Palladium-catalyzed cross-coupling reactions of brominated porphyrins with functionalized organomagnesium reagents: Direct preparation of functional-group-bearing free base porphyrins

Article abstract of DOI:10.3987/COM-15-S(T)20

The direct preparation of free-base porphyrins possessing reactive functional groups such as esters, halides, amide, nitriles, and acetals is described. This method relies on a simple one-pot procedure that involves sequential palladium-catalyzed cross-coupling of brominated free-base porphyrins with functionalized aryl and alkenylmagnesium reagents, which are readily prepared by iodine-magnesium exchange of the corresponding organic iodides with the turbo Grignard reagent i-PrMgCl·LiCl, followed by demetallation of the resulting magnesium porphyrins under very mild conditions involving either a 1.2 M aqueous methanol solution of HCl or a 0.1 M methanol solution of citric acid at ambient temperature.

Full text of DOI:10.3987/COM-15-S(T)20

HETEROCYCLES, Vol. 93, No. 2, 2016
483
HETEROCYCLES, Vol. 93, No. 2, 2016, pp. 483 - 511. © 2016 The Japan Institute of Heterocyclic Chemistry
Received, 24th August, 2015, Accepted, 11th September, 2015, Published online, 1st December, 2015
DOI: 10.3987/COM-15-S(T)20
PALLADIUM-CATALYZED CROSS-COUPLING REACTIONS OF
BROMINATED
PORPHYRINS
WITH
FUNCTIONALIZED
ORGANOMAGNESIUM REAGENTS: DIRECT PREPARATION OF
FUNCTIONAL-GROUP-BEARING FREE BASE PORPHYRINS
Noriaki Sugita, Ikumi Tsuchiya, and Toshikatsu Takanami*
Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588,
Abstract – The direct preparation of free-base porphyrins possessing reactive
functional groups such as esters, halides, amide, nitriles, and acetals is described.
This method relies on a simple one-pot procedure that involves sequential
palladium-catalyzed cross-coupling of brominated free-base porphyrins with
functionalized aryl and alkenylmagnesium reagents, which are readily prepared by
iodine–magnesium exchange of the corresponding organic iodides with the turbo
Grignard reagent i-PrMgCl·LiCl, followed by demetallation of the resulting
magnesium porphyrins under very mild conditions involving either a 1.2 M
aqueous methanol solution of HCl or a 0.1 M methanol solution of citric acid at
ambient temperature.
INTRODUCTION
Porphyrins are becoming increasingly important target structures since compounds of this class have
widespread use in many fields1 including catalysis,2 medicine,3 materials,4 and molecular
recognition/sensing.5 The physical, chemical, and biological properties of porphyrins can be fine-tuned or
dramatically changed by the selection of the peripheral substituents having different electronic and steric
properties and by the central metal ions coordinated to the nitrogen core.1 Accordingly, significant
interest has arisen in developing new synthetic intermediates and strategies for preparing porphyrin
derivatives that possess various peripheral substituents.6,7 In a related contribution, we previously
reported an approach to prepare functionalized porphyrins via palladium-catalyzed Negishi
cross-coupling of bromoporphyrins H2-1 with functional-group-bearing organozinc reagents 2 (Scheme
1).8 The functionalized zinc porphyrin products Zn-3 of the reaction, where the peripheral substituents of
This work is dedicated to Professor Dr. Lutz F. Tietze on the occasion of his 75th birthday.

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HETEROCYCLES, Vol. 93, No. 2, 2016
Previous work
R1
R1
R1
FG-R-ZnBr
CF3CO2H or
conc. H2SO4
NH N
R2
N
N
N
NH N
N HN
2
R2
R2
Zn
Br
R-FG
R-FG
[Pd]/Ligand
N HN
N
harsh conditions
R1
R1
Zn-3
R1
H2-1
H2-3
FG = -CO2Et, -CN, -Cl, etc
This work
FG-R-I
5
i-PrMgCl•LiCl
R1
R1
R1
NH
FG-R-MgCl•LiCl
NH N
R2
N
N
N
4
dil. HCl, etc.
R2
R2
Mg
Br
R-FG
R-FG
[Pd]/Ligand
N HN
N
N
HN
R1
N
milder conditions
R1
R1
Mg-3
H2-3
H2-1
Scheme 1. Preparation of functional-group-bearing free-base porphyrins
Zn-3 bear chemically reactive function- alities such as ester, amide, halogen, and nitrile groups, could
serve as synthetic intermediates for more complicated porphyrin derivatives because these reactive
functional groups can provide a convenient handle for further functionalization. However, when the
desired product is not zinc porphyrin complexes but other metalloporphyrins, multiple chemical
transformations are necessary to remove the central zinc metal from Zn-3 or its zincated derivatives and
install other metals into the resulting free base. In addition, the demetallation of zinc porphyrins typically
requires the use of strong acidic conditions such as those afforded by CF3CO2H and conc. H2SO4, which
might lead to undesired decomposition of the substrates. Therefore, from the perspective of synthetic
divergence and step economy, functional-group-bearing free-base porphyrins H2-3, a demetallated analog
of zinc porphyrins Zn-3, would be more attractive as an efficient and versatile synthetic intermediate in the
construction of complicated porphyrin derivatives. The use of these free-base porphyrins H2-3 as a
synthetic building block for the construction of complex porphyrin derivatives should enable the insertion
of desired metal ions even in the case of the late-stage functionalization of porphyrins in a multistep
synthetic sequence in order to avoid involving a dezincation process under harsh conditions. Despite
recent significant advances in the transition-metal-catalyzed porphyrin functionalization with
organometallic reagents, a majority of the reported methods afford metallated porphyrins, such as zinc(II),
nickel(II), and copper(II) porphyrins, as the products even when free-base porphyrins are used as starting

HETEROCYCLES, Vol. 93, No. 2, 2016
485
substrates.6-9 Thus, a novel, mild, and direct method that can provide functional-group-bearing free-base
porphyrins including H2-3 remains in demand.
Recently, Knochel’s aryl and alkenylmagnesium reagents 4, which are readily prepared in situ from the
corresponding aryl and alkenyl iodides with the turbo Grignard reagent i-PrMgCl·LiCl, have garnered
considerable interest in synthetic chemistry because of their high synthetic potential on the basis of their
facile availability and significant functional tolerability.10 However, despite their numerous elegant
applications in laboratory synthesis and up-scaled industrial processes, to the best of our knowledge, the
literature contains no account of the functionalization of porphyrins utilizing these organomagnesium
reagents 4.7 We expected that the transition-metal-catalyzed cross-coupling reaction of halogenated
free-base porphyrin H2-1 with a functionalized organomagnesium reagent 4 would initially provide the
corresponding functionalized magnesium porphyrin Mg-3 (Scheme 1). Unlike zinc, nickel, and copper
porphyrins,11 magnesium porphyrins are highly sensitive toward acidic conditions.9,12,13 Therefore, the
resulting magnesium complex Mg-3 would be easily transformed into the corresponding free-base
porphyrins H2-3 under very mild conditions without destruction of the acid-sensitive peripheral functional
groups.
Here, we present an efficient, direct method for preparing functional-group-bearing free-base porphyrins
H2-3 via a simple one-pot procedure involving palladium-catalyzed cross-coupling reaction of brominated
free-base porphyrins H2-1 with functionalized aryl and alkenylmagnesium reagents 4, followed by
demetallation of the resulting magnesium porphyrins Mg-3 under very mild acidic conditions using either
a 1.2 M aqueous methanol solution of HCl or a 0.1 M methanol solution of citric acid at ambient
temperature. The exceptional mildness of these reaction conditions offers high functional tolerability to
the present method, thereby providing the desired free-base porphyrins H2-3 bearing reactive functional
groups such as esters, nitriles, amides, silyls, and acetals in good to high yields.
RESULTS AND DISCUSSION
In a preliminary experiment, we examined the cross-coupling of 5-bromo-10,15,20-triphenylporphyrin
H2-1a with 3-(ethoxycarbonyl)phenylmagnesium chloride lithium chloride 4a, which was generated by a
metallation of ethyl 3-iodobenzoate 5a using the turbo Grignard reagent i-PrMgCl·LiCl, in the presence
of Pd(Ph3P)4 as a catalyst in THF at 25 °C (Scheme 2). Upon completion of the reaction, the mixture was
concentrated in vacuo and chromatographed on silica gel to give the desired meso-functionalized
free-base porphyrin H2-3aa along with the debrominated free base H2-6a and their magnesium complexes
Mg-3aa and Mg-6a. These magnesium complexes Mg-3aa and Mg-6a were quantitatively transformed
to the corresponding free bases H2-3aa and H2-6a by hydrolysis upon treatment with a 1.2 M aqueous

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HETEROCYCLES, Vol. 93, No. 2, 2016
Scheme 2. Palladium-catalyzed coupling of free-base bromoporphyrins H2-1 with functionalized aryl-
magnesium reagents 4a and demagnesiation of Mg-3aa and Mg-6a with a 1.2 M aqueous methanol
solution of HCl
Table 1. Ligand screening for the Pd(OAc)2-catalyzed coupling of meso-bromoporphyrin H2-1a with
functionalized arylmagnesium reagent 4a
yielda (%) yielda (%)
of H2-3aa of H2-6a
entry
ligand
1
2
3
4
5
6
7
rac-BINAP
Cy3P
27
38
51
45
75
62
83
61
58
38
49
21
24
12
(t-Bu)3P
Ph3P
SPhos
XPhos
t-BuXPhos
a Isolated yield.

HETEROCYCLES, Vol. 93, No. 2, 2016
487
methanol solution of HCl. As expected, these cross-coupling and demetallation processes could be
conducted in a one-pot manner. Thus, the sequential one-pot treatment of meso-bromoporphyrin H2-1a
with 10 equiv of arylmagnesium reagent 4a in the presence of Pd(Ph3P)4 (5 mol%) in THF followed by
the addition of a 1.2 M aqueous methanol solution of HCl at 25 °C afforded the desired functionalized
base porphyrin H2-3aa and debrominated free base H2-6a in 55% and 38% yields, respectively, without
their magnesium complexes Mg-3aa and Mg-6a.
Having established demetallation conditions, we explored the catalyst systems on the basis of the
combination of Pd(OAc)2 and different phosphine ligands for optimizing the formation of the
functionalized base porphyrin H2-3aa. As shown in Table 1, ligand screening indicated that bidentate
phosphine ligand was less effective (entry 1) and the steric hindrance of monodentate phosphine ligands
greatly influenced the catalytic reactivity (entries 2‒6). Ultimately, t-BuXPhos was the most effective
ligand among those screened as it afforded the desired free-base porphyrin H2-3aa in 83% isolated yield
without erosion of the ester functionality and significantly reduced the formation of the debrominated
free-base byproduct H2-6a to 12% yield.
Having developed an optimum catalyst system, we examined the substrate scope of the method for the
preparation of functional-group-bearing free-base porphyrins. The examples described in Table 2 indicate
that the sequential method involving the palladium-catalyzed cross-coupling followed by demetallation
with a 1.2 M aqueous methanol solution of HCl can be readily applied to the cross-coupling reactions of
the functionalized arylmagnesium reagent 4a with a variety of di- and tri-substituted meso-bromo-
porphyrins H2-1. The reaction tolerated well a range of substituents on the phenyl ring, including alkyl,
vinyl, silylethynyl, and alkoxy groups, to give the corresponding functionalized free bases H2-3 in good
to high yields (entries 5–10). Alkyl-substituted substrates H2-1b and H2-1m could also undergo the
reaction to afford the corresponding functionalized free bases in good yields (entries 2 and 13). The
present catalytic conditions were suitable for C6F5 and thienyl substituents on the meso-brominated
porphyrins, and the desired products were obtained in good yields (entries 11 and 12). As shown in
Scheme 3, performing the reaction with β-bromoporphyrin H2-1n gave the desired β-functionalized
product H2-3na in 86% yield. Under similar conditions, double functionalization at the meso positions
could also proceed smoothly using 5,15-dibromoporphyrin H2-1o as the substrate (Scheme 4).
The scope of functionalized arylmagnesium reagents prepared in situ from the corresponding aryl iodides
and i-PrMgCl·LiCl was then examined. As shown in Table 3, the mild conditions employed with the
Pd(OAc)2/t-BuXPhos catalyst system and a 1.2 M aqueous methanol solution of HCl afforded a range of
functional groups including ester, nitrile, halogenic, amino, and silyl groups on the phenyl ring of
arylmagnesium reagents 4a—4l to be tolerated in the reaction with meso-bromoporphyrin H2-1a. The
ortho-substitution was not consequential with respect to reaction yield (products H2-3ab and H2-3ah,

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HETEROCYCLES, Vol. 93, No. 2, 2016
Table 2. Palladium-catalyzed coupling of 4a with various meso-bromoporphyrins H2-1
entry
R1
R2
substrate
product
yielda (%)
1
2
Ph
Ph
Ph
n-Bu
C6F5
H
83
66
69
75
70
81
62
72
64
70
73
77
69
1a
1b
1c
1d
1e
1f
H2-3aa
H2-3ba
H2-3ca
H2-3da
H2-3ea
H2-3fa
H2-3ga
H2-3ha
H2-3ia
H2-3ja
H2-3ka
H2-3la
H2-3ma
3
Ph
4
Ph
5
p-tolyl
H
6
3-(CH2=CH)C6H4
4-(i-Pr3SiC≡C)C6H4
3-(MeO)C6H4
3,5-(t-Bu)2C6H3
2,4,6-Me3C6H2
C6F5
H
7
H
1g
1h
1i
8
H
9
H
10
11
12
13
H
1j
Ph
H
1k
1l
2-thienyl
i-Bu
H
1m
a Isolated yield.
62% and 64% yields). As expected, heteroarylmagnesium reagents 4k and 4l could also be used to access
free-base porphyrins H2-3ak and H2-3al bearing pyridyl and thienyl groups, respectively, in good yields.
To further demonstrate the generality of this novel preparation of functional-group-bearing free-base
porphyrins, we sought to employ functional-group-bearing alkenylmagnesium reagents, which are readily
prepared from alkenyl iodides and i-PrMgCl·LiCl in a similar manner for the preparation of
arylmagnesium reagents (Table 4). With acyclic alkenylmagnesium reagents 4m‒4r, the present
cross-coupling/demetallation method was again very effective in producing good yields of the desired
free-base alkenylporphyrins H2-3am‒H2-3ar containing various functional groups such as nitrile, ester,
amide, and silyl functionalities, although a longer reaction time and an increased amount of the magnesium

HETEROCYCLES, Vol. 93, No. 2, 2016
489
Scheme 3. Preparation of β-(3-ethoxycarbonylphenyl)-substituted porphyrin H2-3na
Scheme 4. Preparation of bis(3-ethoxycarbonylphenyl)porphyrin H2-3oa
reagents were required to complete the reaction. Notably, the stereochemistry of the parent alkenyl iodides
were completely preserved during the cross-coupling/demetallation (entries 1‒5); in contrast, a previous
method for preparing these alkenylporphyrins via the palladium-catalyzed Heck reaction of
meso-bromoporphyrins with vinyl derivatives such as acrylonitrile has resulted in the formation of an
inseparable mixture of trans and cis isomers.14 As expected, bromo-substituted cyclic alkenylmagnesium
reagent 4s was also suitable for the reaction, affording the desired free base H2-3as in 65% yield; the
bromo functionality on the olefinic moiety was well tolerated (entry 7).
Finally, we examined the coupling reactions of meso-bromoporphyrin H2-1a with arylmagnesium
reagents 4t and 4u, which possess acetal units; these units are more challenging functionalities because of
their highly sensitive nature toward acidic conditions. As illustrated in Schemes 5 and 6, arylmagnesium
reagents of the protected phenol and aldehyde 4t and 4u, respectively, underwent the sequential
cross-coupling/demetallation under optimal conditions using the Pd(OAc)2/t-BuXPhos catalyst system
and a 1.2 M aqueous methanol solution of HCl. However, the free-base products obtained were not the

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HETEROCYCLES, Vol. 93, No. 2, 2016
desired acetal derivatives H2-3at and H2-3au but deprotected phenol and aldehyde derivatives H2-7 and
H2-8. We subsequently reinvestigated the demetallation conditions and observed that a 0.1 M methanol
Table 3. Palladium-catalyzed coupling of H2-1a with various arylmagnesium reagents
entry FG-ArMgCl product yielda (%) entry FG-ArMgCl product
yielda (%)
72
1
83
7
H2-3aa
H2-3ag
2
3
62
81
8
9
64
79
H2-3ab
H2-3ac
H2-3ah
H2-3ai
4
5
73
80
68
10
11
12
81
51
55
H2-3ad
H2-3ae
H2-3af
H2-3aj
H2-3ak
H2-3al
6
a Isolated yield.
solution of citric acid could be sufficient for the demetallation of the initially produced magnesium
complexes yet compatible with the acetal functional groups. Thus, exposure of meso-bromoporphyrin

HETEROCYCLES, Vol. 93, No. 2, 2016
491
H2-3a to arylmagnesium reagents 4t and 4u in the presence of Pd(OAc)2 and t-BuXPhos followed by
treatment with a 0.1 M methanol solution of citric acid afforded the corresponding adducts H2-3at and
H2-3au in 78% and 76% isolated yields, respectively, leaving the highly acid-sensitive acetal groups
untouched.
Table 4. Palladium-catalyzed coupling of H2-1a with various alkenylmagnesium reagents
yielda
(%)
yielda
(%)
entry FG-alkenyl-MgCl product
entry FG-alkenyl-MgCl product
1
2
3
55
52
61
56
5
6
7
74
85
H2-3am
H2-3an
H2-3ao
H2-3ap
H2-3aq
H2-3ar
65
H2-3as
4
a Isolated yield.
Scheme 5. Preparation of free-base porphyrin H2-3at bearing a protected phenol functional group

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HETEROCYCLES, Vol. 93, No. 2, 2016
Scheme 6. Preparation of free-base porphyrin H2-3au bearing a protected aldehyde functional group
In summary, we developed a facile, direct method for the preparation of free-base porphyrins that include
reactive functionalities such as esters, nitriles, amides, halides, silyls, and acetals. The procedure involves
a sequential palladium-catalyzed cross-coupling of free-base bromoporphyrins with functionalized aryl
and alkenylmagnesium reagents, which are readily available from their iodide precursor and the turbo
Grignard reagent i-PrMgCl·LiCl, followed by demagnesiation of the initially formed magnesium
porphyrins with either a 1.2 M aqueous methanol solution of HCl or a 0.1 M methanol solution of citric
acid at room temperature to give the corresponding functional-group-bearing free-base porphyrins in
good to high yields. We expect these functional-group-bearing free-base porphyrins will be a valuable
addition to the building blocks available in the total synthesis of more complicated porphyrin systems,
thereby allowing the insertion of desired metal ions for later transformation in a multistep synthetic
sequence while preventing the demetallation process under harsh conditions. We are currently conducting
further synthetic studies using these functional-group-bearing free-base porphyrins, and the results will be
reported in due course.
EXPERIMENTAL
1
13
General H and C NMR spectra were recorded at rt on 300, 400, and 500 MHz spectrometers using
1
perdeuterated solvents as internal standards. Chemical shifts of H and 13C spectra are given in ppm
relative to residual protiated solvent and relative to the solvent respectively. 19F NMR spectra were
recorded at rt on a 500 MHz spectrometer using benzotrifluoride as an external standard. The chemical
shift values are expressed as δ values (ppm) and the couple constants values (J) are in Hertz (Hz). The
following abbreviations were used for signal multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m,
multiplet; and br, broad. UV–visible spectra were recorded using a dual-beam grating spectrophotometer

HETEROCYCLES, Vol. 93, No. 2, 2016
493
with a 1 cm quartz cell. The melting point data were not available for the porphyrin derivatives obtained
because these compounds are infusible below 300 °C.
Reactions involving moisture sensitive reagents were carried out under an argon atmosphere using
standard vacuum line techniques and glassware that was flame-dried and cooled under argon before use.
Dry THF was purchased for the reactions and used without further desiccation. Bromoporphyrin
derivatives, H2-1a–H2-1b,8 H2-1d–H2-1h,9 H2-1i,8 H2-1j,9 H2-1m,8 H2-1n,9 and H2-1o,8 were prepared
according to the method described in literature. Other chemicals were purchased from commercial
sources and used as received unless stated otherwise.
Preparation of 5,15-diphenyl-10-pentafluorophenylporphyrin. [5,15-Diphenyl-10-pentafluorophenyl-
porphyrinato]zinc(II)15 (830 mg, 1.200 mmol) was dissolved in a mixture of CH2Cl2 (60 mL) and MeOH
(9 mL) and the solution was treated with trifluoroacetic acid (15 mL) at rt for 30 min. The solution was
diluted with CH2Cl2 (300 mL) and washed with saturated NaHCO3 (150 mL × 2) and H2O (150 mL). The
organic solution was dried over MgSO4 and removal of the solvent offered
5,15-diphenyl-10-pentafluorophenylporphyrin (754 mg, quant.) as a purple solid. Rf = 0.55 (1:1
hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 10.21 (1H, s), 9.29 (2H, d, J = 4.8 Hz), 9.02 (2H, d, J =
4.8 Hz), 9.01 (2H, d, J = 4.8 Hz), 8.84 (2H, d, J = 4.8 Hz), 8.29–8.20 (4H, m), 7.85–7.73 (6H, m), –2.90
(2H, br s); 13C NMR (CDCl3, 75 MHz) δ 147.8, 147.3, 146.8 (2C, d, JCF = 246.0 Hz), 145.9, 145.5, 142.0
(1C, d, JCF = 255.9 Hz), 141.5, 137.6 (2C, d, JCF = 254.7 Hz), 134.7, 132.3, 131.8, 131.5, 129.2, 128.0,
126.9, 120.5, 117.4, 106.6, 100.7; 19F NMR (CDCl3, 466 MHz) δ –138.3 (2F, ddd, JFF = 23.1, 8.0, 5.9), –
154.5 (1F, tt, JFF = 20.5, 8.1 Hz), –163.8 (2F, ddd, JFF = 23.1, 20.5, 8.5 Hz); IR (KBr) 3298, 3116, 3062,
1496, 1068, 984, 922, 856, 791, 725 cm-1; UV/vis (CHCl3) λmax (log ε) 417.0 (5.7), 546.5 (4.3) nm ;
HRMS (EI) calcd for C38H22F5N4 629.1765, found 629.1769.
Preparation of 5-bromo-10,20-diphenyl-15-pentafluolophenylporphyrin (H2-1c). To a solution of
5,15-diphenyl-10-pentafluorophenylporphyrin (629 mg, 1.000 mmol) in CHCl3 (200 mL) was added NBS
(196 mg, 1.100 mmol, 1.1 equiv) at rt. After stirring for 15 min, the solution was concentrated in vacuo.
Column chromatography on silica gel (5:1 hexane/toluene) followed by recrystallization from
hexane/CH2Cl2 gave the product H2-1c (672 mg, 95%) as a purple solid. Rf = 0.65 (1:1 hexane/toluene);
1H NMR (CDCl3, 400 MHz) δ 9.65 (2H, d, J = 4.9 Hz), 8.89 (2H, d, J = 4.9 Hz), 8.87 (2H, d, J = 4.9 Hz),
8.75 (2H, d, J = 4.9 Hz), 8.21–8.14 (4H, m), 7.81–7.73 (6H, m), –2.63 (2H, br s); 13C NMR (CDCl3, 100
MHz) δ 147.2 (8C, br), 146.7 (2C, d, JCF = 243.3 Hz), 142.1 (1C, d, JCF = 256.6 Hz), 141.5, 137.7 (2C, d,
19
JCF = 254.9 Hz), 134.6, 133.0, 132.6, 132.4, 129.2, 128.1, 126.9, 121.6, 116.7, 105.2, 101.1; F NMR
(CDCl3, 466 MHz) δ –136.6 (2F, ddd, JFF = 24.0, 8.9, 6.8), –152.3 (1F, tt, JFF = 21.4, 6.8 Hz), –161.8 (2F,
ddd, JFF = 24.0, 21.4, 8.0 Hz); IR (KBr) 3321, 3059, 3028, 1489, 1346, 980, 926, 791, 717 cm-1; UV/vis

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HETEROCYCLES, Vol. 93, No. 2, 2016
(CHCl3) λmax (log ε) 419.0 (5.6), 516.5 (4.2), 549.5 (3.6), 595.0 (3.4), 649.5 (2.9) nm; HRMS-FAB+
([M+H]+) calcd for C38H21BrF5N4 707.0870, found 707.0875.
Preparation of [5,15-bis(pentafluorophenyl)-10-bromoporphyrinato]zinc(II). To a solution of
[5,15-bis(pentafluorophenyl)porphyrinato]zinc(II)16 (690 mg, 0.978 mmol) in CHCl3 (210 mL) and
pyridine (0.8 mL) was added NBS (192 mg, 1.076 mmol, 1.1 equiv) at room temperature. After stirring
for 15 min, the solution was concentrated in vacuo. Column chromatography on silica gel (5:1
hexane/toluene)
followed
by
recrystallization
from
hexane/CH2Cl2
gave
the
[5,15-bis(pentafluorophenyl)-10-bromoporphyrinato]zinc(II) (430 mg, 56%) as a red-purple solid. Rf =
0.57 (2:1 hexane/THF); 1H NMR (THF-d8, 300 MHz) δ 10.31 (1H, s), 9.84 (2H, d, J = 4.8 Hz), 9.47 (2H,
d, J = 4.8 Hz), 9.09 (2H, d, J = 4.8 Hz), 9.08 (2H, d, J = 4.8 Hz); 13C NMR (THF-d8, 100 MHz) δ 152.4,
150.91, 150.86, 150.8, 147.7 (4C, d, JCF = 248.5 Hz), 143.0 (2C, d, JCF = 252.8 Hz), 138.7 (4C, d, JCF
=
19
252.2 Hz), 134.7, 134.4, 131.92, 131.87, 118.4, 107.9, 105.9, 103.2; F NMR (THF-d8, 466 MHz) δ –
142.9 (4F, ddd, JFF = 24.3, 8.0, 6.1 Hz), –160.1 (2F, tt, JFF = 20.7, 6.1 Hz), –168.7 (4F, ddd, JFF = 24.3,
20.7, 8.2 Hz); IR (KBr) 3097, 3028, 2966, 2924, 2862, 2800, 2750, 1493, 1288, 1061, 987, 856, 775 cm-1;
UV/vis (CHCl3) λmax (log ε) 419.5 (5.8), 550.0 (4.4), 584.0 (3.7) nm; HRMS-FAB+ (M+) calcd for
C32H9BrF10N4Zn 781.9142, found 781.9146.
Preparation of 5,15-bis(pentafluorophenyl)-10-bromoporphyrin (H2-1k). [5,15-Bis(pentafluoro-
phenyl)-10-bromoporphyrinato]zinc(II) (300 mg, 0.382 mmol) was dissolved in a mixture of CH2Cl2 (20
mL) and MeOH (3 mL) and the solution was treated with trifluoroacetic acid (5 mL) at rt for 1.5 h. The
solution was diluted with CH2Cl2 (100 mL) and washed with saturated NaHCO3 (50 mL × 2) and H2O (50
mL). The organic solution was dried over MgSO4 and removal of the solvent offered pure compound
1
H2-1k (276 mg, quant.) as a purple solid. Rf = 0.65 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ
10.21 (1H, s), 9.80 (2H, d, J = 4.9 Hz), 9.35 (2H, d, J = 4.9 Hz), 8.88 (2H, d, J = 4.9 Hz), 8.86 (2H, d, J =
4.9 Hz), –3.00 (2H, br s); 13C NMR data was not available due to their poor solubility; 19F NMR (CDCl3,
466 MHz) δ –138.4 (4F, ddd, JFF = 23.2, 8.9, 6.8 Hz), –153.4 (2F, tt, JFF = 19.6, 6.8 Hz), –163.3 (4F, ddd,
JFF = 23.2, 19.6, 8.7 Hz); IR (KBr) 3313, 3101, 3039, 2927, 1500, 1323, 1142, 1045, 980, 918, 771 cm-1;
UV/vis (CHCl3) λmax (log ε) 412.5 (5.6), 507.5 (4.4), 540.5 (3.8) 585.0 (3.9), 640.5 (3.4) nm;
HRMS-FAB+ ([M+H]+) calcd for C32H12BrF10N4 721.0086, found 721.0089; Anal. calcd for
C32H11BrF10N4: C, 53.28; H, 1.54; N, 7.77, found: C, 53.32; H, 1.72; N, 7.52.
Preparation of 10-bromo-5,15-di(2-thienyl)porphyrin (H2-1l). To a solution of 5,15-di-2-thienyl-
porphyrin17 (382 mg, 0.805 mmol) in CHCl3 (160 mL) was added NBS (158 mg, 0.886 mmol, 1.1 equiv)
at rt. After stirring for 15 min, the solution was concentrated in vacuo. Column chromatography on silica
gel (3:1 hexane/toluene) followed by recrystallization from hexane/CH2Cl2 gave the product H2-1l (275
mg, 62%) as a purple solid. Rf = 0.55 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 10.08 (1H, s),

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495
9.70 (2H, d, J = 4.9 Hz), 9.22 (2H, d, J = 4.9 Hz), 9.13 (2H, d, J = 4.9 Hz), 9.12 (2H, d, J = 4.9 Hz), 7.90
(2H, dd, J = 3.4, 1.3 Hz), 7.87 (2H, dd, J = 5.4, 1.3 Hz), 7.51 (2H, dd, J = 5.4, 3.4 Hz), –2.89 (2H, br s);
13C NMR (CDCl3, 100 MHz) δ 148.3 (4C, br), 146.8 (br), 145.8 (br), 142.2, 134.0, 132.7, 131.9, 131.8
(4C), 128.1, 126.3, 112.0, 106.1, 104.5; IR (KBr) 3309, 3105, 1400, 1323, 1242, 1049, 972, 791, 714
cm-1; UV/vis (CHCl3) λmax (log ε) 419.5 (5.6), 515.5 (4.3), 552.5 (4.0), 591.0 (3.8), 650.5 (3.6) nm;
HRMS-FAB+ ([M+H]+) calcd for C28H18BrN4S2 553.0156, found 553.0157.
Preparation of Functionalized Organomagnesium Reagents (4). All the organomagnesium reagents
used were prepared according to the method described in literature18 as follows. To a well-stirred mixture
of aryl or alkenyl iodide 5 (1.620 mmol) in 6.5 mL of THF was slowly added a solution of iPrMgCl·LiCl
(1.250 mL, 1.620 mmol, 1.3 M in THF) at -20 °C. The mixture was stirred for 30 min at this temperature
and was used immediately.
General Procedure for the Palladium-Catalyzed Reaction of Bromoporphyrins with Functionalized
Organomagnesium Reagents. An oven-dried 100 mL two-necked flask equipped with a magnetic
stirring bar and rubber septum was charged with a free base bromoporphyrin H2-1 (0.162 mmol),
Pd(OAc)2 (1.8 mg, 8.1 μmol, 5 mol%), and t-BuXPhos (6.9 mg, 16.2 μmol, 10 mol%). The reaction
vessel was evacuated and flushed with argon (three times), and then dry THF (30 mL) was added. To the
solution was slowly added 0.2 M THF solution of an organomagnesium reagent 4 (8.0 mL, 1.620 mmol,
10 equiv) via cannula at rt. The mixture was stirred at rt (or 40 °C) for several hours (1–24 h), having
been monitored by TLC (2:1 hexane/THF). To the solution of was added 5 mL of a 1.2 M aqueous
methanol solution of HCl (a 1:9 mixture of conc. HCl and MeOH), and the solution was stirred for 5 min.
The solvent was evaporated and the resulting solid was dissolved in CH2Cl2 (50 mL) and washed with
water and brine. The organic layer was dried over MgSO4 and concentrated in vacuo. Column
chromatography on silica gel (1:1 toluene/hexane) followed by recrystallization from MeOH/CH2Cl2 gave
the pure product H2-3.
5-(3-Ethoxycarbonylphenyl)-10,15,20-triphenylporphyrin (H2-3aa): Prepared from bromoporphyrin
H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure; Purple
1
solid; 92.8 mg, 83% yield; Rf = 0.31 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.90 (1H, s),
8.85 (6H, d, J = 4.9 Hz), 8.77 (2H, d, J = 4.9 Hz), 8.48 (1H, d, J = 7.9 Hz), 8.39 (1H, d, J = 7.5 Hz), 8.27–
8.15 (6H, m), 7.82 (1H, dd, J = 7.9, 7.5 Hz), 7.80–7.68 (9H, m), 4.46 (2H, q, J = 7.1 Hz), 1.39 (3H, t, J =
13
7.1 Hz), –2.71 (2H, br s); C NMR (CDCl3, 75 MHz) δ 166.8, 146.9 (8C, br), 142.6, 142.24, 142.21,
138.3, 134.8, 134.6 (6C), 131.2 (6C), 130.8, 129.4, 129.0, 127.8 (3C), 126.8, 126.7 (6C), 120.5, 120.4,
118.7, 61.2, 14.4; IR (KBr) 3317, 3055, 3028, 2981, 1724, 1473, 1281, 1223, 972, 798, 737, 702 cm-1;
UV/vis (CHCl3) λmax (log ε) 418.5 (5.7), 515.5 (4.3), 550.0 (3.9), 645.5 (3.6) nm; HRMS-FAB+ ([M+H]+)

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calcd for C47H35N4O2 687.2760, found 687.2756; Anal. Calcd for C47H34N4O2: C, 82.19; H, 4.99; N, 8.16.
Found: C, 82.17; H, 5.32; N, 7.90.
5-(n-Butyl)-10,20-diphenyl-15-(3-ethoxycarbonylphenyl)porphyrin (H2-3ba): Prepared from bromo-
porphyrin H2-1b (96.8 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure;
Purple solid; 71.4 mg, 66% yield; Rf = 0.35 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 9.47 (2H,
d, J = 4.9 Hz), 8.94 (2H, d, J = 4.9 Hz), 8.93 (1H, s), 8.84 (2H, d, J = 4.9 Hz), 8.76 (2H, d, J = 4.9 Hz),
8.49 (1H, d, J = 8.3 Hz), 8.38 (1H, d, J = 7.4 Hz), 8.27–8.19 (4H, m), 7.82 (1H, dd, J = 8.3, 7.4 Hz),
7.81–7.69 (6H, m), 4.98 (2H, t, J = 7.8 Hz), 4.49 (2H, q, J = 7.0 Hz), 2.56 (2H, tt, J = 7.8, 7.5 Hz), 1.82
13
(2H, tq, J = 7.5, 7.3 Hz), 1.42 (3H, t, J = 7.0 Hz), 1.15 (3H, t, J = 7.3 Hz), –2.58 (2H, br s); C NMR
(CDCl3, 100 MHz) δ 166.8, 146.6 (8C, br), 142.6, 142.5, 138.3, 134.9, 134.5, 131.6, 131.5, 130.4, 129.5,
129.0, 128.1, 127.7, 126.8, 126.6, 121.0, 119.8, 117.9, 61.2, 40.9, 35.3, 23.6, 14.3, 14.1; IR (KBr) 3317,
3101, 3055, 2958, 2924, 2862, 1720, 1473, 1281, 976, 795, 737 cm-1; UV/vis (CHCl3) λmax (log ε) 419.0
(5.9), 516.5 (4.5), 551.0 (4.1), 592.5 (3.9), 648.5 (3.9) nm; HRMS-FAB+ ([M+H]+) calcd for C45H39N4O2
667.3073, found 667.3067; Anal. Calcd for C45H38N4O2: C, 81.05; H, 5.74; N, 8.40. Found: C, 81.09; H,
5.72; N, 8.44.
5,15-Diphenyl-10-(3-ethoxycarbonylphenyl)-20-pentafluorophenylporphyrin (H2-3ca): Prepared
from bromoporphyrin H2-1c (114.6 mg, 0.162 mmol) and arylmagnesium reagent 4a following the
1
general procedure; Purple solid; 85.8 mg, 69% yield; Rf = 0.42 (1:1 hexane/toluene); H NMR (CDCl3,
400 MHz) δ 8.93 (2H, d, J = 4.9 Hz), 8.88 (1H, s), 8.84 (2H, d, J = 4.9 Hz), 8.77 (2H, d, J = 4.9 Hz), 8.76
(2H, d, J = 4.9 Hz), 8.48 (1H, d, J = 8.1 Hz), 8.36 (1H, d, J = 7.8 Hz), 8.23–8.17 (4H, m), 7.82 (1H, dd, J
= 8.1, 7.8 Hz), 7.80–7.71 (6H, m), 4.45 (2H, q, J = 7.0 Hz), 1.39 (3H, t, J = 7.0 Hz), –2.73 (2H, br s); 13C
NMR (CDCl3, 100 MHz) δ 166.7, 146.69 (2C, d, JCF = 247.5 Hz), 146.66 (8C, br), 142.3, 141.9 (1C, d,
JCF = 247.5 Hz), 141.7, 138.2, 137.6 (2C, d, JCF = 249.1 Hz), 134.7, 134.6, 132.7, 131.5 (4C), 129.4,
19
129.2, 129.0, 128.0, 126.8 (5C), 121.1, 120.6, 116.8 (1C, t, JCF = 20.3 Hz), 100.5, 61.3, 14.3; F NMR
(CDCl3, 466 MHz) δ –138.3 (2F, ddd, JFF = 24.9, 8.5, 6.4 Hz), –154.3 (1F, tt, JFF = 20.6, 6.4 Hz), –163.8
(2F, ddd, JFF = 24.9, 20.6, 8.6 Hz); IR (KBr) 3321, 3101, 3059, 2985, 2924, 1716, 1508, 1281, 984, 922,
798, 748 cm-1; UV/vis (CHCl3) λmax (log ε) 417.5 (5.6), 513.5 (4.2), 547.0 (3.5), 588.5 (3.6), 642.0 (3.2)
nm; HRMS-FAB+ ([M+H]+) calcd for C47H30F5N4O2 777.2289, found 777.2296.
5,15-Diphenyl-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3da): Prepared from bromoporphyrin
H2-1d (87.7 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure; Purple
1
solid; 74.2 mg, 75% yield; Rf = 0.32 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 10.23 (1H, s),
9.34 (2H, d, J = 4.8 Hz), 9.02 (2H, d, J = 4.8 Hz), 8.90 (2H, d, J = 4.8 Hz), 8.84 (1H, s), 8.78 (2H, d, J =
4.8 Hz), 8.45 (1H, d, J = 7.9 Hz), 8.37 (1H, d, J = 7.5 Hz), 8.28–8.19 (4H, m), 7.85–7.72 (7H, m), 4.40
(2H, q, J = 7.1 Hz), 1.35 (3H, t, J = 7.1 Hz), –3.02 (2H, br s); 13C NMR (CDCl3, 75 MHz) δ 166.8, 146.9

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(4C, br), 146.0 (4C, br), 142.8, 141.6, 138.2, 134.7, 131.5 (4C), 131.2, 131.0, 129.0 (2C), 127.8 (3C),
126.8, 126.6, 119.8, 119.0, 105.1, 61.2, 14.3; IR (KBr) 3055, 2924, 1720, 1593, 1477, 1404, 1288, 1080,
968, 849, 795, 733 cm-1; UV/vis (CHCl3) λmax (log ε) 413.0 (5.6), 509.5 (4.2), 543.0 (3.7), 583.0 (3.7),
638.5 (3.2) nm; HRMS-FAB+ ([M+H]+) calcd for C41H31N4O2 611.2447, found 611.2446.
5,15-Di(p-tolyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ea): Prepared from bromoporphyrin
H2-1e (92.3 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure; Purple
1
solid; 72.4 mg, 70% yield; Rf = 0.35 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ 10.18 (1H, s),
9.30 (2H, d, J = 4.8 Hz), 9.03 (2H, d, J = 4.8 Hz), 8.92 (2H, d, J = 4.8 Hz), 8.88 (1H, s), 8.77 (2H, d, J =
4.8 Hz), 8.48 (1H, d, J = 8.0 Hz), 8.37 (1H, d, J = 7.6 Hz), 8.11 (4H, d, J = 7.8 Hz), 7.80 (1H, dd, J = 8.0,
7.6 Hz), 7.57 (4H, d, J = 7.8 Hz), 4.45 (2H, q, J = 7.1 Hz), 2.71 (6H, s), 1.38 (3H, t, J = 7.1 Hz), –2.91
(2H, br s); 13C NMR (CDCl3, 100 MHz) δ 166.9, 147.4 (4C, br), 146.1 (br), 145.9 (br), 143.1, 138.9,
138.2, 137.5, 134.7, 134.5, 131.5, 131.3, 131.0 (4C), 129.0, 127.6, 127.3, 126.6, 120.0, 119.8, 104.9, 61.2,
21.5, 14.3; IR (KBr) 3309, 3116, 3024, 2978, 2924, 2870, 1720, 1469, 1404, 1284, 1215, 1103, 968, 795,
737 cm-1; UV/vis (CHCl3) λmax (log ε) 415.0 (5.7), 511.5 (4.3), 546.5 (3.8), 587.0 (3.8), 641.0 (3.4) nm;
HRMS-FAB+ ([M+H]+) calcd for C43H35N4O2 639.2760, found 639.2769.
5,15-Bis(3-vinylphenyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3fa): Prepared from bromo-
porphyrin H2-1f (96.1 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure;
1
Brown-purple solid; 87.1 mg, 81% yield; Rf = 0.35 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ
10.16 (1H, s), 9.29 (2H, d, J = 4.8 Hz), 9.06 (2H, d, J = 4.8 Hz), 9.00 (2H, d, J = 4.8 Hz), 8.99 (1H, s),
8.87 (2H, d, J = 4.8 Hz), 8.54 (1H, d, J = 7.8 Hz), 8.43 (1H, d, J = 7.3 Hz), 8.34 (2H, s), 8.17 (2H, d, J =
6.8 Hz), 7.86 (2H, d, J = 7.5 Hz), 7.84 (1H, dd, J = 7.8, 7.3 Hz), 7.74 (2H, dd, J = 7.5, 6.8 Hz), 7.03 (2H,
dd, J = 17.6, 10.7 Hz), 6.00 (2H, d, J = 17.6 Hz), 5.43 (2H, d, J = 10.7 Hz), 4.51 (2H, q, J = 7.0 Hz), 1.43
13
(3H, t, J = 7.0 Hz), –2.83 (2H, br s); C NMR (CDCl3, 100 MHz) δ 166.8, 147.2 (4C, br), 146.2 (br),
146.1 (br), 143.0, 142.1, 138.2, 136.9, 136.3, 134.8, 134.2, 132.7, 131.4 (4C), 131.2, 131.0, 129.3, 129.1,
127.0, 126.7, 125.7, 119.63, 119.2, 114.8, 105.1, 61.2, 14.3; IR (KBr) 3309, 3097, 3051, 2981, 2927,
1716, 1589, 1473, 1400, 1281, 1099, 976, 910, 791, 733 cm-1; UV/vis (CHCl3) λmax (log ε) 414.0 (5.8),
509.5 (4.4), 543.0 (3.9), 582.5 (3.9), 636.5 (3.4) nm; HRMS-FAB+ ([M+H]+) calcd for C45H35N4O2
663.2760, found 663.2769; Anal. Calcd for C45H34N4O2: C, 81.55; H, 5.17; N, 8.45. Found: C, 81.73; H,
5.28; N, 8.39.
5,15-Bis[4-{2-(triisopropylsilyl)ethynyl}phenyl]-10-(3-ethoxycarbonylphenyl)porphyrin
(H2-3ga):
Prepared from bromoporphyrin H2-1g (146.2 mg, 0.162 mmol) and arylmagnesium reagent 4a following
the general procedure; Brown-purple solid; 97.7 mg, 62% yield; Rf = 0.43 (1:1 hexane/toluene); 1H NMR
(CDCl3, 400 MHz) δ 10.19 (1H, s), 9.31 (2H, d, J = 4.4 Hz), 9.00 (2H, d, J = 4.4 Hz), 8.90 (2H, d, J = 4.9
Hz), 8.88 (1H, s), 8.80 (2H, d, J = 4.4 Hz), 8.49 (1H, d, J = 8.3 Hz), 8.37 (1H, d, J = 7.3 Hz), 8.18 (4H, d,

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J = 7.8 Hz), 7.90 (4H, d, J = 7.8 Hz), 7.82 (1H, dd, J = 8.3, 7.3 Hz), 4.46 (2H, q, J = 7.1 Hz), 1.39 (3H, t,
13
J = 7.1 Hz), 1.35–1.18 (42H, m), –2.94 (2H, br s); C NMR (CDCl3, 100 MHz) δ 166.8, 147.0 (4C, br),
146.2 (4C, br), 142.9, 141.9, 138.2, 134.6, 134.4, 131.6, 131.4, 131.3, 130.8, 130.6, 130.3, 129.1, 126.7,
123.3, 119.4, 119.2, 107.3, 105.3, 92.2, 61.2, 18.8, 14.3, 11.6; IR (KBr) 3309, 3109, 3066, 3032, 2943,
2866, 1724, 1466, 1396, 1281, 1242, 1107, 972, 798, 737, 671 cm-1; UV/vis (CHCl3) λmax (log ε) 417.0
(5.7), 512.0 (4.4), 547.0 (4.0), 586.0 (3.9), 640.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for
C63H71N4O2Si2 971.5116, found 971.5114; Anal. Calcd for C63H70N4O2 Si2: C, 77.89; H, 7.26; N, 5.77.
Found: C, 77.54; H, 7.24; N, 5.43.
5,15-Bis(3-methoxyphenyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ha): Prepared from bromo-
porphyrin H2-1h (97.4 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure;
1
Purple solid; 78.1 mg, 72% yield; Rf = 0.27 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 10.18
(1H, s), 9.30 (2H, d, J = 4.8 Hz), 9.06 (2H, d, J = 4.8 Hz), 8.97 (2H, d, J = 4.8 Hz), 8.91 (1H, s), 8.80 (2H,
d, J = 4.8 Hz), 8.50 (1H, d, J = 7.9 Hz), 8.39 (1H, d, J = 7.7 Hz), 7.90–7.75 (5H, m), 7.66 (2H, dd, J = 8.0,
7.6 Hz), 7.35 (2H, d, J = 8.0 Hz), 4.47 (2H, q, J = 7.1 Hz), 4.00 (6H, s), 1.40 (3H, t, J = 7.1 Hz), –2.91
(2H, br s); 13C NMR (CDCl3, 75 MHz) δ 166.8, 158.3, 147.1 (br), 147.1 (br), 146.2 (br), 146.0 (br), 143.2,
143.0, 138.2, 134.8, 131.5, 131.4, 131.1, 131.0, 129.3, 129.1, 127.8, 127.7, 126.7, 120.9, 119.6, 119.1,
113.8, 105.0, 61.2, 55.6, 14.3; IR (KBr) 3309, 3101, 3059, 2947, 2835, 1716, 1589, 1466, 1277, 1038,
791 cm-1; UV/vis (CHCl3) λmax (log ε) 414.0 (5.8), 509.5 (4.4), 543.0 (3.8), 582.0 (3.9), 636.0 (3.3) nm;
HRMS-FAB+ ([M+H]+) calcd for C43H35N4O4 671.2658, found 671.2659; Anal. Calcd for C43H35N4O4: C,
77.00; H, 5.11; N, 8.35. Found: C, 76.91; H, 5.23; N, 8.16.
5,15-Bis[3,5-di(t-butyl)phenyl]-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ia): Prepared from
bromoporphyrin H2-1i (124.1 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general
1
procedure; Brown-purple solid; 86.6 mg, 64% yield; Rf = 0.38 (1:1 hexane/toluene); H NMR (CDCl3,
300 MHz) δ 10.21 (1H, s), 9.33 (2H, d, J = 4.8 Hz), 9.06 (2H, d, J = 4.8 Hz), 8.95 (2H, d, J = 4.8 Hz),
8.91 (1H, s), 8.80 (2H, d, J = 4.8 Hz), 8.48 (1H, d, J = 8.1 Hz), 8.40 (1H, d, J = 7.7 Hz), 8.13 (4H, d, J =
1.5 Hz), 7.85 (2H, d, J = 1.5 Hz), 7.82 (1H, dd, J = 8.1, 7.7 Hz), 4.46 (2H, q, J = 7.1 Hz), 1.57 (36H, s),
13
1.39 (3H, t, J = 7.1 Hz), –2.83 (2H, br s); C NMR (CDCl3, 75 MHz) δ 166.9, 149.1, 147.6 (br), 147.5
(br), 146.0 (br), 145.8 (br), 143.3, 140.9, 138.2, 134.7, 131.7, 131.2 (4C), 131.0, 130.0, 129.7, 129.0,
126.6, 121.3, 121.2, 118.8, 104.8, 61.2, 35.1, 31.8, 14.3; IR (KBr) 3313, 3066, 2962, 2870, 1720, 1589,
1481, 1365, 1246, 1103, 972, 914, 795, 737 cm-1; UV/vis (CHCl3) λmax (log ε) 416.0 (5.7), 511.5 (4.3),
547.0 (3.9), 586.0 (3.8), 641.5 (3.5) nm; HRMS-FAB+ ([M+H]+) calcd for C57H63N4O2 835.4951, found
835.4952; Anal. Calcd for C57H62N4O2: C, 81.98; H, 7.48; N, 6.71. Found: C, 81.77; H, 7.51; N, 6.57.
5,15-Bis(2,4,6-trimethylphenyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ja): Prepared from
bromoporphyrin H2-1j (101.3 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general

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procedure; Purple solid; 78.9 mg, 70% yield; Rf = 0.38 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz)
δ 10.13 (1H, s), 9.27 (2H, d, J = 4.8 Hz), 8.93 (1H, s), 8.85 (2H, d, J = 4.8 Hz), 8.77 (4H, d, J = 4.8 Hz),
8.49 (1H, d, J = 7.9 Hz), 8.41 (1H, d, J = 7.5 Hz), 7.82 (1H, dd, J = 7.9, 7.5 Hz), 7.33 (4H, s), 4.48 (2H, q,
13
J = 7.0 Hz), 2.66 (6H, s), 1.88 (12H, s), 1.42 (3H, t, J = 7.0 Hz), –2.76 (2H, br s); C NMR (CDCl3, 75
MHz) δ 166.9, 146.9 (4C, br), 146.3 (4C, br), 142.9, 139.5, 138.2, 138.1, 137.9, 134.7, 131.6, 131.4,
130.4, 130.0, 129.3, 129.0, 127.9, 126.6, 118.4, 118.1, 104.4, 61.2, 21.6, 21.4, 14.3; IR (KBr) 3309, 3097,
2970, 2920, 2866, 1724, 1570, 1466, 1277, 1111, 972, 798, 737 cm-1; UV/vis (CHCl3) λmax (log ε) 416.0
(5.6), 512.5 (4.3), 547.5 (3.7), 589.0 (3.7), 647.5 (3.3) nm; HRMS-FAB+ ([M+H]+) calcd for C47H43N4O2
695.3386, found 695.3386.
5,15-Bis(pentafluorophenyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ka): Prepared from bromo-
porphyrin H2-1k (116.9 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general
procedure; Purple solid; 93.6 mg, 73% yield; Rf = 0.43 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz)
δ 10.22 (1H, s), 9.37 (2H, d, J = 4.8 Hz), 8.95 (2H, d, J = 4.6 Hz), 8.91 (2H, d, J = 4.8 Hz), 8.90 (1H, s),
8.86 (2H, d, J = 4.8 Hz), 8.53 (1H, d, J = 7.9 Hz), 8.36 (1H, d, J = 7.5 Hz), 7.84 (1H, dd, J = 7.9, 7.5 Hz),
4.48 (2H, q, J = 7.1 Hz), 1.40 (3H, t, J = 7.1 Hz), –2.99 (2H, br s); 13C NMR (CDCl3, 75 MHz) δ 166.6,
147.0 (4C, br), 146.7 (4C, d, JCF = 252.2 Hz), 146.4 (4C, br), 142.2 (2C, d, JCF = 259.0 Hz), 142.0, 138.2,
137.7 (4C, d, JCF = 253.5 Hz), 134.7 , 132.9, 132.8, 130.0, 129.6, 129.5 (3C), 126.9, 120.6, 116.2 (2C, t,
J
CF = 19.6 Hz), 106.1, 102.0, 61.3, 14.3; 19F NMR (CDCl3, 466 MHz) δ –138.3 (4F, ddd, JFF = 24.1, 8.1,
6.2 Hz), –153.8 (2F, tt, JFF = 21.4, 6.2 Hz), –163.4 (4F, ddd, JFF = 24.1, 21.4, 8.0 Hz); IR (KBr) 3317,
3105, 3043, 2981, 2935, 1720, 1512, 1281, 987, 914, 733 cm-1; UV/vis (CHCl3) λmax (log ε) 409.5 (5.7),
504.5 (4.4), 536.0 (3.9), 579.0 (3.9), 634.0 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C41H21F10N4O2
791.1505, found 791.1501. Anal. Calcd for C41H20F10N4O2: C, 62.29; H, 2.55; N, 7.09. Found: C, 62.38;
H, 2.84; N, 6.82.
5,15-Di(2-thienyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3la): Prepared from bromoporphyrin
H2-1l (89.7 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure; Purple
1
solid; 77.8 mg, 77% yield; Rf = 0.30 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 10.15 (1H, s),
9.29 (2H, d, J = 4.8 Hz), 9.21 (2H, d, J = 4.8 Hz), 9.11 (2H, d, J = 4.8 Hz), 8.88 (1H, s), 8.78 (2H, d, J =
4.8 Hz), 8.49 (1H, d, J = 7.9 Hz), 8.36 (1H, d, J = 7.5 Hz), 7.93 (2H, dd, J = 3.5, 1.3 Hz), 7.86 (2H, dd, J
= 5.1, 1.3 Hz), 7.82 (1H, dd, J = 7.9, 7.5 Hz), 7.51 (2H, dd, J = 5.1, 3.5 Hz), 4.46 (2H, q, J = 7.1 Hz), 1.39
13
(3H, t, J = 7.1 Hz), –2.83 (2H, br s); C NMR (CDCl3, 75 MHz) δ 166.8, 148.1 (br), 148.0 (br), 146.4
(br), 146.2 (br), 142.8, 142.5, 138.2, 134.8, 133.9, 131.6, 131.43, 131.38, 130.9, 129.4, 129.1, 128.0,
126.7, 126.2, 119.9, 111.5, 105.7, 61.2, 14.3; IR (KBr) 3305, 3105, 3074, 2962, 2927, 2866, 1712, 1589,
1365, 1288, 1103, 949, 795, 702 cm-1; UV/vis (CHCl3) λmax (log ε) 417.5 (5.7), 512.5 (4.3), 550.5 (4.0),
587.5 (3.9), 643.0 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C37H27N4O2S2 623.1575, found 623.1579.

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5,15-Di(i-butyl)-10-(3-ethoxycarbonylphenyl)porphyrin (H2-3ma): Prepared from bromoporphyrin
H2-1m (81.2 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general procedure;
1
Brown-purple solid; 63.8 mg, 69% yield; Rf = 0.33 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ
10.05 (1H, s), 9.51 (2H, d, J = 4.8 Hz), 9.41 (2H, d, J = 4.8 Hz), 9.32 (2H, d, J = 4.8 Hz), 8.90 (1H, s),
8.80 (2H, d, J = 4.8 Hz), 8.52 (1H, d, J = 7.9 Hz), 8.36 (1H, d, J = 7.5 Hz), 7.82 (1H, dd, J = 7.9, 7.5 Hz),
4.83 (4H, d, J = 7.2 Hz), 4.49 (2H, q, J = 7.0 Hz), 2.92–2.69 (2H, m), 1.41 (3H, t, J = 7.0 Hz), 1.22 (12H,
13
d, J = 6.4 Hz), –2.74 (2H, br s); C NMR (CDCl3, 75 MHz) δ 166.9, 148.1, 147.9, 145.0, 144.9, 143.6,
138.1, 134.6, 131.6, 131.5, 129.1, 128.9, 128.7, 128.1, 126.5, 118.4, 118.0, 104.2, 61.2, 43.4, 36.7, 23.3,
14.3; IR (KBr) 3290, 3116, 2954, 2870, 1716, 1581, 1466, 1281, 1107, 787 cm-1; UV/vis (CHCl3) λmax
(log ε) 412.5 (5.6), 511.5 (4.3), 544.5 (3.8), 586.0 (3.8), 642.0 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for
C37H39N4O2 571.3073, found 571.3073.
2-(3-Ethoxycarbonylphenyl)-5,10,15,20-tetraphenylporphyrin (H2-3na): Prepared from bromo-
porphyrin H2-1n (112.4 mg, 0.162 mmol) and arylmagnesium reagent 4a following the general
1
procedure; Purple solid; 106.3 mg, 86% yield; Rf = 0.32 (1:1 hexane/toluene); H NMR (CDCl3, 400
MHz) δ 8.95 (1H, d, J = 4.9 Hz), 8.94 (2H, d, J = 4.9 Hz), 8.92 (1H, d, J = 4.9 Hz), 8.88 (1H, s), 8.86 (1H,
d, J = 4.9 Hz), 8.81 (1H, d, J = 4.9 Hz), 8.36–8.27 (6H, m), 8.07 (1H, s), 8.03–7.95 (2H, m), 7.90 (1H, d,
J = 8.3 Hz), 7.86–7.76 (9H, m), 7.67 (1H, d, J = 7.8 Hz), 7.36–7.22 (4H, m), 4.47 (2H, q, J = 7.2 Hz),
1.48 (3H, t, J = 7.2 Hz), –2.49 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 166.6, 148.1 (br), 147.3 (2C, br),
146.9 (3C, br), 144.8, 144.1 (br), 143.4 (br), 142.6, 142.4, 142.0, 140.6, 139.1, 135.7 (2C), 134.6 (2C),
134.6 (2C), 134.6 (2C), 134.3, 134.3, 131.8, 131.6 (2C), 131.4, 131.0 (2C), 130.8, 129.7, 127.8 (3C),
127.5, 127.4, 127.1, 126.8 (2C), 126.7 (4C), 126.1 (2C), 121.2, 120.5, 120.2, 120.0, 60.8, 14.4; IR (KBr)
3321, 3055, 3028, 2981, 2931, 2908, 1716, 1597, 1473, 1281, 1107, 987, 798, 725 cm-1; UV/vis (CHCl3)
λmax (log ε) 422.0 (5.8), 518.5 (4.4), 553.5 (3.9), 593.0 (3.7), 650.5 (3.4) nm; HRMS-FAB+ ([M+H]+)
calcd for C53H39N4O2 763.3073, found 763.3067.
5,15-Diphenyl-10,20-di(3-ethoxycarbonylphenyl)porphyrin (H2-3oa): The general procedure with
dibromoporphyrin H2-1o (100.5 mg, 0.162 mmol) and 20 equiv instead of 10 equiv of arylmagnesium
reagent 4a (16 mL of its ca. 0.2 M solution in THF, ca. 3.2 mmol) gave the title compound as a purple
1
solid (80.0 mg, 65% yield); Rf = 0.22 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ 8.96 (2H, s),
8.91 (4H, d, J = 4.9 Hz), 8.83 (4H, d, J = 4.9 Hz), 8.52 (2H, d, J = 7.8 Hz), 8.43 (2H, d, J = 7.3 Hz), 8.30–
8.21 (4H, m), 7.84 (2H, dd, J = 7.8, 7.3 Hz), 7.81–7.71 (6H, m), 4.50 (4H, q, J = 7.2 Hz), 1.43 (6H, t, J =
7.2 Hz), –2.61 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 166.8, 146.8 (8C, br), 142.6, 142.2, 138.3,
134.9, 134.6, 131.5, 130.9, 129.5, 129.1, 127.8, 126.8, 126.7, 120.6, 119.0, 61.2, 14.3; IR (KBr) 3317,
3097, 3059, 3032, 2985, 2931, 2908, 1712, 1435, 1358, 1281, 1107, 972, 802, 744 cm-1; UV/vis (CHCl3)

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501
λmax (log ε) 419.0 (5.7), 505.0 (4.2), 549.0 (3.6), 588.5 (3.4), 644.5 (2.9) nm; HRMS-FAB+ ([M+H]+)
calcd for C50H39N4O4 759.2971, found 759.2968.
5-(2-Ethoxycarbonylphenyl)-10,15,20-triphenylporphyrin (H2-3ab): Prepared from bromoporphyrin
H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4b following the general procedure; Purple
solid; 69.1 mg, 62% yield; Rf = 0.32 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 8.86 (2H, d, J =
4.9 Hz), 8.85 (2H, d, J = 4.9 Hz), 8.83 (2H, d, J = 4.9 Hz), 8.70 (2H, d, J = 4.9 Hz), 8.41 (1H, d, J = 7.8
Hz), 8.28–8.20 (6H, m), 8.18 (1H, d, J = 7.3 Hz), 7.87 (1H, dd, J = 7.8, 7.6 Hz), 7.81 (1H, dd, J = 7.6, 7.3
13
Hz), 7.78–7.71 (9H, m), 3.21 (2H, q, J = 7.0 Hz), –0.42 (3H, t, J = 7.0 Hz), –2.56 (2H, br s); C NMR
(CDCl3, 100 MHz) δ 167.5, 146.8 (8C, br), 142.5, 142.44, 142.35, 135.8, 135.1, 134.60, 134.57, 131.2,
131.0 (4C), 130.4, 129.6, 129.5, 128.3, 127.7 (3C), 126.7 (6C), 120.20, 120.16, 119.3, 60.0, 12.4; IR
(KBr) 3317, 3059, 3028, 2981, 2924, 1720, 1469, 1254, 1080, 968, 798, 737 cm-1; UV/vis (CHCl3) λmax
(log ε) 419.0 (5.7), 516.0 (4.3), 550.5 (3.7), 591.0 (3.6), 646.5 (3.2) nm; HRMS-FAB+ ([M+H]+) calcd for
C47H35N4O2 687.2760, found 687.2757; Anal. Calcd for C47H34N4O2: C, 82.19; H, 4.99; N, 8.16. Found:
C, 82.38; H, 5.07; N, 8.03.
5-(4-Ethoxycarbonylphenyl)-10,15,20-triphenylporphyrin (H2-3ac): Prepared from bromoporphyrin
H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4c following the general procedure; Purple
solid; 90.2 mg, 81% yield; Rf = 0.32 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 8.86 (6H, d, J =
4.9 Hz), 8.80 (2H, d, J = 4.9 Hz), 8.45 (2H, d, J = 8.2 Hz), 8.31 (2H, d, J = 8.2 Hz), 8.25–8.17 (6H, m),
7.83–7.66 (9H, m), 4.59 (2H, q, J = 7.1 Hz), 1.56 (3H, t, J = 7.1 Hz), –2.67 (2H, br s); 13C NMR (CDCl3,
75 MHz) δ 166.8, 147.1, 146.9 (8C, br), 142.2 (3C), 134.6 (8C), 131.4, 131.2 (4C), 130.7, 130.2, 127.9,
127.8 (3C), 126.7 (6C), 120.6, 120.4, 118.7, 61.3, 14.5; IR (KBr) 3317, 3105, 3055, 3028, 2978, 2927,
2858, 1720, 1604, 1481, 1358, 1273, 1180, 1107, 964, 802, 706 cm-1; UV/vis (CHCl3) λmax (log ε) 419.0
(5.7), 515.5 (4.3), 551.5 (4.0), 590.5 (3.8), 645.0 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C47H35N4O2
687.2760, found 687.2756; Anal. Calcd for C47H34N4O2: C, 82.19; H, 4.99; N, 8.16. Found: C, 82.01; H,
5.25; N, 7.91.
5-(3-Cyanophenyl)-10,15,20-triphenylporphyrin (H2-3ad): Prepared from bromoporphyrin H2-1a
(100.0 mg, 0.162 mmol) and arylmagnesium reagent 4d following the general procedure; Purple solid;
1
75.6 mg, 73% yield; Rf = 0.35 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.90 (2H, d, J = 4.8
Hz), 8.86 (4H, d, J = 4.8 Hz), 8.71 (2H, d, J = 4.8 Hz), 8.54 (1H, s), 8.45 (1H, d, J = 7.9 Hz), 8.27–8.16
(6H, m), 8.07 (1H, d, J = 7.7 Hz), 7.84 (1H, dd, J = 7.9, 7.7 Hz), 7.80–7.70 (9H, m), –2.68 (2H, br s); 13C
NMR (CDCl3, 75 MHz) δ 147.0 (8C, br), 143.9, 142.2, 142.1, 138.2, 137.1, 134.6 (6C), 131.7, 131.5,
131.3 (4C), 130.2, 127.9 (3C), 127.6, 126.8, 126.7, 121.0, 120.7, 118.8, 116.6, 111.5; IR (KBr) 3317,
3101, 3059, 3028, 2233, 1562, 1473, 1349, 1184, 972, 798, 729, 702 cm-1; UV/vis (CHCl3) λmax (log ε)

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419.0 (5.7), 515.0 (4.3), 550.0 (3.9), 591.0 (3.8), 647.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for
C45H30N5 640.2501, found 640.2504.
5-(4-Chlorophenyl)-10,15,20-triphenylporphyrin (H2-3ae): Prepared from bromoporphyrin H2-1a
(100.0 mg, 0.162 mmol) and arylmagnesium reagent 4e following the general procedure; Purple solid;
1
84.0 mg, 80% yield; Rf = 0.65 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.88 (4H, d, J = 4.8
Hz), 8.86 (2H, d, J = 4.8 Hz), 8.83 (2H, d, J = 4.8 Hz), 8.28–8.19 (6H, m), 8.15 (2H, d, J = 8.2 Hz), 7.82–
13
7.67 (11H, m), –2.66 (2H, br s); C NMR (CDCl3, 75 MHz) δ 146.9 (8C, br), 142.3 (3C), 140.9, 135.6
(6C), 134.6, 134.3, 131.2 (6C), 130.7, 127.8 (3C), 127.0, 126.7 (6C), 120.5, 120.4, 118.4; IR (KBr) 3317,
3055, 1558, 1473, 1350, 1180, 1088, 968, 798, 729 cm-1; UV/vis (CHCl3) λmax (log ε) 418.5 (5.7), 515.0
(4.4), 550.0 (4.1), 591.0 (4.0), 645.5 (3.9) nm; HRMS-FAB+ ([M+H]+) calcd for C44H30ClN4 649.2159,
found 649.2159; Anal. Calcd for C44H29ClN4: C, 81.41; H, 4.50; N, 8.63. Found: C, 81.78; H, 4.70; N,
8.70.
5-(3-Bromophenyl)-10,15,20-triphenylporphyrin (H2-3af): Prepared from bromoporphyrin H2-1a
(100.0 mg, 0.162 mmol) and arylmagnesium reagent 4f following the general procedure; Purple solid;
1
76.7 mg, 68% yield; Rf = 0.62 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.89 (2H, d, J = 4.9
Hz), 8.86 (4H, d, J = 4.9 Hz), 8.85 (2H, d, J = 4.9 Hz), 8.41 (1H, s), 8.28–8.19 (6H, m), 8.17 (1H, d, J =
7.5 Hz), 7.92 (1H, d, J = 8.2 Hz), 7.82–7.70 (9H, m), 7.61 (1H, dd, J = 8.2, 7.5 Hz), –2.77 (2H, br s); 13C
NMR (CDCl3, 75 MHz) δ 146.9 (8C, br), 144.5, 142.3, 142.2 , 137.3 , 134.6 (6C), 133.2, 131.4, 131.2
(4C), 131.0, 130.7, 128.1, 127.8 (3C), 126.7 (6C), 121.2, 120.6, 120.4, 118.0; IR (KBr) 3317, 3101, 3055,
3028, 1585, 1558, 1469, 1350, 972, 798, 702 cm-1; UV/vis (CHCl3) λmax (log ε) 418.5 (5.8), 515.5 (4.4),
550.5 (4.0), 590.0 (3.9), 645.5 (3.8) nm; HRMS-FAB+ ([M+H]+) calcd for C44H30BrN4 693.1654, found
693.1645.
5-[3,5-Bis(trifluoromethyl)phenyl]-10,15,20-triphenylporphyrin (H2-3ag): Prepared from bromo-
porphyrin H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4g following the general
procedure; Purple solid; 87.6 mg, 72% yield; Rf = 0.70 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz)
δ 8.98 (2H, d, J = 4.9 Hz), 8.92 (2H, d, J = 4.9 Hz), 8.91 (2H, d, J = 4.9 Hz), 8.78 (2H, s), 8.75 (2H, d, J =
13
4.9 Hz), 8.41 (1H, s), 8.30–8.22 (6H, m), 7.84–7.74 (9H, m), –2.62 (2H, br s); C NMR (CDCl3, 100
MHz) δ 147.1 (8C, br), 144.8, 142.11, 142.05, 134.6 (6C), 133.9, 132.1, 131.6, 131.5, 130.5 (2C, q, JCF
=
33.7 Hz), 129.9, 128.0, 127.9, 126.81, 126.78, 123.8 (2C, q, JCF = 273.1 Hz), 121.9–121.6 (1C, m), 121.3,
120.9, 115.5; 19F NMR (CDCl3, 466 MHz) δ –63.9 (6F, s); IR (KBr) 3317, 3051, 1381, 1346, 1273, 1176,
1138, 968, 910, 798, 717 cm-1; UV/vis (CHCl3) λmax (log ε) 419.0 (5.7), 515.0 (4.4), 551.0 (4.0), 590.5
(3.9), 645.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C46H29F6N4 751.2296, found 751.2302.
5-(2-Methoxyphenyl)-10,15,20-triphenylporphyrin (H2-3ah): Prepared from bromoporphyrin H2-1a
(100.0 mg, 0.162 mmol) and arylmagnesium reagent 4h following the general procedure; Purple solid;

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503
1
66.8 mg, 64% yield; Rf = 0.48 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.81 (6H, d, J = 4.9
Hz), 8.78 (2H, d, J = 4.9 Hz), 8.28–8.13 (6H, m), 8.01 (1H, d, J = 7.3 Hz), 7.81–7.62 (10H, m), 7.39–7.29
(2H, m), 3.58 (3H, s), –2.64 (2H, br s); 13C NMR (CDCl3, 75 MHz) δ 159.7, 146.8 (8C, br), 142.5, 142.4,
135.7, 134.6, 131.4, 131.1, 130.9 (6C), 129.9, 127.7 (3C), 126.6 (6C), 120.2, 119.9, 119.6, 116.2, 111.3,
56.0;IR (KBr) 3321, 3132, 3055, 3024, 2939, 1593, 1473, 1250, 972, 798, 737 cm-1; UV/vis (CHCl3) λmax
(log ε) 418.5 (5.7), 515.0 (4.3), 549.5 (3.7), 589.0 (3.6), 644.5 (3.1) nm; HRMS-FAB+ ([M+H]+) calcd for
C45H33N4O 645.2654, found 645.2656.
5-(4-N,N-Dimethylaminophenyl)-10,15,20-triphenylporphyrin (H2-3ai): Prepared from bromo-
porphyrin H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4i following the general procedure;
Purple solid; 84.2 mg, 79% yield; Rf = 0.24 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 8.98 (2H,
d, J = 4.8 Hz), 8.86 (4H, d, J = 4.6 Hz), 8.85 (2H, d, J = 4.8 Hz), 8.29–8.19 (6H, m), 8.10 (2H, d, J = 8.6
13
Hz), 7.81–7.70 (9H, m), 7.10 (2H, d, J = 8.6 Hz), 3.22 (6H, s), –2.58 (2H, br s); C NMR (CDCl3, 00
MHz) δ 150.2, 146.8 (8C, br), 142.54, 142.46, 135.7, 134.6 (6C), 131.5, 131.0, 130.8 (4C), 130.4, 127.6
(3C), 126.6 (6), 121.5, 120.0, 119.6, 110.8, 40.7; IR (KBr) 3317, 3028, 2897, 2854, 2800, 1604, 1516,
1473, 1354, 1188, 968, 802, 741 cm-1; UV/vis (CHCl3) λmax (log ε) 420.0 (5.5), 519.5 (4.3), 558.5 (4.1),
596.0 (3.9), 651.0 (3.9) nm; HRMS-FAB+ ([M+H]+) calcd for C46H36N5 658.2971, found 658.2971; Anal.
Calcd for C46H35N5: C, 83.99; H, 5.36; N, 10.65. Found: C, 83.98; H, 5.35; N, 10.56.
5-(4-Trimethylsilylphenyl)-10,15,20-triphenylporphyrin (H2-3aj): Prepared from bromoporphyrin
H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4j following the general procedure; Purple
solid; 90.2 mg, 81% yield; Rf = 0.75 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 8.91 (2H, d, J =
4.9 Hz), 8.87 (4H, d, J = 4.9 Hz), 8.87 (2H, d, J = 4.9 Hz), 8.29–8.20 (8H, m), 7.92 (2H, d, J = 7.8 Hz),
13
7.82–7.69 (9H, m), 0.55 (9H, s), –2.62 (2H, br s); C NMR (CDCl3, 100 MHz) δ 146.9 (8C, br), 142.7,
142.41 (3C), 139.7, 134.61 (6C), 134.1, 131.7, 131.1 (8C), 127.7 (3C), 126.7 (6C), 120.4, 120.2 (3C), –
0.81; IR (KBr) 3321, 3059, 3024, 2954, 1597, 1473, 1350, 1250, 972, 841, 798, 737 cm-1; UV/vis
(CHCl3) λmax (log ε) 419.0 (5.8), 516.0 (4.4), 551.0 (4.0), 590.5 (3.8), 646.0 (3.7) nm; HRMS-FAB+
([M+H]+) calcd for C47H39N4Si 687.2944, found 687.2946; Anal. Calcd for C47H38N4Si: C, 82.18; H,
5.58; N, 8.16. Found: C, 82.47; H, 5.81; N, 7.86.
5-(3-Pyridyl)-10,15,20-triphenylporphyrin (H2-3ak): Prepared from bromoporphyrin H2-1a (100.0 mg,
0.162 mmol) and heteroarylmagnesium reagent 4k following the general procedure; Purple solid; 50.9 mg,
1
51% yield; Rf = 0.28 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 9.50 (1H, s), 9.04 (1H, d, J =
3.8 Hz), 8.91 (2H, d, J = 4.8 Hz), 8.88 (2H, d, J = 4.8 Hz), 8.87 (2H, d, J = 4.8 Hz), 8.80 (2H, d, J = 4.8
Hz), 8.51 (1H, d, J = 7.7 Hz), 8.28–8.18 (6H, m), 7.83–7.66 (10H, m), –2.65 (2H, br s); 13C NMR (CDCl3,
75 MHz) δ 153.8, 149.1, 147.0 (8C, br), 142.18, 142.16, 140.8, 138.3, 134.6 (6C), 131.7, 131.3 (4C),
130.4, 127.8 (3C), 126.7 (6C), 121.9, 120.8, 120.6, 115.5; IR (KBr), 3317, 3055, 3028, 1558, 1473, 1404,

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1350, 1184, 972, 798, 729, 706 cm-1; UV/vis (CHCl3) λmax (log ε) 418.5 (5.8), 515.5 (4.4), 550.0 (4.0),
590.5 (3.9), 645.5 (3.7) nm; HRMS-FAB+ ([M+H]+) calcd for C43H30N5 616.2501, found 616.2501.
5-(3-Thienyl)-10,15,20-triphenylporphyrin (H2-3al): Prepared from bromoporphyrin H2-1a (100.0 mg,
0.162 mmol) and heteroarylmagnesium reagent 4l following the general procedure; Purple solid; 55.4 mg,
1
55% yield; Rf = 0.40 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ 8.98 (2H, d, J = 4.9 Hz), 8.86
(2H, d, J = 4.9 Hz), 8.85 (4H, d, J = 4.9 Hz), 8.25–8.20 (6H, m), 8.02 (1H, dd, J = 2.9, 1.0 Hz), 8.00 (1H,
13
ddd, J = 4.9, 2.9, 1.0 Hz), 7.81–7.72 (9H, m), 7.70 (1H, ddd, J = 4.9, 2.9, 1.0 Hz), –2.65 (2H, br s); C
NMR (CDCl3, 100 MHz) δ 146.9 (8C, br), 142.5, 142.4 (3C), 134.6 (6C), 131.1 (6C), 130.8, 128.3, 127.8
(3C), 126.7 (6C), 123.4 (2C), 120.4, 120.3, 114.5; IR (KBr) 3321, 3101, 3055, 3028, 1473, 1346, 1176,
972, 798, 741, 702 cm-1; UV/vis (CHCl3) λmax (log ε) 419.0 (5.4), 516.0 (4.3), 552.5 (4.0), 590.5 (3.8),
647.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C42H29N4S 621.2113, found 621.2114.
(Z)-5-(2-Ethoxycarbonyl)vinyl-10,15,20-triphenylporphyrin (H2-3am): The general procedure with
bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv instead of 10 equiv of alkenykmagnesium
reagent 4m (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple
1
solid (56.7 mg, 55%); Rf = 0.34 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ 10.33 (1H, d, J =
15.6 Hz), 9.55 (2H, d, J = 4.9 Hz), 8.99 (2H, d, J = 4.9 Hz), 8.87 (2H, d, J = 4.9 Hz), 8.85 (2H, d, J = 4.9
Hz), 8.31–8.21 (6H, m), 7.86–7.72 (9H, m), 6.92 (1H, d, J = 15.6 Hz), 4.60 (2H, q, J = 7.0 Hz), 1.59 (3H,
t, J = 7.0 Hz), –2.36 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 166.3, 146.8 (8C, br), 145.7, 142.1, 141.9,
134.54, 134.49, 132.1, 131.4, 131.3 (4C), 128.8, 127.9 (3C), 126.8 (6C), 121.8, 121.1, 112.3, 60.9, 14.5;
IR (KBr) 3317, 3055, 2981, 2904, 1712, 1620, 1469, 1362, 1273, 1165, 972, 725 cm-1; UV/vis (CHCl3)
λmax (log ε) 425.0 (5.6), 522.0 (4.1), 565.5 (4.1), 657.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for
C43H33N4O2 637.2604, found 637.2599; Anal. Calcd for C43H32N4O2: C, 81.11; H, 5.07; N, 8.80. Found:
C, 81.17; H, 5.19; N, 8.58.
(Z)-5-(2-Cyano)vinyl-10,15,20-triphenylporphyrin (H2-3an): The general procedure with bromo-
porphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv instead of 10 equiv of alkenykmagnesium reagent
4n (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple solid (49.7
mg, 52%); Rf = 0.37 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 9.64 (1H, d, J = 11.2 Hz), 9.24
(2H, d, J = 4.9 Hz), 8.93 (2H, d, J = 4.9 Hz), 8.80 (2H, d, J = 4.9 Hz), 8.78 (2H, d, J = 4.9 Hz), 8.28–8.12
13
(6H, m), 7.84–7.67 (9H, m), 6.59 (1H, d, J = 11.2 Hz), –2.55 (2H, br s); C NMR (CDCl3, 100 MHz) δ
151.2, 146.9 (8C, br), 142.0 (3C), 134.6, 134.5, 132.4, 131.5, 131.2, 128.6, 127.9 (3C), 126.8, 126.7,
122.1, 121.1, 116.5, 109.6, 106.5; IR (KBr) 3321, 3055, 3032, 2954, 2920, 2222, 1601, 1558, 1469, 1354,
1157, 1072, 972, 798, 706 cm-1; UV/vis (CHCl3) λmax (log ε) 423.0 (5.7), 519.5 (4.4), 558.5 (4.2), 594.5
(4.0), 652.5 (3.5) nm; HRMS-FAB+ ([M+H]+) calcd for C41H28N5 590.2345, found 590.2350.

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505
(E)-5-(2-Cyano)vinyl-10,15,20-triphenylporphyrin (H2-3ao): The general procedure with bromo-
porphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv, instead of 10 equiv, of alkenykmagnesium
reagent 4o (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple
solid (58.3 mg, 61%); Rf = 0.37 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 9.92 (1H, d, J = 16.1
Hz), 9.32 (2H, d, J = 4.9 Hz), 8.92 (2H, d, J = 4.9 Hz), 8.79 (2H, d, J = 4.9 Hz), 8.76 (2H, d, J = 4.9 Hz),
8.22–8.12 (6H, m), 7.84–7.68 (9H, m), 6.20 (1H, d, J = 16.1 Hz), –2.46 (2H, br s); 13C NMR (CDCl3, 100
MHz) δ 151.8, 146.8 (8C, br), 141.9, 141.7, 134.51, 134.47, 132.6, 131.6, 131.4, 128.1, 128.03, 127.95,
126.9, 126.8, 122.6, 121.6, 118.2, 110.4, 107.8; IR (KBr) 3317, 3105, 3059, 3028, 2214, 1604, 1477,
1354, 1165, 968, 798, 733 cm-1; UV/vis (CHCl3) λmax (log ε) 427.5 (5.5), 525.5 (4.1), 566.5 (4.1), 659.0
(3.8) nm; HRMS-FAB+ ([M+H]+) calcd for C41H28N5 590.2345, found 590.2350; Anal. Calcd for
C41H27N5: C, 83.51; H, 4.61; N, 11.88. Found: C, 83.73; H, 4.72; N, 12.02.
(E)-5-(2-N,N-Dimethylaminocarbonyl)vinyl-10,15,20-triphenylporphyrin (H2-3ap): The general
procedure with bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv instead of 10 equiv of
alkenykmagnesium reagent 4p (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title
1
compound as a purple solid (57.8 mg, 56%); Rf = 0.24 (1:1 hexane/toluene); H NMR (THF-d8, 400
MHz) δ 10.08 (1H, d, J = 15.1 Hz), 9.48 (2H, d, J = 4.9 Hz), 8.85 (2H, d, J = 4.9 Hz), 8.76 (2H, d, J = 4.9
Hz), 8.75 (2H, d, J = 4.9 Hz), 8.23–8.08 (6H, m), 7.79–7.63 (9H, m), 7.26 (1H, d, J = 15.1 Hz), 3.18 (6H,
br s), –2.45 (2H, br s); 13C NMR (THF-d8, 100 MHz) δ 165.0, 146.7 (8C, br), 142.4, 142.2, 141.8, 134.37,
134.35, 132.9, 131.4, 130.8 (4C), 128.9, 127.7 (3C), 126.6 (6C), 120.8, 120.5, 114.7, 36.3 (br), 34.9 (br);
IR (KBr) 3317, 3105, 3055, 2920, 2858, 1647, 1608, 1473, 1396, 1350, 1142, 972, 802, 741 cm-1; UV/vis
(CHCl3) λmax (log ε) 425.5 (5.6), 524.5 (4.2), 563.0 (4.2), 657.0 (3.8) nm; HRMS-FAB+ ([M+H]+) calcd
for C43H34N5O 636.2763, found 636.2766.
(E)-5-(2-Trimethylsilyl)vinyl-10,15,20-triphenylporphyrin (H2-3aq): The general procedure with
bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv instead of 10 equiv of alkenykmagnesium
reagent 4q (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple
solid (76.2 mg, 74%); Rf = 0.68 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 9.49 (1H, d, J = 18.9
Hz), 9.47 (2H, d, J = 4.8 Hz), 8.94 (2H, d, J = 4.8 Hz), 8.84 (4H, d, J = 4.8 Hz), 8.30–8.20 (6H, m), 7.84–
13
7.71 (9H, m), 6.97 (1H, d, J = 18.9 Hz), 0.60 (9H, s), –2.48 (2H, br s); C NMR (CDCl3, 75 MHz) δ
148.3, 146.7 (8C, br), 144.2, 142.5, 142.3, 134.6, 134.5, 131.2, 131.1, 131.0, 129.4, 127.7 (3C), 126.7
(6C), 120.24, 120.17, 119.6, –0.9; IR (KBr) 3317, 3055, 2951, 2924, 2854, 1593, 1469, 1250, 976, 864,
795, 729 cm-1; UV/vis (CHCl3) λmax (log ε) 421.5 (5.6), 520.5 (4.2), 558.5 (4.0), 598.0 (3.8), 654.0 (3.7)
nm; HRMS-FAB+ ([M+H]+) calcd for C43H37N4Si 637.2787, found 637.2797; Anal. Calcd for
C43H36N4Si: C, 81.09; H, 5.70; N, 8.80. Found: C, 80.76; H, 5.66; N, 8.62.

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5-(1-Trimethylsilyl)vinyl-10,15,20-triphenylporphyrin (H2-3ar): The general procedure with bromo-
porphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv, instead of 10 equiv, of alkenykmagnesium
reagent 4r (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple
solid (87.8 mg, 85%); Rf = 0.70 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 9.22 (2H, d, J = 4.8
Hz), 8.87 (2H, d, J = 4.8 Hz), 8.83 (2H, d, J = 4.8 Hz), 8.81 (2H, d, J = 4.8 Hz), 8.37–8.06 (6H, m), 7.84–
7.64 (9H, m), 6.84 (1H, d, J = 3.3 Hz), 6.69 (1H, d, J = 3.3 Hz), 0.18 (9H, s), –2.70 (2H, br s); 13C NMR
(CDCl3, 75 MHz) δ 155.8, 146.7 (6C), 145.0, 142.49, 142.45, 134.6 (6C), 132.4, 131.2, 130.9, 130.7,
130.6, 127.7 (3C), 126.7 (6C), 124.1, 119.9, 119.3, -0.7; IR (KBr) 3317, 3055, 2954, 2897, 1469, 1346,
1250, 972, 845, 737 cm-1; UV/vis (CHCl3) λmax (log ε) 419.0 (5.7), 517.5 (4.3), 553.0 (4.0), 593.5 (3.7),
648.5 (3.7) nm; HRMS-FAB+ ([M+H]+) calcd for C43H37N4Si 637.2787, found 637.2789; Anal. Calcd for
C43H36N4Si: C, 81.09; H, 5.70; N, 8.80. Found: C, 81.01; H, 5.66; N, 8.80.
5-(2-Bromocyclopent-1-enyl)-10,15,20-triphenylporphyrin (H2-3as): The general procedure with
bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and 40 equiv instead of 10 equiv of alkenylmagnesium
reagent 4s (32 mL of its ca. 0.2 M solution in THF, ca. 6.4 mmol) gave the title compound as a purple
solid (72.0 mg, 65%); Rf = 0. 68 (1:1 hexane/toluene); 1H NMR (CDCl3, 400 MHz) δ 9.21 (2H, d, J = 4.9
Hz), 8.96 (2H, d, J = 4.9 Hz), 8.86 (2H, d, J = 4.9 Hz), 8.85 (2H, d, J = 4.9 Hz), 8.32–8.19 (6H, m), 7.83–
7.70 (9H, m), 3.62 (2H, t, J = 7.3 Hz), 3.48 (2H, t, J = 7.6 Hz), 2.68 (2H, tt, J = 7.6, 7.3 Hz), –2.66 (2H,
br s); 13C NMR (CDCl3, 75 MHz) δ 146.9 (8C, br), 143.2, 142.4, 142.2, 134.6, 134.5, 131.8, 131.2, 131.0,
129.4, 127.7 (3C), 126.7, 126.6, 125.5, 120.6, 112.0, 114.6, 45.1, 41.8, 23.9; IR (KBr) 3321, 3093, 3055,
3024, 2943, 2850, 1558, 1473, 1350, 1184, 972, 798, 733 cm-1; UV/vis (CHCl3) λmax (log ε) 418.5 (5.7),
514.5 (4.3), 549.5 (3.9), 590.5 (3.8), 645.5 (3.6) nm; HRMS-FAB+ ([M+H]+) calcd for C43H32BrN4
683.1810, found 683.1813; Anal. Calcd for C43H31BrN4: C, 75.55; H, 4.57; N, 8.20. Found: C, 75.44; H,
4.56; N, 8.03.
5-[4-{(Tetrahydro-2H-pyran-2-yl)oxy}phenyl]-10,15,20-triphenylporphyrin (H2-3at): The general
procedure with bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 4t, followed
by demetalation with 5 mL of a 0.1 M methanol solution of citric acid, instead of a 1.2 M aqueous MeOH
solution of HCl (a 1:9 mixture of conc. HCl and MeOH), gave the title compound as a purple solid (90.2
1
mg, 78%); Rf = 0.42 (1:1 hexane/toluene); H NMR (CDCl3, 400 MHz) δ 8.93 (2H, d, J = 4.9 Hz), 8.86
(6H, d, J = 4.9 Hz), 8.28–8.20 (6H, m), 8.14 (2H, d, J = 8.3 Hz), 7.81–7.70 (9H, m), 7.45 (2H, d, J = 8.3
Hz), 5.73 (1H, t, J = 3.4 Hz), 4.20 (1H, td, J = 10.4, 3.8 Hz), 3.85–3.77 (1H, m), 2.26–2.12 (1H, m), 2.11–
2.02 (2H, m), 1.88–1.69 (3H, m), –2.67 (2H, br s); 13C NMR (CDCl3, 100 MHz) δ 157.2, 146.9 (8C, br),
142.4, 135.6 (3C), 135.5, 134.6 (6C), 131.0 (8C, br), 127.7 (3C), 126.7 (6C), 120.2, 120.1, 120.0, 114.8,
97.0, 62.5, 30.7, 25.4, 19.1; IR (KBr) 3321, 3101, 3055, 3028, 2943, 2873, 1601, 1470, 1350, 1230, 964,
798, 741 cm-1; UV/vis (CHCl3) λmax (log ε) 419.5 (5.8), 516.0 (4.3), 552.0 (3.9), 591.5 (3.6), 647.0 (3.5)

HETEROCYCLES, Vol. 93, No. 2, 2016
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nm; HRMS-FAB+ ([M+H]+) calcd for C49H39N4O2 715.3073, found 715.3080; Anal. Calcd for
C49H38N4O2: C, 82.33; H, 5.36; N, 7.84. Found: C, 82.28; H, 5.42; N, 7.74.
5-(4-Hydroxyphenyl)-10,15,20-triphenylporphyrin (H2-7): Prepared from bromoporphyrin H2-1a
(100.0 mg, 0.162 mmol) and arylmagnesium reagent 4t following the general procedure; Purple solid;
74.6 mg, 73% yield; Rf = 0.22 (1:1 hexane/toluene); 1H NMR (THF-d8, 400 MHz) δ 8.92 (2H, d, J = 4.9
Hz), 8.81 (6H, d, J = 4.9 Hz), 8.58 (1H, br s), 8.24-8.15 (6H, m), 8.03 (2H, d, J = 8.3 Hz), 7.75-7.65 (9H,
m), 7.17 (2H, d, J = 8.3 Hz), -2.58 (2H, br s); 13C NMR (THF-d8, 100 MHz) δ 158.8, 147.7 (8C, br),
143.5, 143.4, 136.4, 135.3 (6C), 134.1, 131.9, 131.5 (6C, br), 128.5 (3C), 127.5 (6C), 121.6, 120.9, 120.7,
114.6; IR (KBr) 3317, 3051, 1701, 1601, 1562, 1473, 1350, 1211, 968, 798, 702 cm-1; UV/vis (CHCl3)
λmax (log ε) 420.0 (5.6), 516.5 (4.4), 552.5 (3.9), 592.0 (3.6), 647.5 (3.5) nm; HRMS-FAB+ ([M+H]+)
calcd for C44H31N4O 631.2498, found 631.2496; Anal. Calcd for C44H30N4O: C, 83.79; H, 4.79; N, 8.88.
Found: C, 83.62; H, 5.00; N, 8.71.
5-[4-(1,3-Dioxolan-2-yl)phenyl]-10,15,20-triphenylporphyrin (H2-3au): The general procedure with
bromoporphyrin H2-1a (100.0 mg, 0.162 mmol) and arylmagnesium reagent 2u, followed by
demetalation with 5 mL of a 0.1 M MeOH solution of citric acid, instead of a 1.2 M aqueous MeOH
solution of HCl (a 1:9 mixture of conc. HCl and MeOH), gave the title compound as a purple solid (84.8
1
mg, 76%); Rf = 0.43 (1:1 hexane/toluene); H NMR (CDCl3, 300 MHz) δ 8.87 (8H, d, J = 4.8 Hz), 8.26
(2H, d, J = 8.2 Hz), 8.24–8.19 (6H, m), 7.88 (2H, d, J = 8.2 Hz), 7.82–7.67 (9H, m), 6.15 (1H, s), 4.35
(2H, t, J = 7.0 Hz), 4.21 (2H, t, J = 7.0 Hz), –2.69 (2H, br s); 13C NMR (CDCl3, 75 MHz) δ 146.8 (8C, br),
143.3, 142.3 (3C), 137.4, 134.6 (8C), 131.1 (8C, br), 127.7 (3C), 126.7 (6C), 124.9, 120.3, 120.2, 119.6,
104.1, 65.6; IR (KBr) 3317, 3055, 3028, 2954, 2924, 2877, 1601, 1473, 1350, 1219, 1076, 972, 802, 737
cm-1; UV/vis (CHCl3) λmax (log ε) 418.5 (5.8), 515.5 (4.3), 550.0 (3.8), 589.5 (3.6), 645.5 (3.3) nm;
HRMS-FAB+ ([M+H]+) calcd for C47H35N4O2 687.2760, found 687.2756; Anal. Calcd for C47H34N4O2: C,
82.19; H, 4.99; N, 8.16. Found: C, 82.10; H, 5.05; N, 7.86.
5-(4-Formylphenyl)-10,15,20-triphenylporphyrin (H2-8): Prepared from bromoporphyrin H2-1a (100.0
mg, 0.162 mmol) and arylmagnesium reagent 4u following the general procedure; Purple solid; 73.9 mg,
71% yield; Rf = 0.41 (1:1 hexane/toluene); 1H NMR (CDCl3, 300 MHz) δ 10.34 (1H, s), 8.89 (4H, d, J =
4.8 Hz), 8.88 (2H, d, J = 4.8 Hz), 8.78 (2H, d, J = 4.8 Hz), 8.39 (2H, d, J = 7.9 Hz), 8.27-8.19 (8H, m),
13
7.80-7.71 (9H, m), -2.68 (2H, br s); C NMR (CDCl3, 75 MHz) δ 192.2, 148.7, 146.7 (8C, br), 142.09,
142.07, 135.7, 135.2, 134.5 (6C), 131.6, 131.3 (4C, br), 130.5, 127.9, 127.8 (3C), 126.7 (6C), 120.8,
120.5, 118.1; IR (KBr) 3579, 3518, 3425, 3317, 3055, 3028, 1601, 1473, 1350, 1265, 1176, 972, 802, 706
cm-1; UV/vis (CHCl3) λmax (log ε) 419.5 (5.8), 516.5 (4.3), 551.5 (3.8), 590.5 (3.6), 647.0 (3.3) nm;
HRMS-FAB+ ([M+H]+) calcd for C45H31N4O 643.2498, found 643.2495; Anal. Calcd for C45H30N4O: C,
84.09; H, 4.70; N, 8.72. Found: C, 84.39; H, 4.80; N, 8.48.

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ACKNOWLEDGEMENTS
This study was supported by a Grant-in-Aid for Scientific Research (KAKENHI: #15K07874) from the
Japan Society for the Promotion of Science.
REFERENCES AND NOTES
1. For reviews, see (a) The Porphyrin Handbook, ed. by K. M. Kadish, K. M. Smith, and R. Guilard,
Academic Press, San Diego, 1999−2003, Vol. 1−20; (b) Handbook of Porphyrin Science ed. by K. M.
Kadish, K. M. Smith, and R. Guilard, World Scientific, Singapore, 2010; Vol. 1–25.
2. For selected recent examples, see (a) J. R. Frost, S. M. Huber, S. Breitenlechner, C. Bannwarth, and
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