Journal of Porphyrins and Phthalocyanines Published at https://www.worldscinet.

com/jpp/
J. Porphyrins Phthalocyanines 2021; 1015–1021
DOI: 10.1142/S1088424621501005

10,15-Bis(ethoxycarbonyl)-5-(4-methoxycarbonylphenyl)
B(III)subchlorin: A photosensitizer with high singlet
oxygen producing efficiency

Ishfaq A. Bhat, Rahul Soman◊, Brijesh Chandra, Sameeta Sahoo◊,

Vikranth Thaltiri and Pradeepta K. Panda◊,*

School of Chemistry, University of Hyderabad, Hyderabad-500046, India

Received 19 March 2021

Accepted 12 July 2021

Dedicated to Professors Lechosław Latos-Grażyński and Hiroyuki Furuta

on the occasion of their 70th and 65th birthdays, respectively

ABSTRACT: A novel A2B-type B(III)subchlorin has been synthesized for the first time in two ways
possessing two different ester moieties upon macrocyclic periphery from meso-diethoxycarbonyl
tripyrrane. Its photophysical and electrochemical properties have been explored. Introduction of the third
meso-substituent resulted in the synthesis of the B(III)subchlorin as the major product with the formation
of minor oxidized B(III)subporphyrin analogue. This subchlorin derivative was found to generate singlet
oxygen much efficiently with quantum yield (fD) 0.88.
KEYWORDS: subchlorin, meso-functionalization, oxidative stability, unsymmetrical substitution,
singlet oxygen, photodynamic therapy.

INTRODUCTION synthesis of its oxidized counterpart B(III)subporphyrin

Chlorins are naturally occurring porphyrin analogue
endowed with a b,b-reduced bond and owing to their
relatively lower symmetry than porphyrins, they display
quite intense absorption in red regions unlike the latter [1].
They are ubiquitous in nature with several new chlorins
being isolated from marine microbes in recent years [2].
In order to mimic their structure-function relationship,
several new synthetic analogues have been realized [3].
Further, chlorins also emerged as ideal photosensitizers
for photodynamic therapy (PDT) [4]. In 2008, the first
contracted congener of chlorin viz. subchlorin was reported
by Osuka and coworkers as B(III)-complexes of its meso-
triaryl derivatives (Fig. 1). They first noticed its presence
as a minor product in the reaction mixture during the
◊
 SPP full member in good standing.
*Correspondence to: Prof. P. K. Panda, School of Chemistry,
University of Hyderabad, Hyderabad-500046, India. Phone
number: +91-40-2313 4818, email: pradeepta.panda@uohyd.
ac.in ; pkpsc@uohyd.ernet.in.
and isolated it via tedious repeated chromatographic
purification [5]. Subsequently, through post-synthetic
manipulation, they could isolate pure subchlorins in two
ways. Either by reduction of parent B(III)subporphyrin or
more selectively by oxidation of B(III)subbacteriochlorins,
which were synthesized on the other hand by reduction
of the corresponding subporphyrins [6]. Although the
chemistry of subporphyrins was first initiated through
independent contributions from Osuka and coworkers
and Kobayashi and coworkers [7] and flourished greatly
like that of B(III)subphthalocyanines [8], but there was no
subsequent report related to subchlorins.
Recently, our group reported a facile and exclusive
synthesis of B(III)subchlorins endowed with ethoxy­
carbonyl substituents at two of their meso-positions [9].
Another striking observation we found was the noticeable
interaction between the two B(III)subchlorin moieties in
the m-oxo dimer 3. Therefore, we intended to synthesize
the more conjugated dimer through the free-meso position
in order to explore the electronic effect along with its
photophysical and electrochemical properties.

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 1016 I. A. BHAT ET AL.
Fig. 1. Molecular Structures of reported B(III)subchlorin (1–3) and synthesized B(III)subchlorin (4) and B(III)subporphyrin (5).
Scheme 1. Bromination of B(III)subchlorin 2 using N-Bromosuccinimide (NBS).
RESULTS AND DISCUSSION
In order to synthesize the arene bridged dimers
through Suzuki protocol, we started with the bromination
of B(III)subchlorin 2. However, to our surprise, meso-
bromination did not occur like that noticed in case of
the meso-free B(III)subporphyrin reported by Osuka
and coworkers [10]. Instead, we noticed the bromination
occurring at the b-positions and their isolation in pure
form was found to be very difficult (Scheme 1).
To understand this unusual reaction of subchlorin 2, we
performed density-functional theory (DFT) calculations
to determine their reactive sites (electrophilic and
nucleophilic centers) using the Fukui function and dual
descriptor analysis in the Multiwfn program (Supporting
information) [11]. The result clearly indicates the
electrophilic sites residing on the b-pyrrolic positions
(C11 and C21) and the meso-position becoming least
reactive towards electrophiles in subchlorin 2 (Fig. 2).
Therefore, we condensed the B(III)-complex of the
diester tripyrrane 8 with terephthaloyl chloride to obtain
the desired arene-bridged dimer 9 by adapting similar
procedure reported by Osuka and coworkers (Scheme 2)
for A2B type subporphyrins [12]. The crude reaction
mixture of subporphyrinoids, was subjected to an axial
ligand exchange reaction in methanol-THF mixture.
Interestingly, we found two intensely fluorescent very
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2150100.indd 1016
close spots in thin layer chromatography, a greenish-yellow
band, followed by a reddish-orange one. The compounds
were separated by column chromatography by eluting
with ethyl acetate and hexane mixture. The absorption
spectral analysis to our surprise showed a subchlorin
(reddish-orange fraction) and subporphyrin (greenish-
yellow fraction) pattern, respectively, unlike the exclusive
formation of 2. Further, surprise came from mass spectral
analysis, where the high-resolution mass spectrometry
(HRMS) data (m/z 522.1715, 520.1645) of the major
band didn’t correspond to desired dimeric compound 9,
instead appeared to be a monomeric analogue.
The single crystal X-ray diffraction (SCXRD)
analysis of crystals obtained by slow evaporation of
chloroform solution reddish orange fraction, confirmed
our presumption and the obtained structure was found
to be B(III)subchlorin 4 with a phenyl ester substituent
at the third meso-position (Fig. 3). Similar to reported
subporphyrinoid structures, compound 4 also displayed
a bowl-shaped structure with central boron having an
axial methoxy group and connected to three nitrogen
atoms of the macrocyclic core. In the case of 4, the
reduced pyrrolidine ring C-C bond length is 1.560(4) Å,
and found to be slightly longer than the reported diester
subchlorin 2 and triaryl subchlorin 1 (1.537(4) and
1.501(16) Å, respectively) [8]. The corresponding bond
lengths for the other pyrrolic units of 4 are found to be
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 10,15-BIS(ETHOXYCARBONYL)-5-(4-METHOXYCARBONYLPHENYL) B(III)SUBCHLORIN 1017

Electron density surfaces

Transparent color (cyan = - ve; violet = + ve)

Fig. 2. Exact evaluation of dual descriptor based on electron density of subchlorin 2.

Scheme 2. Synthesis of B(III)subchlorin 4 and B(III)subporphyrin 5.

1.366(3) and 1.365(4) Å and are in good agreement with
reported compound 2. The bowl depth of the compound
is found to be 1.305 Å, which is slightly less than that
of 2 (1.358 Å). The dihedral angle of meso-arene unit
with macrocyclic plane (Cα-Cmeso-Cα″) is 48.62°, which
is comparable with that for the reported A3-subchlorin 1
(48.57°) (Supporting information Fig. S11). The structu­
ral analysis confirms that only one of the acid chloride
groups underwent the ring closing condensation to form
the B(III)subchlorin, while the unused acid chloride unit
reacted with methanol to form the methoxycarbonyl
moiety. Use of stoichiometric amount of terephthaloyl

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 1018 I. A. BHAT ET AL.

Fig. 3. X-ray crystal structure and selected bond lengths of B(III)subchlorin 4 (a) top view, (b) side view in 30% elipsoid probability,
peripheral hydrogens are omitted for clarity.

Fig. 4. (a) Absorption and (b) emission spectra of 2 (black) and 4 (red) in toluene.

chloride did not yield any subporphyrinoid. The major
fraction, the B(III)subchlorin 4 could be isolated in
5% yield. Subsequently, we synthesized macrocycle 4
in 9% yield by replacing the acid chloride with methyl
4-(chloroformyl)benzoate to investigate its photophysical,
electrochemical properties and singlet oxygen generation
ability in order to study its efficacy as a photosensitizer
for photodynamic therapy.
1
H NMR spectral data of the major fraction complied
with the structure of macrocycle 4, which showed typical
subchlorin characteristic peak i.e. two pseudo-doublets
coming from pyrrolidine residue, one at 4.4 ppm and
other pseudo doublet merging with methoxy of phenyl
ester and resonate at 4.0 ppm and it is clearly evident
from 2D-NMR (1H–1H COSY) spectrum (Supporting
Information). The b-pyrrolic peaks resonate at 8.32 and
7.21 ppm. All these b-pyrrolic and pyrrolidine peaks are
in good agreement with the reported diester subchlorin
2. The four benzene protons resonates as a multiplet at
8.0 ppm. Axial methoxy group resonate at 1.25 ppm.
One the other hand, the 1H NMR spectrum of the minor
fraction found to match with the corresponding oxidized
counter i.e. B(III)subporphyrin 5 with the disappearance
of the pseudo-doublets (Supporting information).
The absorption spectrum of macrocycle 4 is slightly
bathochromically shifted compared with subchlorin 2
(Fig. 4). In addition, the relative absorbance intensities
of the split Soret like bands those appeared at 322 and
356 nm were reversed compared to those in compound 2,
with the intensity of second Soret band at lower energy
is slightly higher than the first Soret band. Interestingly,
the higher energy Q bands around 400 nm in subchlorin
2, found to be quite red shifted and clearly split in
macrocycle 4 (407 and 432 nm), with a broader lowest-
energy Q-band appeared at 538 nm, which is 10 nm
red shifted than the former. The relative intensities of
Soret and lowest energy Q-bands are found to increase
with the introduction of the third substituent (2 vs. 4).

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 10,15-BIS(ETHOXYCARBONYL)-5-(4-METHOXYCARBONYLPHENYL) B(III)SUBCHLORIN 1019

As discussed earlier, subchlorin 4 displayed a redish

orange fluorescence with a maxima at 571 nm having
a Stoke shift of 1074 cm-1. The compound showed a
broader emission spectrum tailing upto ~750 nm (Fig. 4).
The fluorescence quantum yield is found to be 0.12 for
4, (5,10,15,20-Tetrakis(phenyl)porphyrin (H2TPP) in
toluene was used as reference, Ff = 0.11) which is less
than that of reported subchlorin 2 and comparable with
that of 1 and showed a triple exponential decay curve with
an average lifetime of 1.44 ns (Supporting information).
The utility of compound 4 as a potential photosensitizer
for photodynamic therapy was probed by measuring the
near infrared (NIR) steady state luminescence spectrum
of singlet oxygen appearing as a broad peak at ~1279 nm
in aerated toluene (Fig. 5), and compared with that from Fig. 5. Singlet oxygen luminescence of optically matched
freebase tetraphenylporphyrin (H2TPP) as the reference H2TPP (reference fD 0.7) and subchlorin 4 in air saturated
[13]. The singlet oxygen quantum yield (fD) was found to toluene solution (lex = 550 nm).
be quite high (0.88) for 4 compared to diester subchlorin
2 (0.54). This clearly indicates that the former may
act as an excellent photosensitizer in photodynamic indicates introduction of meso-phenyl ester group to
therapy compared to chlorin e6, a second generation compound 2 made the compound even more electron
photosensitizer having fD 0.64 [14]. In addition to this, deficient.
the compound 4 is expected to show a better activity Macrocycle 4 is the first example of a subchlorin
because of its smaller molecular size and bowl-shaped possessing two different kinds of ester moieties upon
structure that prevents molecular aggregation [15]. its periphery. As our efforts to hydrolyze the ethyl esters
Electrochemical analysis of B(III)subchlorin 4 was in 2 had so far not yielded any desired carboxylic acid
performed by cyclic voltammetry (CV) and differential derivatives, we therefore further checked if the methyl
pulse voltammetry (DPV) in dichloromethane solution ester could be selectively hydrolyzed keeping in view
using TBAPF6 as supporting electrolyte and glassy carbon the importance of the acid functionalities upon the
as working electrode. The first oxidation potential of 4 macrocyclic periphery [16]. Our attempt to hydrolyze
was found to be 0.59 V and is irreversible in nature. The one/more of the ester groups again did not yield the
compound showed two reversible reduction potentials desired product. So we are looking at further fine tuning
at -1.68 and -1.91 V. (Fig. 6). The electrochemical data our target while exploring alternate ways to hydrolyse the
ester moieties in order to exploit its potential utility.
Table 1. Oxidation potential (E1/2
ox red
), reduction potential (E1/2 )
+
vs. Fc/Fc in V, and electrochemical HOMO–LUMO gaps
EXPERIMENTAL
(ΔE) for 2 and 4.

Comp. ox1
E1/2 ox2
E1/2 Red1
E1/2 Red2
E1/2 DE [eV] Measurements

2[9] 0.55(Irri) 0.651(Rev) -1.8(Irri) 2.35 NMR spectra were recorded on Bruker 500 MHz FT
NMR spectrometer and for 1H NMR, tetramethylsilane
4 0.59(Irri) -1.68(Rev) -1.91(Rev) 2.27
(TMS, d = 0 ppm) in CDCl3 used as an internal standard

Fig. 6. Cyclic (black-line) and differential pulse (red-line) voltammograms of macrocycle 4, oxidation (a) and reduction (b) potentials
recorded in dichloromethane with TBAPF6 as supporting electrolyte with scan rate of 50 mV/sec (potentials are referenced vs.
external ferrocene/ferrocinium couple).

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 1020 I. A. BHAT ET AL.
at room temperature and for 13C NMR solvent peak was
used as reference. The mass spectral determinations were
carried out by Bruker Maxis HRMS spectrometer by
ESI techniques. The UV-Vis spectra were recorded using
Perkin Elmer Lambda-750 UV/VIS spectrophotometer.
All fluorescence spectra were recorded in Fluorolog-3-221
spectrofluorometer equipped with Hamamatsu H10330-75
TE cooled NIR detector working at -60 °C.
Crystallographic data for B(III)subchlorin 4 was
collected on Rigaku XtaLAB Synergy, Single source
X-ray diffractometer. Mo-Ka (l = 0.71073 Å) radiation
was used to collect X-ray reflections on the single
crystal. Data reduction was performed using CrysAlisPro
1.171.40.35a (Rigaku OD, 2018). Both aromatic and
nonaromatic C–H atoms were fixed geometrically.
Empirical absorption correction was done using
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction,
2018) and refined using SHELXL-2014/7 with
anisotropic displacement parameters for non-H atoms.
Detailed synthetic procedure
Synthesis of B(III)subchlorin 4 using terephthaloyl
chloride: Diester tripyrrane 8 (1.7 mmol) was taken in a
500 mL two-necked round bottom flask and dissolved in
1,2-dichlorobenzene (50 mL) under nitrogen atmosphere.
Borane triethylamine complex (5.1 mmol) was added
and the reaction mixture was heated in an oil bath at
150 °C for 2 h. The reaction temperature was adjusted to
100 °C and the reaction mixture was slowly diluted with
1,2-dichlorobenzene (350 mL) containing terephthaloyl
chloride (8.5 mmol). The reaction mixture was heated
at 150 °C for 30 min. Pyridine (17 mmol) was added
to neutralize the reaction mixture. After 5 min nitrogen
atmosphere was removed and the reaction mixture was
heated at reflux under open air atmosphere for another
2 h. 1,2-dichlorobenzene was removed under reduced
pressure. The mixture was refluxed in THF:MeOH
for 12 h to perform the ligand exchange. The minor
subporphyrin was eluted with ethylacetate:hexane (3:7)
and the first as an orange-coloured band having green
fluorescence followed by the major subchlorin band with
reddish fluorescence.
Synthesis of B(III)subchlorin 4 using methyl (chlo­
roformyl)benzoate: Diester tripyrrane 8 (1.05 mmol)
was taken in a 500 mL two-necked round bottom flask
and dissolved in 1,2-dichlorobenzene (30 mL) under
nitrogen atmosphere. Borane triethylamine complex
(3.16 mmol) was added and the reaction mixture was
heated in an oil bath at 150 °C for 2 h. The reaction bath
was cooled to 100 °C and the reaction mixture was slowly
diluted with 1,2-dichlorobenzene (750 mL) containing
acid methyl 4-(chloroformyl)benzoate (5.2 mmol).
The reaction mixture was heated at 150 °C for 30 min.
Pyridine (15 mmol) was added to neutralize the reaction
mixture. After 5 min nitrogen atmosphere was removed
and the reaction mixture was heated at reflux under open
Copyright © World Scientific Publishing Company J. Porphyrins Phthalocyanines 2021; 25: 1020–1021
2150100.indd 1020
air atmosphere for another 2 h. 1,2-dichlorobenzene
was removed under reduced pressure. The product was
refluxed in THF:MeOH for 12 h to perform the ligand
exchange. The work up and purification were carried out
as per the above mentioned procedure.
4: Yield: 84 mg (9 %) 1H NMR (500 MHz, CDCl3)
δ (ppm) 8.30 (d, J = 8.0 Hz, 2H, b-CH), 7.9 (m, 4H,
o-m Ph), 7.70 (d, J = 4.5 Hz, 2H, b-CH), 4.56 (q, J =
7.0 Hz, 4H, CH3CH2-), 4.45 (dd, J = 15.0 Hz and 19.5
Hz, 1H, methylene), 4.25 (dd, J = 15.0 Hz and 19.5 Hz,
1H, methylene), 4.03 (dd, J = 15.0 Hz and 20.5 Hz, 1H,
methylene), 4.02 (m, 5H, OCH3), 4.00 (dd, J = 15.0
Hz and 20.5 Hz, 1H, methylene), 1.56 (t, J = 7.06, 6H,
CH3CH2-), 1.25 (s, 3H, axial OCH3). 11B NMR (192
MHz, CDCl3) (BF3.OEt2 as internal standard) δ (ppm)
-12.50 . 13C NMR (125 MHz, CDCl3) δ (ppm) 166.83,
159.25, 144.52, 140.52, 134.18, 131.88, 129.80, 123.77,
118.25, 102.58, 61.00. 52.46, 47.95, 33.60, 14.68. HRMS
(ESI-MS) m/z: [M ]+ Calcd for C29H25BN3O4 522.1836;
Found 522.1715. UV-vis (in toluene) l [nm] (e [M-1cm-1])
322 (24925), 356 (26355), 432 (5131), 412 (7337), 538
(10275). Emission (in toluene) l [nm] (ff) 571 (0.12).
5: Yield: 14 mg (1.5 %), 1H NMR (500 MHz, CDCl3)
d (ppm) 8.60 (s, 2H, b-CH), 8.65 (d, J = 4.5, 2H, β-CH ),
8.31 (d, J = 8.0, 2H, b-CH), 8. 01 (m, 4H, o-m Ph), 4.71
(q, J = 7.0, 2H, CH3CH2- ), 3.98 (s, 3H, OCH3), 1.64 (t,
J = 7.0, 6H, CH3CH2-), 0.70 (s, 3H, axail OCH3). HRMS
(ESI-MS) m/z: (M-OMe)+; Calcd for C29H25BN3O6:
520.1679; found: 520.1645. UV-vis (in toluene) l [nm]
(e [M-1cm-1]) 380 (58277), 478 (5551), 508 (5047).
Emission (in toluene) l [nm] 521, 555.
CONCLUSIONS
In conclusion, we have synthesized a new A2B-type
B(III)subchlorin endowed with two different types of
ester moieties at its periphery first serendipitously and
through a rational and efficient approach. In addition,
its photophysical and electrochemical properties have
also been evaluated along with its structure to enrich the
burgeoning chemistry of subchlorins. The introduction of
phenyl ester group into the meso-position of 2 resulted
not only a slightly red shifted absorption spectral pattern
but also broadened Q-bands. The compound is found to
be emissive in the red region and showed a Stoke shift of
1074 cm-1. The subchlorin 4 showed very good singlet
oxygen producing efficiency in toluene and is expected
to show better theranostic ability.
Acknowledgments
This work was supported by DAE-BRNS, India (Pro­
ject No. 37(2)/14/06/2017-BRNS/37204). I.A.B. thanks
UGC, and SERB, India; R.S. thanks UGC-­DSKPDF (CH/
17-18/0252) and SERB-NPDF (PDF/2016/000685),
India; B.C. thank DST, India; S.S. thank DST-INSPIRE;
T.V. thank DRDO, India for the financial support.
11-05-21 13:50:19
 10,15-BIS(ETHOXYCARBONYL)-5-(4-METHOXYCARBONYLPHENYL)
Authors thank CMSD, University of Hyderabad for the
computational facility. The authors also thank Dr. Saddam
Hussain and Mr. Sumanta Paul (School of Chemistry,
University of Hyderabad) for their help in fluorescence
lifetime and singlet oxygen generation measurements.
Supporting information
Additional information (Figs S1–S11 and Tables S1–
S3) are given in the supplementary material. This
material is available free of charge via the Internet at
https://www.worldscientific.com/doi/suppl/10.1142/
S1088424621501005.
Crystallographic data (including the structure factor)
for compound 4 in this paper has been deposited
in the Cambridge Crystallographic Data Centre as
supplementary publication number CCDC 2061874.
Copies can be obtained on request, free of charge, via
https://www.ccdc.cam.ac.uk/structures/ or from the
Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44 1223-336-033
or email: deposit@ccdc.cam.ac.uk).
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