m, 4H, CH2CH3), 3.87 (m, 2H, CH2CH3), 3.74 (m,
2H, CH2CH3), 2.97 (t, 2H, J¼7.29 Hz, pentyl-CH2), 2.74 (m, 2H,
CH2CH3), 2.61 (m, 2H, CH2CH3), 2.25 (m, 4H, CH2CH3), 1.86 (t,
6H, J¼7.25 Hz, CH2CH3), 1.62 (t, 3H, J¼7.35 Hz, CH2CH3), 1.52 (m,
3H, CH2CH3; 6H, pentyl-CH2), 1.01 (m, 3H, CH2CH3), 0.70 (t, 3H,
J¼7.21 Hz, CH2CH3), 0.42 (t, 3H, J¼7.23 Hz, pentyl-CH3), 0.40 (m, 6H,
CH2CH3), ꢀ2.53 ppm (br s, 2H, NH); 13C NMR (100 MHz, CDCl3):
d
¼16.2, 16.6, 17.1, 17.8, 19.3, 19.5, 20.4, 20.5, 114.6, 122.8, 126.4, 126.6,
127.1, 127.4, 128.1, 128.9, 129.1, 130.9, 131.0 ppm; UV/vis (CH2Cl2):
lmax (log
3
)¼472 (5.14), 564 (sh), 608 (3.38), 663 nm (3.70); MS
(ESþ), m/z (%): 963 (15) [MþH]þ, 964 (10) [Mþ2H]þ; HRMS
[C70H66N4]: calcd 963.5366, found 963.5388.
3.4.28. 2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(4-pentyl-phenyl)-
porphyrin (37). The reaction was performed following the
procedure given in Section 3.3.1 using 40 equiv of 1-bromo-4-
pentylbenzene (0.83 mL, 4.68 mmol) and 50 equiv of n-BuLi
(2.34 mL, 5.87 mmol) at ꢀ20 ꢁC to rt. Free base 11 (80 mg,
0.117 mmol) in THF (50 mL) was added after 80 min at rt, followed
by stirring for 1 h at the same temperature. Then the reaction was
quenched with water at 0 ꢁC to yield 46 mg (0.055 mmol, 47%) of
a purple solid after work-up. Mp 68 ꢁC; 1H NMR (500 MHz, CDCl3):
d
¼14.1, 16.4, 16.7, 17.3, 18.0, 18.1, 19.3, 19.4, 19.6, 19.7, 20.6, 20.5, 22.6,
31.2, 31.4, 35.8, 94.8, 95.1, 116.0, 119.2, 119.8, 122.5, 122.9, 126.4,
126.6, 126.7, 127.1, 127.2, 129.1, 129.5, 130.7, 131.0, 134.1, 135.1, 136.5,
137.4, 138.7, 143.1 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼460 (5.25),
d
¼9.62 (s, 2H, Hmeso), 8.19 (d, 4H, J¼7.45 Hz, HAr), 7.48 (d, 4H,
589 (4.19), 639 nm (4.07); MS (ESþ), m/z (%): 857 (48) [MþH]þ;
J¼7.45 Hz, HAr), 3.83 (q, 4H, J¼7.44 Hz, CH2CH3), 3.81 (m, 4H,
CH2CH3), 2.95 (t, 4H, J¼7.45 Hz, pentyl-CH2), 2.70 (br m, 4H,
CH2CH3), 2.28 (br m, 4H, CH2CH3), 1.88 (m, 4H, pentyl-CH2), 1.81 (t,
6H, J¼7.45 Hz, CH2CH3), 1.57 (t, 6H, J¼7.51 Hz, CH2CH3), 1.49 (m, 8H,
HRMS [C61H68N4]: calcd 857.5522, found 857.5526.
3.4.31. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-pentylphenyl)-10,20-bis(9-
phenanthrenyl)porphyrin (40). The title compound was isolated

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3519
from reaction in Section 3.4.30 as a green solid. NMR spectroscopy
indicated the formation of atropoisomers due to hindered phe-
(3.74); MS (ESþ), m/z (%): 798 (40) [MþH]þ; HRMS [C51H58N5F3]:
calcd 798.4723, found 798.4743.
nanthrenyl rotation. Mp 136 ꢁC; 1H NMR (400 MHz, CDCl3):
d¼9.50,
(br s, 1H, Hmeso), 8.98 (t, 4H, J¼8.80 Hz, Hphenanthrenyl), 8.67, 8.68
(each s, each 1H, Hphenanthrenyl), 8.32–8.15 (br s, 1H, Hphenanthrenyl),
8.28 (d, 1H, J¼7.82 Hz, Hphenanthrenyl), 8.12 (d, 2H, J¼7.73 Hz,
Hphenanthrenyl), 7.87 (t, 2H, J¼7.50 Hz, Hphenanthrenyl), 7.80 (t, 2H,
J¼7.31 Hz, Hphenanthrenyl), 7.72 (m, 4H, HAr), 7.46 (d, 2H, J¼7.76 Hz,
Hphenanthrenyl), 7.34 (m, 2H, Hphenanthrenyl), 3.67 (m, 4H, CH2CH3),
2.90 (t, 2H, J¼7.29 Hz, pentyl-CH2), 2.59 (m, 2H, CH2CH3), 2.22 (m,
10H, CH2CH3), 1.84 (m, 2H, pentyl-CH2), 1.51 (m, 4H, pentyl-CH2;
6H, CH2CH3), 0.94 (m, 3H, pentyl-CH3), 0.53 (t, 6H, J¼0.53 Hz,
CH2CH3), 0.37 (m, 6H, CH2CH3), 0.29 (m, 6H, CH2CH3), ꢀ1.73 ppm (s,
3.4.34. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-naphthyl)-10-(4-pentyl-
phenyl)porphyrin (43). The reaction was performed as described in
Section 3.3.1 using 40 equiv of 1-bromo-4-pentylphenyl (0.85 mL,
4.84 mmol) and 50 equiv of n-BuLi (2.42 mL, 6.05 mmol) at ꢀ30 ꢁC
to rt. The free base 19 (80 mg, 0.121 mmol) in 50 mL THF was added
after 80 min at ꢀ0 ꢁC. After 30 min at rt the reaction was quenched
at ꢀ0 ꢁC with water to yield 46 mg (0.057 mmol, 47%) of a purple
solid. Mp 133 ꢁC; 1H NMR (500 MHz, CDCl3):
d¼9.67 (s, 1H, Hmeso),
9.66 (s, 1H, Hmeso), 8.41 (d, 1H, J¼6.87 Hz, Hnaphthyl), 8.28 (d, 1H,
J¼8.26 Hz, Hnaphthyl), 8.20 (d, 2H, J¼7.84 Hz, HAr), 8.11 (d, 1H,
J¼7.94 Hz, Hnaphthyl), 7.81 (t, 2H, J¼8.10 Hz, Hnaphthyl), 7.52 (t, 1H,
J¼6.85, Hnaphthyl), 7.47 (d, 2H, J¼7.80 Hz, HAr), 7.20 (t, 1H, J¼7.65 Hz,
Hnaphthyl), 3.95 (q, 4H, J¼7.08 Hz, CH2CH3), 3.83 (m, 2H, CH2CH3),
3.73 (m, 2H, CH2CH3), 2.95 (t, 2H, J¼7.41 Hz, pentyl-CH2), 2.70 (m,
2H, CH2CH3), 2.40 (m, 2H, CH2CH3), 2.25 (m, 2H, CH2CH3), 2.11 (m,
2H, CH2CH3), 1.83 (m, 6H, CH2CH3), 1.59 (t, 3H, J¼7.52 Hz, CH2CH3),
1.53 (m, 6H, pentyl-CH2; 3H, CH2CH3), 0.99 (m, 3H, pentyl-CH3),
0.67 (t, 3H, J¼7.38 Hz, CH2CH3), 0.45 (m, 6H, CH2CH3), 0.33 (t, 3H,
J¼7.15 Hz, CH2CH3), ꢀ2.61 ppm (s, 2H, NH); 13C NMR (100 MHz,
2H, NH); 13C NMR (100 MHz, CDCl3):
d
¼14.1, 16.3, 16.7, 17.1, 17.9,
19.2,19.4, 19.5, 20.4, 20.6, 22.5, 29.2, 31.2, 31.3, 31.7, 35.8, 53.7, 114.6,
122.6, 122.9, 126.7, 126.8, 126.5, 127.1, 129.0, 129.1, 129.6, 131.0,
133.6, 133.8, 135.9,136.2, 136.6, 138.7, 140.2, 142.5, 142.1, 143.0 ppm;
UV/vis (CH2Cl2): lmax (log
3
)¼442 (5.06), 470 (4.76), 537 (3.95), 609
(3.75), 665 nm (3.72); MS (ESþ), m/z (%): 1034 (100) [MþH]þ; HRMS
[C75H76N4]: calcd 1033.6148, found 1033.6157.
3.4.32. 2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(4-ethynyl-phenyl)-
porphyrin (41). A solution of porphyrin 12 (150 mg, 0.24 mmol) in
60 ml THF was cooled to ꢀ20 ꢁC added to a vigorously stirred so-
lution of 4-lithioethynylphenyl lithium. Subsequent steps followed
the procedure given in Section 3.3.1. TLC of the crude reaction
mixture showed several red, brown-green, and blue bands, which
could not be separated completely. Column chromatography on
alumina gel eluting with dichloromethane/n-hexane (1:20, v/v)
eluted first recovered starting material 12 (35 mg, 0.05 mmol, 20%)
followed by the product. Recrystallization from CH2Cl2/MeOH gave
purple crystals (128 mg, 0.16 mmol, 65%). Note, this compound was
also obtained as a side product during the synthesis of 12 (see
Section 3.4.5). Mp 220 ꢁC; (CH2Cl2/CH3OH); Rf¼0.22 (dichloro-
methane/n-hexane 1:10, v/v, alumina, 6ꢂ3 cm); 1H NMR (500 MHz,
CDCl3):
d
¼14.1, 16.5, 16.9, 17.3, 17.9, 18.1, 19.4, 19.5, 19.6, 20.4, 20.5,
22.6, 26.9, 31.2, 31.4, 35.8, 94.8, 95.0, 116.2, 124.4, 125.8, 126.0, 126.7,
127.7, 128.1, 128.9, 132.7, 133.4, 135.1, 137.2, 139.2, 143.1 ppm; UV/vis
(CH2Cl2): lmax (log
3
)¼426 (4.88), 519 (3.74), 555 (3.61), 592 (3.72),
643 nm (3.48); MS (ESþ), m/z (%): 807 (100) [MþH]þ; HRMS
[C57H66N4]: calcd 807.5366, found 807.5374.
3.4.35. 2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(1-naphth-yl)porphyrin
(44). The reaction was performed as described in Section 3.3.1
using 60 equiv of 1-bromonaphthalene (1.08 mL, 8.00 mmol) and
75 equiv of n-BuLi (3.99 mL, 9.97 mmol) at ꢀ20 ꢁC to rt. The free
base 19 (88 mg, 0.133 mmol) in THF was added after 45 min at rt
and after stirring for 25 min the reaction was quenched at rt with
water to yield 46 mg (0.060 mmol, 44%) of a purple solid. Mp
CDCl3, SiMe4):
d
¼ ꢀ2.85 (s (br), 2H, NH), 0.35, 0.55, 1.50, 1.79 (each
t, 24H, 3J¼7.5 Hz, CH2CH3), 2.20, 2.63 (each m, 8H, CH2CH3), 3.27 (s,
2H, C^CH), 3.75, 3.85 (each q, 8H, 3J¼7.5 Hz, CH2CH3), 7.59 (each d,
4H, J¼4.7, HPh), 7.64 (each d, 4H, J¼4.7, HPh), 9.60 ppm (s, 2H, Hmeso);
MS (EI, 80 eV, 200 ꢁC), m/z (%): 734 (100) [Mþ], 706 (5)
[MþꢀCH2CH2], 633 (3) [MþꢀC8H5], 367 (25) [M2þ]; UV/vis
178 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼9.69 (s, 1H, Hmeso), 9.67 (s, 1H,
Hmeso), 8.47 (d, 1H, J¼6.87 Hz, Hnaphthyl), 8.40 (d, 1H, J¼6.89 Hz,
Hnaphthyl), 8.27 (d, 2H, J¼8.20 Hz, Hnaphthyl), 8.09 (t, 2H, J¼7.19 Hz,
Hnaphtyl), 7.81 (m, 2H, Hnaphthyl), 7.50 (m, 4H, Hnaphthyl), 7.20 (m, 2H,
Hnaphthyl), 3.98 (m, 4H, CH2CH3), 3.75 (m, 4H, CH2CH3), 2.60 (m, 2H,
CH2CH3), 2.42 (m, 2H, CH2CH3), 2.23–2.00 (m, 4H, CH2CH3), 1.84 (m,
6H, CH2CH3), 0.89 (m, 6H, CH2CH3), 0.45 (m, 6H, CH2CH3), 0.26 (m,
6H, CH2CH3), ꢀ2.44 (s, 1H, NH), ꢀ2.52 ppm (s, 1H, NH); 13C NMR
(CH2Cl2): lmax (log
(3.54); HRMS [C52H54N4]: calcd 734.4349, found 734.4346.
3)¼426 (5.17), 523 (4.01), 559 (3.49), 597 nm
3.4.33. 5-(4-jDimethylaminophenyl-2,3,7,8,12,13,17,18-octaethyl-10-
(3-trifluoromethylphenyl))porphyrin (42). The reaction was per-
formed as described in Section 3.3.1. using 60 equiv of 1-bromo-
dimethylaniline (1.0088 g, 5.04 mmol) and 75 equiv of n-BuLi
(2.52 mL, 6.30 mmol) at ꢀ20 ꢁC to rt. Free base 17 (57 mg,
0.084 mmol) in 50 mL THF (low solubility) was added after 40 min
at rt and after stirring for 25 min it was quenched at the same
(100 MHz, CDCl3):
d
¼13.9, 14.0, 14.1, 16.6, 16.7, 16.93, 16.95, 18.01,
18.02, 18.6, 19.4, 19.6, 20.5, 22.4, 22.5, 22.6, 31.2, 31.5, 33.7, 35.2,
35.5, 95.0, 95.1, 116.0, 124.3, 124.4, 125.9, 126.2, 127.7, 127.9, 128.0,
128.2, 129.0, 132.6, 132.7, 133.2, 133.3, 137.2, 137.3, 138.8, 139.1 ppm;
UV/vis (CH2Cl2): lmax (log
3
)¼426 (4.89), 521 (3.79), 592 nm (3.53);
MS (ESþ), m/z (%): 787 (90) [MþH]þ; HRMS [C56H58N4]: calcd
787.4740, found 787.4733.
temperature with water to yield 33 mg of
a
purple solid
¼9.64,
(0.041 mmol, 48%). Mp 125 ꢁC; 1H NMR (400 MHz, CDCl3):
d
3.4.36. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-naphthyl)-10-(9-phenan-
threnyl)porphyrin (45). The reaction was performed as described in
Section 3.3.1 using 40 equiv of 9-bromophenanthrene (1.2427 g,
4.84 mmol) and 50 equiv of n-BuLi (2.42 mL, 6.05 mmol) at ꢀ30 ꢁC
to rt. Free base 19 (80 mg, 0.121 mmol) in 50 mL THF was added
after 1 h at ꢀ10 ꢁC. After stirring for 30 min at rt it was quenched at
ꢀ0 ꢁC to yield 47 mg (0.056 mmol, 46%) of a purple solid as a red-
green fraction. Addition of ethylacetate eluted a second fraction
to yield 14% (22 mg, 0.0217 mmol) of 46. Data for 45: NMR spec-
troscopy indicated the formation of atropoisomers due to hindered
phenanthrenyl rotation. Mp 140 ꢁC; 1H NMR (500 MHz, CDCl3):
9.61 (each s, each 1H, Hmeso), 8.66 (s, 1H, HF3C–Ph), 8.50 (d, 1H,
J¼7.49 Hz, HF3C–Ph), 8.11 (d, 2H, J¼7.99 Hz, HMe2N–Ph), 8.05 (d, 1H,
J¼7.87 Hz, HF3C–Ph), 7.82 (t, 1H, J¼7.72 Hz, HF3C–Ph), 7.04 (d, 2H,
J¼8.48 Hz, HMe2N–Ph), 3.93 (q, 4H, J¼7.32 Hz, CH2CH3), 3.81 (m, 4H,
CH2CH3), 3.23 (s, 6H, N(CH3)2), 2.62 (m, 4H, CH2CH3), 2.35 (m, 4H,
CH2CH3), 1.81 (t, 6H, J¼7.84 Hz, CH2CH3), 0.89 (m, 6H, CH2CH3), 0.63
(m, 6H, CH2CH3), 0.45 (t, 3H, J¼6.33 Hz, CH2CH3), 0.39 (t, 3H,
J¼6.71 Hz, CH2CH3), ꢀ2.68 ppm (s, 2H, NH); 13C NMR (100 MHz,
CDCl3):
d
¼14.0, 14.7, 17.2, 17.3, 17.9, 18.1, 18.3, 19.2, 19.3, 19.4, 19.5,
20.3, 20.4, 20.6, 22.6, 25.2, 26.8, 28.9, 29.6, 31.5, 34.6, 39.8, 40.6,
74.1, 94.5, 95.1, 110.4, 110.5, 110.9, 112.4, 116.7, 120.6, 124.7, 125.0,
126.8, 127.1, 130.1, 136.1, 138.3, 142.1, 150.5, 153.1 ppm; UV/vis
d¼9.71 (s, 1H, Hmeso), 9.68 (s, 1H, Hmeso), 8.99–8.93 (m, 2H,
Hphenanthrenyl), 8.72–8.67 (br s, 1H, Hphenanthrenyl), 8.49–8.39 (d, 1H,
J¼7.02 Hz, Hnaphthyl H), 8.26 (d, 1H, J¼8.24 Hz, Hnaphthyl), 8.09 (m,
(CH2Cl2): lmax (log
3)¼429 (4.72), 513 (sh), 595 (3.67), 663 nm

3520
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
2H, Hphenanthrenyl), 7.88–7.77 (m, 3H, Hphenanthrenyl), 7.69 (t, 1H,
J¼6.87 Hz, Hphenanthrenyl), 7.59–7.48 (m, 4H, Hnaphthyl), 7.20 (m, 1H,
Hnaphthyl), 3.97 (m, 4H, CH2CH3), 3.75 (m, 4H, CH2CH3), 2.57–2.00
(br m, 8H, CH2CH3), 1.85 (m, 6H, CH2CH3), 0.89 (m, 6H, CH2CH3),
0.47 (m, 6H, CH2CH3), 0.31–0.22 (m, 6H, CH2CH3), ꢀ2.42 (s, 1H, NH),
ꢀ50 ꢁC and after 45 min stirring at rt the reaction was quenched at
ꢀ30 ꢁC with water to yield 81 mg (0.093 mmol, 43%) purple crys-
tals after crystallization from MeOH/CH2Cl2 as the first green-red
fraction. Its formation was accompanied by the meso tri-
substituted product 49 (fraction 3, light-green, 57 mg, 0.053 mmol,
25%, green solid) and the meso tetrasubstituted product (66, see
Section 3.4.52) (fraction 4, dark green, 21 mg, 0.0169 mmol, 7%,
green solid). Data for 48: Mp >300 ꢁC; 1H NMR (400 MHz, CDCl3):
ꢀ2.50 ppm (s, 1H, NH); 13C NMR (100 MHz, CDCl3):
¼11.0, 11.4,
d
14.1, 16.5, 16.9, 18.0, 18.3, 19.4, 19.5, 19.6, 20.4, 20.6, 20.7, 22.7, 25.2,
26.8, 27.6, 29.0, 31.5, 34.7, 35.9, 41.4, 95.3, 116.0, 122.4, 122.9, 124.4,
125.9, 126.5, 127.0, 127.6, 128.8, 129.1, 129.6, 130.8, 132.5, 133.3,
d¼9.73, 9.70 (each s, each 1H, Hmeso), 8.98, 8.94 (each d, each 2H,
133.9, 136.5, 137.4 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼430 (5.01),
J¼8.38 HZ, J¼7.26 Hz, Hphenanthrenyl), 8.74, 8.65 (each s, each 1H,
Hphenanthrenyl), 8.12, 8.08 (each d, each 1H, each J¼7.69 Hz, Hphenan-
threnyl), 7.87 (t, 2H, J¼7.57, Hphenanthrenyl), 7.78 (m, 2H, Hphenanthrenyl),
7.69 (m, 2H, Hphenanthrenyl), 7.60 (t, 2H, J¼8.70 Hz, Hphenanthrenyl), 7.31
(m, 2H, Hphenanthrenyl), 3.98 (m, 4H, CH2CH3), 3.74 (m, 4H, CH2CH3),
2.57 (m, 2H, CH2CH3), 2.28 (m, 2H, CH2CH3), 2.02 (m, 4H, CH2CH3),
1.85 (m, 6H, CH2CH3), 1.53 (m, 6H, CH2CH3), 0.49 (m, 6H, CH2CH3),
455 (5.01), 519 (3.90), 591 (4.04), 643 nm (3.81); MS (ESþ), m/z (%):
837 (19) [MþH]þ; HRMS [C60H60N4]: calcd 837.4896, found
837.4871.
3.4.37. 2,3,7,8,12,13,17,18-Octaethyl-5-(1-naphthyl)-10,20-bis(9-
phenanthrenyl)porphyrin (46). The compound was obtained from
the reaction described in Section 3.4.36. NMR spectroscopy in-
dicated the formation of atropoisomers due to hindered phenan-
threnyl/naphthyl rotation in about a 1:1 ratio. Mp 132 ꢁC; 1H NMR
0.30 (m, 6H, CH2CH3), ꢀ2.40, ꢀ2.41 ppm (each s, each 1H, NH); 13
C
NMR (100 MHz, CDCl3):
d
¼116.4, 16.7, 17.9, 18.1, 19.4, 19.5, 20.7, 29.6,
32.0, 55.3, 55.5, 95.2, 115.8, 122.3, 122.8, 123.0, 124.3, 125.8, 126.4,
126.5, 127.1, 127.5, 128.5, 128.6, 128.8, 129.0, 129.1, 129.2, 129.4,
133.9, 134.7, 136.4, 137.0, 137.3, 203.3, 205.3 ppm; UV/vis (CH2Cl2):
(400 MHz, CDCl3):
d
¼9.54–9.49 (s, 1H Hmeso), 8.98 (m, 4H,
Hphenanthrenyl), 8.76–8.74 (s, 1H, Hphenanthrenyl), 8.67, 8.64 (each s,
each 0.5H, Hphenanthrenyl), 8.58, 8.48 (each d, each 0.5H, J¼7.23 Hz,
Hnaphthyl), 8.36–8.27 (m, 1H, Hnaphthyl), 8.22 (m, 1H, Hnaphthyl), 8.12
(m, 2H, Hnaphthyl/phenanthryl), 8.05 (m, 1H, Hphenanthrenyl), 7.87 (m, 2H,
Hphenanthrenyl), 7.81–7.71 (m, 7H, Hphenanthrenyl/naphthyl), 7.53 (m, 2H,
Hnaphthyl), 7.39 (m, 2H, Hphenanthrenyl), 7.30 (m,1H, Hnaphthyl), 3.69 (m,
4H, CH2CH3), 2.71–2.13 (m, 6H, CH2CH3), 1.88 (m, 6H, CH2CH3), 1.51
(m, 6H, CH2CH3), 0.88 (m, 6H, CH2CH3), 0.53 (m, 6H, CH2CH3),
0.30 ppm (m, 6H, CH2CH3); ꢀ1.51 ppm (s, 2H, NH); 13C NMR
lmax (log
3
)¼426 (5.45), 455 (5.03), 519 (4.56), 592 nm (sh, 4.35) MS
(ESþ), m/z (%): 887 (14) [MþH]þ; HRMS [C64H62N4]: calcd 887.5053,
found 887.5009.
3.4.40. 2,3,7,8,12,13,17,18-Octaethyl-5,10,15-tris(9-phenan-
threnyl)porphyrin (49). The title compound was isolated from re-
action described in Section 3.4.39. NMR spectroscopy indicated the
formation of atropoisomers due to hindered phenanthrenyl rota-
tion in about a 2:1 ratio. Mp 179 ꢁC; 1H NMR (400 MHz, CDCl3):
(100 MHz, CDCl3):
29.6, 31.9, 122.5, 122.9, 125.9, 126.5, 126.9, 127.1, 128.8, 129.2, 130.7,
d
¼14.1, 16.2, 16.7, 18.7, 19.2, 19.3, 19.4, 22.6, 29.3,
d¼9.54–9.50 (s, 1H, Hmeso), 8.99–8.89 (m, 6H, Hphenanthrenyl),
130.9 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼445 (4.89), 472 (3.65), 538
8.84, 8.73 (br s, 1H, atropisomers, Hphenanthrenyl), 8.77 (m, 1H,
Hphenanthrenyl), 8.66–8.61 (s, 1H, atropisomers, Hphenanthrenyl), 8.15
(br d, 2H, J¼8.11 Hz, Hphenanthrenyl), 8.09 (br d, 1H, J¼8.09 Hz,
Hphenanthrenyl), 7.90–7.67 (m, 12H, Hphenanthrenyl), 7.46–7.36 (m, 3H,
Hphenanthrenyl), 3.71 (m, 4H, CH2CH3), 2.69–2.52 (m, 2H, CH2CH3),
2.42–2.29 (m, 2H, CH2CH3), 2.18–2.05 (m, 4H, CH2CH3), 1.96–1.84
(m, 4H, CH2CH3), 1.50 (m, 6H, CH2CH3), 0.88 (m, 6H, CH2CH3), 0.54
(m, 6H, CH2CH3), 0.25 (m, 3H, CH2CH3), 0.13 (t, 3H, J¼7.67 Hz,
CH2CH3), ꢀ1.53 ppm (br s, 2H, NH); 13C NMR (100 MHz, CDCl3):
(3.78), 611 (3.64), 665 nm (3.51); MS (ESþ), m/z (%): 1013 (50)
[MþH]þ; HRMS [C74H68N4]: calcd 1013.5522, found 1013.5505.
3.4.38. 5-(4-Dimethylaminophenyl)-2,3,7,8,12,13,17,18-octaethyl-10-
(9-phenanthrenyl)porphyrin (47). The reaction was performed as
described in Section 3.3.1 using 40 equiv of bromo 4-dimethyla-
minophenyl (0.942 g, 4.71 mmol) and 50 equiv of n-BuLi (2.35 mL,
5.88 mmol) at ꢀ30 ꢁC to rt. The free base 21 (80 mg, 0.117 mmol) in
50 mL THF was added after 1 h at 0 ꢁC and after 30 min stirring at rt
it was quenched at the same temperature to yield 70 mg
(0.084 mmol, 71%) of a purple solid. Mp >300 ꢁC; 1H NMR
d
¼14.1, 16.3, 16.5, 16.7, 17.8, 19.3, 19.5, 20.6, 22.6., 29.3, 29.6, 31.9,
94.1, 114.6,114.7, 116.0, 116.2, 116.3, 122.5, 122.9, 126.5, 127.2, 128.8,
129.2, 129.4, 129.6, 130.7, 130.9, 133.5, 133.6, 133.8, 134.5, 134.7,
136.3, 136.5, 137.9, 137.2, 140.8, 140.9, 141.7 ppm; UV/vis (CH2Cl2):
(500 MHz, CDCl3):
d¼9.64 (s, 1H, Hmeso), 9.61 (s, 1H, Hmeso), 8.96 (m,
2H, Hphenanthrenyl), 8.66 (s, 1H, Hphenanthrenyl), 8.09 (t, 3H, J¼7.9 Hz,
Hphenanthrenyl), 7.85 (m, 2H, Hphenanthrenyl), 7.76 (t, 1H, J¼8.1 Hz,
Hphenanthrenyl), 7.61 (d, 1H, J¼7.8 Hz, phenyl H), 7.28 (d, 1H, J¼7.1 Hz,
HAr), 7.00 (d, 2H, J¼8.6 Hz, jHAr), 3.93 (m, 4H, CH2CH3), 3.81 (m, 2H,
CH2CH3), 3.70 (m, 2H, CH2CH3), 3.19 (s, 6H, N(CH3)2), 2.83 (m, 2H,
CH2CH3), 2.55 (m, 2H, CH2CH3), 2.22 (m, 4H, CH2CH3), 1.80 (m, 6H,
CH2CH3), 1.55 (t, 3H, J¼7.6 Hz, CH2CH3), 1.48 (m, 3H, CH2CH3), 0.63
(t, 3H, J¼7.3 Hz, CH2CH3), 0.44 (t, 3H, J¼7.3 Hz, CH2CH3), 0.32 (m,
6H, CH2CH3), ꢀ2.55 ppm (s, 2H, NH); 13C NMR (100 MHz, CDCl3):
lmax (log
3
)¼445 (4.38), 473 (4.14), 539 (3.14), 608 (3.09), 665 nm
(2.95); MS (ESþ), m/z (%): 1063 (5) [MþH]þ; HRMS [C78H70N4]:
calcd 1063.5679, found 1063.5652.
3.4.41. {2,3,7,8,12,13,17,18-Octaethyl-5-(3-trifluoro-methyl-
phenyl)porphyrinato}palladium(II) (53). The title compound was
isolated from a reaction of the respective free base using procedure
B and afforded 117 mg (0.149 mmol, 93%) of purple crystals. Mp
236 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼10.10 (s, 2H, Hmeso), 10.03 (s,
d
¼16.3, 16.6, 17.1, 17.4, 17.9, 18.2, 19.2, 19.4, 19.6, 19.8, 20.5, 26.8, 40.1,
1H, Hmeso), 8.57 (s, 1H, HAr), 8.30 (d, 1H, J¼7.6 Hz, HAr), 8.08 (d, 1H,
J¼7.8 Hz, HAr), 7.87 (s,1H, HAr), 7.77 (t,1H, J¼7.6 Hz, HAr), 4.03 (q, 8H,
J¼7.6 Hz, CH2), 3.95 (q, 4H, J¼7.3 Hz, CH2), 2.71 (q, 2H, J¼7.3 Hz,
CH2), 2.48 (q, 2H, J¼7.3 Hz, CH2), 1.90 (m, 12H, CH3), 1.84 (t, 6H,
J¼7.9 Hz, CH3),1.12 ppm (t, 6H, J¼7.3 Hz, CH3); UV/vis (CH2Cl2): lmax
40.8, 94.3, 94.9, 110.6, 115.8, 120.2, 122.2, 122.9, 126.7, 127.1, 129.1,
129.6, 130.2, 130.7, 131.0, 134.2, 136.3, 136.3, 137.4, 150.6 ppm; UV/
vis (CH2Cl2): lmax (log
3
)¼433 (4.93), 521 (4.04), 596 (3.63), 664
(3.45) nm; UV/vis (CH2Cl2): lmax (log
3
)¼433 (4.93), 521 (4.04), 596
(3.63), 664 nm (3.45); MS (ESþ), m/z (%): 830 (60) [MþH]þ; HRMS
(log
3)¼400 (5.41), 516 (3.89), 550 nm (4.53).
[C58H63N5]: calcd 830.5162, found 830.5185.
3.4.42. {2,3,7,8,12,13,17,18-Octaethyl-5-(2-naphthyl)-porphyr-
inato}palladium(II) (54). The title compound was isolated from
a reaction of the respective free base using procedure B and affor-
ded 10 mg (0.013 mmol, 20%) of purple crystals. Mp 253 ꢁC; 1H
3.4.39. 2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(9-phenan-threnyl)por-
phyrin (48). The reaction was performed as described in Section
3.3.1 using 40 equiv of 9-bromophenanthrene (2.137 g, 8.44 mmol)
and 40 equiv of n-BuLi (3.37 mL, 8.44 mmol) at ꢀ50 ꢁC to rt. Free
base 21 (150 mg, 0.221 mmol) in 50 mL THF was added after 1 h at
NMR (400 MHz, CDCl3):
d
¼10.12 (s, 2H, Hmeso), 10.04 (s, 1H, Hmeso),
8.66 (s, 1H, Hnaphthyl), 8.33 (d, 1H, J¼8.1 Hz, Hnaphthyl), 8.18 (d, 1H,

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3521
J¼7.9 Hz, Hnaphthyl), 8.12 (d, 1H, J¼8.4 Hz, Hnaphthyl), 8.01 (d, 1H,
J¼7.8 Hz, Hnaphthyl), 7.70 (m, 2H, Hnaphthyl), 4.05 (q, 8H, J¼7.7 Hz,
CH2), 3.94 (q, 4H, J¼7.6 Hz, CH2), 2.68 (m, 2H, CH2), 2.46 (m, 2H,
CH2), 1.94 (m, 12H, CH3), 1.84 (t, 6H, J¼7.7 Hz, CH3), 1.03 ppm (t, 6H,
8.08 (m, 2H, Hnaphthyl), 7.81 (m, 2H, Hnaphthyl), 7.50 (m, 2H, Hnaphthyl),
7.34–7.25 (m, 2H, Hnaphthyl), 7.16 (m, 2H, Hnaphthyl), 3.98 (m, 4H,
CH2CH3), 3.77 (m, 4H, CH2CH3), 2.48–2.21 (m, 2H, CH2CH3), 2.21–
2.20 (m, 6H, CH2CH3), 1.87 (t, 6H, J¼7.52, CH2CH3), 1.65 (m, 6H,
CH2CH3), 0.55 (t, 6H, J¼7.17 Hz, CH2CH3), 0.39 ppm (m, 6H,
J¼7.5 Hz, CH3); 13C NMR (100 MHz, CDCl3):
¼11.4, 14.0, 17.8, 18.3,
d
19.8, 21.5, 22.6, 25.3, 26.9, 27.6, 28.9, 31.4, 34.7, 41.4, 53.2, 95.7, 98.7,
125.5,126.2, 126.7,128.2, 128.4, 131.6,131.7,131.8, 132.0, 133.2,138.1,
138.4, 139.0, 139.3, 141.4, 143.4, 143.6 ppm; UV/vis (CH2Cl2): lmax
CH2CH3); 13C NMR (100 MHz, CDCl3):
d
¼14.0, 16.8, 17.2, 18.0, 19.6,
20.2, 20.6, 21.2, 22.5, 25.2, 29.0, 29.7, 31.5, 34.6, 97.6, 117.3, 124.4,
125.9, 127.6, 127.8, 128.1, 128.8, 132.4, 132.7, 137.0, 139.0, 139.2,
(log
3)¼400 (4.90), 516 (3.80), 550 nm (4.14).
140.4, 141.6, 143.3, 144.7 ppm; UV/vis (CH2Cl2): lmax (log
(3.94), 412 (4.98), 527 (3.95), 561 (4.08) nm.
3)¼340
3.4.43. (5-n-Butyl-2,3,7,8,12,13,17,18-octaethyl-10-phenyl-
porphyrinato)palladium(II) (55). The title compound was isolated
from a reaction of 50 with 25 equiv 1-bromonaphthalene and
95 equiv. BuLi mixed at ꢀ50 ꢁC followed by addition of the por-
phyrin (60 mg, 0.084 mmol) at rt, then stirring for 20 min at ꢀ20 ꢁC
and then stirring for 40 min at rt. Work-up gave a pink solid
3.4.47. {2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(4-ethynyl-phenyl)-
porphyrinato}nickel(II) (61). The free base porphyrin 41 (200 mg,
0.27 mmol) was dissolved in 60 ml DMF, 1.5 g of nickel(II)acetate
was added and the mixture heated to reflux for 3 h. The solvent was
removed in vacuo and the residue taken up in dichloromethane,
washed three times with water, and the organic phase dried over
Na2SO4. Chromatography on alumina (dichloromethane/n-hexane,
1:5, v/v) gave 183 mg (0.23 mmol, 85%) of the title compound after
recrystallization from CH2Cl2/MeOH. Mp 280 ꢁC; Rf¼0.27
(dichloromethane/n-hexane, 1:10, v/v, alumina, 6ꢂ3 cm); 1H NMR
(0.0428 mmol, 50%). 1H NMR (400 MHz, CDCl3):
d¼9.76 (s, 2H,
Hmeso), 7.86–7.49 (br m, 5H, HPh), 4.77 (br m, 2H, Bu–CH2), 3.94 (m,
12H, CH2, 2H, Bu–CH2), 2.92–2.35 (br m, 4H, CH2), 2.01 (t, 3H,
J¼7.5 Hz, CH3), 1.86 (m,12H, CH3, 2H, Bu-CH2), 1.76 (t, 3H, J¼7.5 Hz,
CH3), 1.12 (m, 6H, CH3), 0.56 ppm (t, 3H, J¼7.2 Hz, Bu-CH3).
(500 MHz, CDCl3, SiMe4):
d
¼0.40, 0.55, 1.46, 1.67 (each t, 24H,
3.4.44. (5-sec-Butyl-2,3,7,8,12,13,17,18-octaethyl-10-phenyl-
porphyrinato)palladium(II) (56a). The title compound was isolated
from a reaction of 50 with 10 equiv s-BuLi at ꢀ60 ꢁC with the
porphyrin (80 mg, 0.112 mmol) following procedure A using a re-
action time of 10 min. Work-up gave a single dark red fraction of
a mixture of the two regioisomers 56a and 56b (35 mg 37%). Pre-
cipitation from CH2Cl2/MeOH gave 9 mg of red crystals of 56b while
56a remained in solution and was used for characterization via
3J¼7.5 Hz, CH2CH3), 2.23, 2.47 (each m, 8H, CH2CH3), 3.20 (s, 2H,
C^CH), 3.55, 3.65 (each q, 8H, 3J¼7.5 Hz, CH2CH3), 7.68 (each d, 4H,
J¼4.7, HAr), 7.95 (each d, 4H, J¼4.7, HAr), 9.25 ppm (s, 2H, Hmeso); MS
(EI, 80 eV, 270 ꢁC), m/z (%): 790 (100) [Mþ], 395 (26) [M2þ]; UV/vis
(CH2Cl2): lmax (log
[C52H52N4Ni]: calcd 790.3549, found 790.3587.
3
)¼414 nm (5.19), 535 (3.97), 571 (4.10); HRMS
3.4.48. 5-(4-Dimethylaminophenyl)-2,3,7,8,12,13,17,18-octaethyl-
10,15-diphenylporphyrin (62). The reaction was performed as
described in Section 3.3.1 using 60 equiv of 1-bromo-4-dimethy-
laniline (1.048 g, 5.24 mmol) and 75 equiv of n-BuLi (2.60 mL,
6.55 mmol) at ꢀ40 ꢁC to rt. The free base 6012 (60 mg, 0.087 mmol)
in 50 mL THF was added after 1 h at rt and after 1 h further stirring
at the same temperature the reaction was quenched at 0 ꢁC with
water to yield 60 mg (0.074 mmol, 69%) of a purple solid. Mp 90 ꢁC;
NMR. 1H NMR (400 MHz, CDCl3):
d
¼9.58 (s, 1H, Hmeso), 9.50 (s, 1H,
Hmeso), 8.19–8.08 (m, 2H, HPh), 7.74 (t, 1H, J¼7.7 Hz, HPh), 7.62 (t, 2H,
J¼7.7 Hz, HPh), 4.49 (m, 1H, sBu–CH), 3.97–3.73 (m, 12H, CH2), 2.68–
2.32 (m, 4H, CH2), 2.30 (d, 3H, J¼7.0 Hz, sBu–CH3), 1.79 (m, 12H,
CH3), 1.64 (t, 3H, J¼7.6 Hz, CH3), 1.52 (t, 3H, J¼7.2 Hz, CH3), 0.98 (m,
2H, sBu–CH2), 0.86 (m, 6H, CH3), 0.48 ppm (t, 3H, J¼7.3 Hz, sBu–
CH3).
1H NMR (400 MHz, CDCl3):
d
¼9.40 (s, 1H, Hmeso), 8.36 (d, 2H,
3.4.45. (5-sec-Butyl-2,3,7,8,12,13,17,18-octaethyl-15-phenyl-
porphyrinato)palladium(II) (56b). The title compound was isolated
from reaction described in Section 3.4.42 (9 mg, 0.011 mmol, 9%).
J¼6.90 Hz, HPh), 8.25 (d, 2H, J¼6.84 Hz, HPh), 8.07 (d, 2H, J¼8.43 Hz,
HNMe2Ph), 7.73 (m, 2H, HPh), 7.65 (t, 4H, J¼7.32 Hz, HPh), 7.02 (d, 2H,
J¼8.47 Hz, HNMe2Ph), 3.72 (q, 4H, CH2CH3), 3.21 (s, 6H, N(CH3)2), 2.82
(m, 2H, CH2CH3), 2.67 (m, 2H, CH2CH3), 2.34 (m, 2H, CH2CH3), 2.26–
2.17 (m, 6H, CH2CH3), 1.54 (m, 6H, CH2CH3), 0.92 (m, 6H, CH2CH3),
0.70 (m, 6H, CH2CH3), 0.43 (m, 3H, CH2CH3), 0.33 (m, 3H, CH2CH3),
1H NMR (400 MHz, CDCl3):
d
¼9.76 (s, 2H, Hmeso), 8.08 (d, 2H,
J¼7.6 Hz, HPh), 7.43 (t, 1H, J¼7.4 Hz, HPh), 7.60 (t, 2H, J¼7.9 Hz, HPh),
4.51 (m, 1H, sBu–CH), 4.16 (m, 2H, CH2), 3.92–3.83 (m, 12H, CH2),
2.67 (m, 4H, CH2, sBu–CH2), 2.58 (d, 3H, J¼7.74 Hz, sBu–CH3), 1.77 (t,
12H, J¼7.6 Hz, CH3), 1.64 (t, 6H, J¼7.6 Hz, CH3), 1.02 (t, 6H, J¼7.2 Hz,
CH3), 0.11 ppm (t, 3H, J¼7.3 Hz, sBu–CH3). 13C NMR (100 MHz,
ꢀ2.05 ppm (br s, 2H, NH); 13C NMR (100 MHz, CDCl3):
¼14.0, 14.1,
d
17.1, 17.9, 19.2, 19.5, 20.4, 22.7, 31.9, 29.7, 31.6, 31.9, 40.7, 40.8, 93.4,
110.7, 112.3,112.5,125.2, 126.7,126.9,128.1,134.9, 135.7,136.0, 140.2,
CDCl3):
d
¼13.3, 14.1, 17.9, 18.2, 19.5, 19.7, 21.1, 22.0, 24.5, 29.6, 31.5,
141.5 ppm; UV/vis (CH2Cl2): lmax (log
3
)¼446 (4.10), 480 (4.02), 623
33.3, 40.6, 50.9, 98.6, 126.3, 133.2, 136.8, 137.6, 138.2, 141.4, 142.4,
(3.09), 682 nm (3.47); MS (ESþ), m/z (%): 806 (15) [MþH]þ; HRMS
143.4, 143.6, 144.2 ppm; UV/vis (CH2Cl2): lmax (log
533 (3.53), 563 nm (3.48).
3)¼417 (4.55),
[C56H64N5]: calcd 806.5162, found 806.5122.
3.4.49. 5-(4-Bromophenol)-2,3,7,8,12,13,17,18-octaethyl-10,15-diphe-
nylporphyrin (63). The reaction was performed as described in
Section 3.3.1 using 60 equiv of 1,4-dibromobenzene (1.8823 g,
8.13 mmol) and 75 equiv of n-BuLi (4.05 mL, 10.125 mmol) at
ꢀ30 ꢁC to rt. Free base 60 (93 mg, 0.135 mmol) in THF (50 mL) was
added after 1 h stirring at rt. The reaction mixture was quenched
after another hour with water at 0 ꢁC to yield 44 mg (0.052 mmol,
3.4.46. {2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(1-naph-thyl)porphyr-
inato}palladium(II) (59a). The reaction was performed as described
in Section 3.3.1 using 60 equiv of 1-bromoaphthalene (0.80 mL,
5.96 mmol) and 75 equiv of n-BuLi (2.97 mL, 7.42 mmol) at ꢀ20 ꢁC
to rt. The metal complex 52 (76 mg, 0.099 mmol) in 50 mL THF was
added after 1 h at rt. After stirring for 1 h at the same temperature
the reaction was quenched water at ꢀ0 ꢁC followed by standard
work-up to yield 56 mg (0.060 mmol, 61%) of a pink-red solid.
Alternatively, the compound was prepared via metallation of the
respective free base following procedure B in 65% yield (34 mg,
0.0381 mmol). NMR spectroscopy indicated the formation of two
atropoisomers in a ratio of 1:1 due to hindered naphthyl rotation.
38%) of a green solid. Mp 75 ꢁC; 1H NMR (400 MHz, CDCl3):
d¼9.43
(s, 1H, Hmeso), 8.36 (d, 2H, J¼7.15 Hz, HPh), 8.28 (d, 2H, J¼7.02 Hz,
HPh), 8.17 (d, 2H, J¼8.22 Hz, HBr–Ph), 7.84 (d, 2H, J¼8.17 Hz, HBr–Ph),
7.73 (m, 2H, HPh), 7.67 (m, 4H, HPh), 3.73 (m, 4H, CH2CH3), 2.67 (m,
4H, CH2CH3), 2.26–2.20 (m, 8H, CH2CH3), 1.55 (m, 6H, CH2CH3), 0.71
(m, 6H, CH2CH3), 0.44 (t, 6H, J¼7.24 Hz, CH2CH3), 0.36 (t, 6H,
J¼7.29 Hz, CH2CH3), ꢀ2.11 ppm (s, 2H, NH); 13C NMR (100 MHz,
Mp 245 ꢁC; 1H NMR (400 MHz, CDCl3):
1H, Hmeso), 8.40 (m, 2H, Hnaphthyl), 8.27 (d, 2H, J¼8.28 Hz, Hnaphthyl),
d¼9.88 (s,1H, Hmeso), 9.87 (s,
CDCl3):
d¼14.0, 16.8, 17.2, 17.7, 19.2, 19.5, 20.5, 22.3, 22.7, 25.2, 26.8,

3522
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
29.7, 34.5, 93.8, 126.7, 128.3, 130.0, 132.4, 134.9, 136.0, 136.4 ppm;
atropoisomers due to hindered phenanthrenyl rotation.; 13C NMR
(100 MHz, CDCl3):
¼16.1, 16.4, 19.0, 19.9, 122.5, 122.9, 126.6, 127.1,
UV/vis (CH2Cl2): lmax (log
(3.20), 676 (3.31) nm.
3
)¼441 (4.35), 465 (4.46), 533 (3.30), 610
d
129.7, 129.8, 130.7, 136.3, 136.4 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼493 (5.37), 697 nm (4.13); MS (ESþ), m/z (%): 1240 (20)
3.4.50. 2,3,7,8,12,13,17,18-Octaethyl-5-(4-pentylphenyl)-10,15-diphe-
nylporphyrin (64). The reaction was performed as described in
Section 3.3.1 using 60 equiv of 1-bromo-4-pentylbenzene (1.63 mL,
9.22 mmol) and 75 equiv of n-BuLi (4.19 mL, 11.5 mmol) at ꢀ30 ꢁC
to rt. Free base 60 (106 mg, 0.1537 mmol) in THF (50 mL) was added
after 1 h at rt and after stirring for 3 h at the same temperature the
reaction was quenched at 0 ꢁC with water to yield 23 mg
(0.027 mmol, 17%) of a green solid. Mp 68 ꢁC; 1H NMR (400 MHz,
[MþH]þ; HRMS [C92H78N4]: calcd 1240.6383, found 1240.6368.
3.4.53. {2,3,7,8,12,13,17,18-Octaethyl-5,10-bis(9-phenan-threnyl)por-
phyrinato}palladium(II) (67). Palladium insertion was performed
with the respective free base 48 (40 mg, 0.045 mmol), following the
procedure given in Section 3.3.2 and using palladium acetate
(20 mg, 0.09 mmol) in a mixture of CHCl3 (20 mL) and MeOH (5 mL).
Red crystals were obtained (26 mg, 0.025 mmol, 55%). Mp 238 ꢁC;
CDCl3):
d
¼9.43 (s, 1H, Hmeso), 8.35 (d, 2H, J¼7.13 Hz, HPh), 8.28 (d,
1H NMR (400 MHz, CDCl3):
d¼9.88 (s, 1H, Hmeso), 9.86 (s, 1H, Hmeso),
2H, J¼7.09 Hz, HPh), 8.17 (d, 2H, J¼7.72 Hz, HPh), 7.74 (m, 2H, HPh),
7.66 (t, 2H, J¼7.2 Hz, HPh), 7.64 (d, 4H, J¼7.6 Hz, HPh), 3.73 (m, 4H,
CH2CH3), 2.95 (m, 2H, pentyl-CH2), 2.69 (m, 4H, CH2CH3), 2.57 (m,
4H, CH2CH3), 2.24 (m, 4H, CH2CH3), 1.86 (m, 4H, pentyl-CH2), 1.58
(m, 6H, CH2CH3), 1.47 (m, 2H, pentyl-CH2), 0.99 (m, 3H, pentyl-CH3),
0.70 (t, 6H, J¼7.3 Hz, CH2CH3), 0.44 (m, 6H, CH2CH3), 0.35 (m, 6H,
CH2CH3), ꢀ2.12 ppm (s, 2H, NH); 13C NMR (100 MHz CDCl3):
8.96 (d, 2H, J¼8.50 Hz, Hphenanthrenyl), 8.92 (m, 2H, Hphenanthrenyl),
8.64 (s, 1H, Hphenanthrenyl), 8.58 (s, 1H, Hphenanthrenyl), 8.06 (d, 1H,
J¼7.86 Hz, Hphenanthrenyl), 8.03 (d, 1H, J¼7.81 Hz, Hphenanthrenyl), 7.85
(m, 2H, Hphenanthrenyl), 7.75 (m, 2H, Hphenanthrenyl), 7.68 (m, 2H,
Hphenanthrenyl), 7.43 (d, 1H, J¼8.15 Hz, Hphenanthrenyl), 7.36 (d, 1H,
J¼8.07 Hz, Hphenanthrenyl), 7.28 (m, 1H, Hphenanthrenyl), 7.22 (m, 1H,
Hphenanthrenyl), 3.97 (m, 4H, CH2CH3), 3.75 (m, 4H, CH2CH3), 2.59–
2.49 (m, 2H, CH2CH3), 2.23–1.95 (m, 6H, CH2CH3), 1.85 (t, 6H,
J¼7.56 Hz, CH2CH3), 1.62 (m, 6H, CH2CH3), 0.54 (m, 6H, CH2CH3),
0.39 (t, 3H, J¼7.36 Hz, CH2CH3), 0.35 ppm (t, 3H, J¼7.35 Hz, CH2CH3);
d
¼14.0, 17.1, 17.9, 19.0, 19.2, 19.5, 20.4, 22.4, 27.9, 29.4, 29.5, 30.9,
31.5, 35.3, 35.9, 38.6, 93.4, 125.8, 126.7, 127.0, 127.7, 128.1, 128.5,
134.7, 135.8, 136.1, 140.4, 142.7 ppm; UV/vis (CH2Cl2): lmax
(log
3
)¼438 (4.65), 533 (3.72), 605 (3.43), 673 (3.24) nm; MS (ESþ),
13C NMR (100 MHz, CDCl3):
d
¼16.6, 16.9, 18.2, 18.1, 18.2, 19.5, 19.6,
m/z (%): 833 (25) [MþH]þ], 578 (70); HRMS [C59H68N4]: calcd
20.4, 21.3, 21.9, 97.8, 117.0, 122.5, 122.9, 126.4, 127.1, 127.2, 128.9,
129.12, 129.17, 130.6, 130.82, 130.86, 136.41, 136.45, 137.2, 137.3,
140.0, 140.1. 140.3, 140.4, 141.5, 143.3, 143.4, 143.6, 144.5,144.6 ppm;
833.5514, found 833.5522.
3.4.51. 2,3,7,8,12,13,17,18-Octaethyl-5,10,15-tris(1-naphthyl)por-
phyrin (65). The green title compound was obtained as a minor
side product (<1%) from the preparation of the respective meso
monosubstituted compound 19 and was identified after accumu-
lation of several reactions. NMR spectroscopy indicated the for-
mation of atropoisomers due to hindered naphthyl rotation. Mp
UV/vis (CH2Cl2): lmax (log
3
)¼414 (5.15), 5.27 (4.09), 562 (4.24) nm.
3.4.54. {2,3,7,8,12,13,17,18-Octaethyl-5,10,15-tris(9-phenan-
threnyl)porphyrinato}palladium(II) (68). Palladium insertion was
performed following procedure B with 44 mg (0.410 mmol) of the
respective free base 49, 18 mg (0.082 mmol) palladium acetate in
a mixture of 25 mL CHCl3 and 8 mL MeOH and using a reaction time
of 30 min at 50 ꢁC under Ar. Red crystals (40 mg, 0.033 mmol, 80%)
were obtained. NMR spectroscopy indicated a mixture of atro-
poisomers due to hindered phenanthrenyl rotation. Mp 268 ꢁC;
<75 ꢁC; 1H NMR (400 MHz, CDCl3):
d
¼9.46 (s, 1H, Hmeso), 8.57
(d, 1H, J¼8.63 Hz, Hnaphthyl), 8.53 (d, 1H, J¼7.01 Hz, Hnaphthyl), 8.46
(m, 2H, Hnaphthyl), 8.41–8.34 (m, 2H, Hnaphthyl), 8.25 (d, 2H,
J¼8.31 Hz, Hnaphthyl), 8.23 (d, 2H, J¼8.64 Hz, Hnaphthyl), 8.09–7.89 (m,
8H, Hnaphthyl), 7.30 (m, 3H, Hnaphthyl), 3.67 (m, 6H, CH2CH3), 2.50–
1.80 (m, 10H, CH2CH3), 1.51 (t, 6H, J¼7.35 Hz, CH2CH3), 0.51 (m, 6H,
CH2CH3), 0.26 (m, 6H, CH2CH3), 0.12 (m, 6H, CH2CH3), ꢀ1.64 ppm
1H NMR (400 MHz, CDCl3):
d
¼9.70, 9.69, 9.67 (each s, 1H, Hmeso),
8.99–8.88 (m, 6H, Hphenanthrenyl), 8.77, 8.73 (s, 1H, atropisomers,
Hphenanthrenyl), 8.69, 8.65 (s, 1H, atropisomers, Hphenanthrenyl), 8.59,
8.55, 8.52 (s, 1H, atropisomers, Hphenanthrenyl), 8.14–8.03 (m, 3H,
Hphenanthrenyl), 7.89–7.67 (m, 12H, Hphenanthrenyl), 7.54–7.33 (m, 3H,
Hphenanthrenyl), 3.65 (m, 4H, CH2CH3), 2.56–2.49 (m, 2H, CH2CH3),
2.16 (m, 6H, CH2CH3), 1.97 (m, 4H, CH2CH3), 1.54 (m, 6H, CH2CH3),
0.51 (m, 6H, CH2CH3), 0.31 (t, 6H, J¼7.43 Hz, CH2CH3), 0.24 ppm (m,
(s, 2H, NH); 13C NMR (100 MHz, CDCl3):
19.1, 19.2, 20.5, 22.6, 25.5, 26.7, 27.4, 29.7, 31.6, 34.6, 38.9, 114.6,
124.4, 125.7, 127.9, 128.9, 132.9, 137.3, 138.3, 140.8, 141.8, 142.9 ppm;
d
¼13.0, 14.0, 16.4, 16.7, 17.7,
UV/vis (CH2Cl2): lmax (log
3
)¼488 (5.08), 636 (3.56), 692 nm (4.00);
MS (ESþ), m/z (%): 913 (10) [MþH]þ; HRMS [C66H64N4]: calcd
913.5209, found 913.5180.
6H, CH2CH3); 13C NMR (100 MHz, CDCl3):
d
¼16.5, 16.6, 16.9, 17.9,
19.4, 20.0, 20.9, 29.6, 53.4,116.2,117.3,117.4,122.6,122.9,126.5,127.1,
127.2,128.2,129.2,129.4,130.7,130.9,133.3,136.0,136.5,136.7,136.9,
141.0, 141.2, 141.4, 142.3, 142.5, 143.0, 143.8, 144.4, 144.5, 144.6 ppm;
3.4.52. 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetrakis-(9-phenan-
threnyl)porphyrin (66). This product was obtained from the reaction
described in Section 3.4.39. When free base 21 (66 mg, 0.092 mmol)
were reacted with 60 equiv of 9-bromophenanthrene (1.431 mg,
5.57 mmol) and 60 equiv n-BuLi (2.2 mL, 5.57 mmol) an increased
yield for the meso tetrasubstituted product 66 was observed. A crude
mixture of di- and trisubstituted product (63 mg) was isolated fol-
lowed by the green tetrasubstituted product (63 mg, 0.050 mmol,
54%, precipitated from n-hexane/MeOH by addition of perchloric
acid). It was deprotonated by further purification on aluminum oxide
for the subsequent palladium insertion to yield 48 mg of a green-
brown solid (0.0392 mmol, 42%). Mp <86 ꢁC; 1H NMR (400 MHz,
UV/vis (CH2Cl2): lmax (log
3)¼429 (4.11), 539 (4.04), 575 nm (4.06).
3.4.55. {2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetra-kis(9-phenan-
threnyl)porphyrinato}palladium(II) (69). Palladium insertion was
performed with the respective free base 66 (48 mg, 0.039 mmol) as
described in Section 3.3.2. The reaction was performed with pal-
ladium acetate (17 mg, 0.078 mmol) in a mixture of CHCl3 (20 mL)
and MeOH (8 mL). The reaction mixture was stirred for three days
at rt. Red crystals were obtained from CH2Cl2/MeOH (12 mg,
0.0094 mmol, 12%). NMR spectroscopy indicated a mixture of
atropoisomers due to hindered phenanthrenyl rotation. Mp 290 ꢁC;
CDCl3):
d
¼8.96 (m, 8H, phenanthrenyl H), 8.90 (m,1H, phenanthrenyl
H), 8.86 (m, 1H, phenanthrenyl H), 8.72 (m, 1H, phenanthrenyl H),
8.61 (m, 1H, phenanthrenyl H), 8.23–8.14 (m, 4H, phenanthrenyl H),
8.02 (m, 2H, phenanthrenyl H), 7.81 (m, 14H, phenanthrenyl H), 7.62
(m, 2H, phenanthrenyl H), 7.53 (m, 2H, phenanthrenyl H), 2.18 (m,
12H, CH2), 1.58 (m, 4H, CH2), 1.24 (m, 24H, CH3), ꢀ1.14 ppm (s, 2H,
NH), NMR spectroscopy indicated the existence of several
1H NMR (400 MHz, CDCl3):
d
¼8.95–8.91 (m, 8H, Hphenanthrenyl),
8.85, 8.79, 8.71, 8.66, 8.53, 8.50, 7.97, 7.95 (s, 6H, atropisomers,
Hphenanthrenyl, Hphenanthrenyl), 8.13–7.95 (m, 6H, Hphenanthrenyl), 7.84–
7.70 (m, 14H, Hphenanthrenyl), 7.62 (m, 2H, Hphenanthrenyl), 7.51 (m, 2H,
Hphenanthrenyl), 7.62–7.42 (m, 6H, Hphenanthrenyl), 1.88 (m, 2H,
CH2CH3), 1.72 (m, 4H, CH2CH3), 1.56 (m, 10H, CH2CH3), 1.16–1.08 (m,

M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
3523
Table 2
Crystal Summary of crystal data, data collection and refinement for the crystal structure determinations
Compound
8
12
12$CH2Cl2
16
55
Chemical formula
Mol. wt.
C
41H54N4
C44H50N4
634.88
CH2Cl2/CH3OH
Red plate
0.15ꢂ0.08ꢂ0.02
Triclinic
P-1
7.118(3)
10.327(4)
25.080(11)
86.94(3)
87.76(4)
74.66(4)
1774.9(13)
2
C44H50N4$CH2Cl2
719.81
CH2Cl2/n-hexane
Red block
0.8ꢂ0.8ꢂ0.8
Triclinic
C42H49BrN4
689.76
CH2Cl2/n-hexane
Red plate
0.43ꢂ0.08ꢂ0.05
Monoclinic
P21/n
7.0107(14)
35.111(7)
14.455(3)
90
97.17(3)
90
3530.4(12)
4
1.298
1.200
C46H56N4Pd
771.37
602.88
Crystallization
Color, habit
Crystal size (mm)
Lattice type
Space group
a (Å)
CH2Cl2/CH3OH
Red rhombus
0.25ꢂ0.15ꢂ0.15
Triclinic
P-1
9.5656(5)
12.6775(7)
14.7408(8)
93.3810(10)
103.8620(10)
95.7670(10)
1720.35(16)
2
CH2Cl2/CH3OH
Red plate
0.3ꢂ0.16ꢂ0.13
Triclinic
P-1
10.250(2)
14.531(3)
14.880(3)
64.425(3)
89.108(4)
72.679(3)
1892.0(7)
2
P-1
10.136(6)
14.276(7)
15.195(10)
66.55(4)
82.14(5)
75.85(4)
1954(2)
b (Å)
c (Å)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
Z
2
dcalcd (Mg mꢀ3
)
1.164
0.;068
1.188
0.527
1.223
0.203
1.354
0.529
m
(mmꢀ1
)
Tmax, Tmin
0.99, 0.99
31.51
0.99, 0.92
56.45
0.86, 0.85
0.94, 0.63
31.51
0.93, 0.86
23.24
max (ꢁ)
q
T, K
91
120
114
91
123
Collec. reflections
Indep. reflections
Reflections with F>4.0
Rint
24,356
10,694
4965
0.0697
425
1.616
5152
4697
3632
0.0437
441
34,954
11,170
7256
0.0458
428
12,633
5356
5009
0.0216
469
0.524
s
(F)
No. of parameters
D
/
rmax (e Åꢀ3
)
0.243
2.295
S
0.891
1.017
1.157
1.038
R1 [F>4.0
wR2 [F>4.0
R1 (all data)
wR2 (all data)
s
(F)]
0.0643
0.1634
0.1423
0.1926
0.0647
0.1683
0.0838
0.1853
0.0764
0.2001
0.1197
0.2217
0.0280
0.0697
0.0305
0.0713
s(F)]
a
a
Unit cell data only, no refinement.
6H, CH2CH3), 0.29 ppm (m, 18H, CH2CH3); 13C NMR (100 MHz,
CDCl3):
123.0, 126.6, 127.2, 128.3, 129.3, 129.7, 130.8, 131.1, 133.4, 133.6,
133.8, 135.9, 136.4, 136.6, 136.8, 144.1, 144.5 ppm; UV/vis (CH2Cl2):
structures were solved with Direct Methods using the SHELXTL
PLUS program system32a and refined against jF2j with the program
XL from SHELX-97 using all data.32b Nonhydrogen atoms were re-
fined with anisotropic thermal parameters. Hydrogen atoms were
generally placed into geometrically calculated positions and refined
using a ridging model. The N–H hydrogen atoms were located in
difference maps and refined using the standard riding model.
Crystal data and refinement parameters are compiled in Table 2.
d¼14.1, 16.5, 19.7, 22.7, 29.8, 31.6, 31.9, 53.4, 116.8, 122.7,
lmax (log
3)¼443 (4.43), 553 (3.89), 590 nm (3.75).
3.4.56. {2,3,7,8,12,13,17,18-Octaethyl-5,15-bis(9-phenan-threnyl)-10-
phenylporphyrinato}palladium(II) (70). Palladium insertion was
performed following procedure B with the respective free base 34
and stirring for 30 min to yield 52 mg (0.047 mmol, 54%) of the title
compound as red crystals. Mp 257 ꢁC; 1H NMR (400 MHz, CDCl3):
3.5.2. Special comments: 8. One side chain ethyl group at C2 was
disordered and refined with two split positions; the occupancy
was refined using a free variable. Hydrogen atoms at N22 and N24
were located in a difference map and then refined using a standard
riding model. The residual electron density accounts for a small
amount of nickel(II)porphyrin impurity. 12$CH2Cl2: The crystals
exhibited low high angle diffraction and refinement converged
only to about 0.13. The overall structure and conformation of the
porphyrin macrocycle was very similar to that of the structure of
the unsolvated compound 12. Compound 16: the ethyl side chain
at C7 was disordered and refined with two split positions of equal
occupancy for C72. Residual electron density is located in the
disordered region.
d¼9.70 (s, 1H, Hmeso), 8.99, 8.98 (each d, 2H, J¼7.8 Hz, Hphenanthrenyl),
8.64 (s, 1H, Hphenanthrenyl), 8.60 (s, 1H, Hphenanthrenyl), 8.36, 8.23 (m,
1H, HPh), 8.33 (d, 1H, J¼6.9 Hz, HPh), 8.09 (m, 2H, Hphenanthrenyl),
7.88 (t, 2H, J¼7.88 Hz, Hphenanthrenyl), 7.79 (each d, 2H, J¼7.5 Hz,
Hphenanthrenyl), 7.73 (m, 2H, Hphenanthrenyl, 1H, HPh), 7.68–7.63 (m, 2H,
Hphenanthrenyl, 2H, HPh), 7.41–7.34 (m, 2H, Hphenanthrenyl), 3.67 (m, 4H,
CH2CH3), 2.59–2.30 (m, 4H, CH2CH3), 2.24–2.19 (m, 4H, CH2CH3),
2.12–2.04 (m, 4H, CH2CH3), 1.56 (m, 6, CH2CH3), 0.51–0.40 ppm (m,
16H, CH2CH3); 13C NMR (100 MHz, CDCl3):
17.41, 17.52, 17.94, 19.4, 19.7, 20.0, 20.8, 20.9, 122.6, 122.9, 126.5,
126.6, 126.7, 126.74, 127.1, 127.2, 128.2, 128.9, 129.1, 129.4, 130.9,
131.0, 133.4, 134.9, 135.0, 136.9, 141.1, 141.6, 141.9, 142.1, 142.8, 142.9,
d
¼16.55, 16.90, 16.96,
143.5, 143.7, 143.8 ppm; UV/vis (CH2Cl2): lmax (log
539 (3.78), 573 nm (3.72).
3)¼427 (4.87),
3.5.3. Supplementary data. CCDC-756278 to 756281 contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
3.5. Crystal structure determinations
3.5.1. General. Growth and handling of crystals followed the con-
Acknowledgements
cept developed by Hope.31 Intensity data were collected with
a Siemens SMART system with Mo Ka radiation (
16, and 55, for 12 with a Siemens P4 rotating anode system with Cu
Ka radiation (
¼1.54178 Å), and for 12$CH2Cl2 with a Siemens
R3mV system with Mo-Ka radiation (
¼0.71073 Å). The intensities
were corrected for Lorentz, polarization and extinction effects. The
l
¼0.71073 Å) for 8,
This work was generously supported by a Science Foundation
Ireland Research Professorship Award (SFI 04/RP1/B482). We are
indebted to Dr. John O’Brien for help with the NMR measurements
and to Prof. Marilyn M. Olmstead (UC Davis, USA) for assistance
with the X-ray data collections.
l
l

3524
M.O. Senge et al. / Tetrahedron 66 (2010) 3508–3524
2002, 4, 3807–3809; Hatscher, S.; Senge, M. O. Tetrahedron Lett. 2003, 44, 157–
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