Highly regioselective α-formylation and α-acylation of BODIPY dyes via tandem cross-dehydrogenative coupling with in situ deprotection

Article abstract of DOI:10.1039/c9ob00927b

A metal-free C-H formylation and acylation of BODIPY dyes using a variety of dioxolane derivatives as aldehyde equivalents is reported, providing a postfunctionalization method for controllable synthesis of BODIPYs with carbonyl groups at 3,5-positions vi

Full text of DOI:10.1039/c9ob00927b

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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DOI: 10.1039/C9OB00927B
ARTICLE
Highly Regioselective -Formylation and -Acylation of BODIPY
Dyes via Tandem Cross-Dehydrogenative Coupling with in situ
Deprotection
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
b
a
DOI: 10.1039/x0xx00000x
Fan Lv, Yang Yu, Erhong Hao, * Changjiang Yu, Hua Wang, Noёl Boens * and Lijuan Jiao *
A metal-free C-H formylation and acylation of BODIPY dyes using a variety of dioxolane derivatives as aldehyde equivalent
is reported, providing a postfunctionalization method for controllable synthesis of BODIPYs with carbonyl groups at 3,5-
positions via a radical process. The photophysical properties of resultant dyes from this efficient one-pot, chemo- and site-
selective transformation have been studied.
during the direct acylation of dipyrromethane using acyl
1
0b
chloride. In addition, limited stability of dipyrromethanes
and their acylated derivatives further complicated the
synthesis. Formylation of dipyrromethanes which is highly -
regioselective, followed by standard oxidation, base-promoted
Introduction
Small-molecule fluorophores are critically important tools to
investigate biological processes and are prevalent in many
modern applications, including bioimaging, sensing and
therapy.1 Recently, boron dipyrromethene (BODIPY) dyes
have been widely used in highly diverse research fields, due
to their excellent spectroscopic and photophysical properties.
Rapid and reliable access to functionalized BODIPY
chromophores,7
applications in chemical biology and materials chemistry. To
this end, aldehydes and ketones are versatile and high-value
functional handles that can be rapidly elaborated or tethered
3 2
deprotonation and complexation with BF .OEt yielded 3(,5)-
di)formylated BODIPYs.
formyl group at the 3-position was created by 2,3-dichloro-5,6-
dicyano-1,4-benzoquinone
2
9d,e
(
A fully alkylated BODIPY having a
3
-6
(DDQ)
9g
oxidation
of
the
corresponding 3-methyl group.
,8
therefore, greatly expedites their
Ar
B
O

(a)
O
Cl
R
E+

N
N
BF3.OEt2
R = alkyl or aryl
O
N
N
N
N
B
R
B

F
F
F
F
-
F F
Nu , R BODIPY
9
(b)
Ar
Ar
to compounds of biological interest. The synthesis of -
Ar
acylated BODIPYs from ready-made BODIPY frameworks has
not yet been described. However, acylation with acid chloride
Cl
R
NH HN
dipyrromethane
NH
N
N
N
B
X
O
F F
X
E+
O
R
R
through traditional Friedel-Crafts electrophilic aromatic
mixture of

and acylation isomers
X = H or COR
Ar


.
substitution using BF
3
OEt
2
as Lewis acid catalyst gave
(c)
Ar
B
Ar
O
regioselectively 2-acylated BODIPYs due to the least positive
charge on the 2(,6)-position(s) of the BODIPy core (Scheme
deprotection
R
N
N
O
N
N
N
N
B
B
O
R
F
F
F
F
O
F F
HAT
R = H, alkyl or aryl
R
1
0a
O
1
a). A potential, as yet not reported, de novo synthesis route
O
O
O
H
one-pot -regioselective reaction
protection
this work
toward -acylated BODIPYs might comprise direct (di)acylation
H
R
R
radical C-H activation
of dipyrromethane, followed by classic oxidation, base-
promoted deprotonation and complexation with BF .OEt
3 2
Scheme 1. Reported acylation of BODIPY (a), potential -acylated BODIPYs
through de novo synthesis (b) and our tandem cross-dehydrogenative coupling
between BODIPY and 1,3-dioxolane derivative with in situ deprotection (c). HAT:
(Scheme 1b). However, mixtures of products were formed hydrogen atom transfer.
Due to the most positive charge of -position of BODIPY
core, various -regioselective postfunctionalizations, such as
a. The Key Laboratory of Functional Molecular Solids, Ministry of Education; School
of Chemistry and Materials Science, Anhui Normal University, Wuhu, China
1
1
12
SNAr reaction and radical reaction, have been developed.
Particularly, radical reactions on BODIPYs have received
increasing interest due to their advantages of high reactivity,
high regioselectivity and atom-economy. The highly
regioselective cross-dehydrogenative coupling (CDC) has
2
41000.
b.
Department of Chemistry, KU Leuven (Katholieke Universiteit Leuven),
Celestijnenlaan 200f, 3001 Leuven, Belgium
Email: haoehong@ahnu.edu.cn; jiao421@ahnu.edu.cn; noel.boens@kuleuven.be
Electronic Supplementary Information (ESI) available: Experimental details,
spectroscopic/photophysical properties of selected BODIPYs, NMR and HRMS
1
2a-e
spectra for all new compounds. CCDC 1811936-1811938 and 1815587. For ESI and played a vital role in the construction of C–C
and C–X (N,
crystallographic data in CIF or other electronic format, see DOI:
1
2f-h
S)
bonds on BODIPY core. Acetals and hemiacetals are very
1
0.1039/x0xx00000x
common protective groups of carbonyls. The weak C−H bonds
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ARTICLE
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α to both O atoms in acetals and hemiacetals can undergo showed inferior results (entries 9-11).
activation through hydrogen atom transfer in the presence of
reactive radical species. We envisioned a complementary found the optimal ratio of TBHP was 4 equiv. After a brief
View Article Online
DOI: 10.1039/C9OB00927B
We further optimized the ratio of TBHP (entries 12-13) and
1
3
approach that harnesses the direct activation of weak C−H survey of reaction temperature, we found that the optimal
o
bonds in 1,3-dioxolane derivatives and couples these reaction temperature was 90 C (entries 14-15). Finally, we
intermediates with a CDC mechanism to achieve -formylation obtained the optimized reaction conditions to be 0.2 equiv of
o
and -acylation of BODIPYs after in situ deprotection (Scheme Bu
c).
4
NI, 4 equiv of TBHP, at 90 C in 8 h.
1
1) Bu4NI (0.2 equiv)
TBHP (5 equiv)
90 oC, 8 h
TFA, rt
CH Cl
O
O
Results and discussion
N
N
N
N
2) TFA, CH Cl , rt
N
N
B
2
2
B
2
2
B
48%
2
a
F
F
O
90%
F
F
F F
O
3a
O
4a
H
1a
We explored the viability of the above process with meso-
mesityl BODIPY 2a and 1,3-dioxolane as substrates in the
presence of a radical initiator. To our delight, when the
reaction was conducted using Bu
tert-butyl hydroperoxide (TBHP, 4 equiv) as oxidant at 90 C
for 8 h, the major product 3a was isolated in 56% yield (Table
Scheme 2. Synthesis of -formylBODIPY 4a.
Ar
4
NI (20 mol%) as catalyst and
(a)
Ar
R
1) Bu NI (0.2 equiv)
4
o
O
TBHP (5 equiv)
O
90 oC, 8 h
N
N
N
N
B
B
F
4
2) TFA, CH2Cl2, rt
F
F
F
2
R
1
O
1
4 2
, entry 1). Other catalysts, including Bu NBr, KI, Pd(OAc) and
Cu(OAc) , gave lower yields (entries 2-5). In the absence of
2
Cl
Cl
catalyst, the yield of corresponding product 3a was drastically
decreased to 15% yield (entry 6). Reducing the amount of
catalyst to 10 mol% also decreased the yield and, conversely,
no significant improvement in product yield was observed with
N
N
N
N
N
N
N
N
B
B
B
B
F
F
F
F
F
F
F
4e
48%
F
4 9
C H
O
O
4b
H
4c
H
4d
40%
O
O
43%
38%
3
0 mol% of the catalyst (entries 7-8). These results
demonstrate that catalysts play an important role in this
transformation. Subsequently, other oxidants were studied
N
N
N
N
N
N
including DDQ, K
S O
2 2 8
and even its analogue di-tert-butyl
B
B
B
F
F
F
F
4g
55%
F F
4h
47%
peroxide (DTBP) either failed in promoting this reaction or
4f
5
O
O
OCH3
O
Cl
0%
Table 1. Optimization of the reaction conditions a
(b)
1) Bu4NI (0.2 equiv)
TBHP (5 equiv)
90 oC, 8 h
O
N
N
O
N
N
B
B
F
F
2) TFA, CH2Cl2, rt
F F
O
1d
2a
4i
4%
H
3
O
catalyst
O
Scheme 3. One-pot synthesis of BODIPYs 4 from BODIPY 1 and 1,3-dioxolane 2a
and its derivatives 2b-f.
oxidant
temp.
N
N
N
N
2a
B
B
F
F
O
F
F
O
1a
3a
Ar
Ar
R
1) Bu4NI (0.2 equiv)
TBHP (5 equiv)
90 oC, 16 h
o
yield [%)]b
O
entry
catalysts
Bu NI
Bu NBr
oxidants
temp. ( C)
O
N
N
N
N
B
B
2) TFA, CH2Cl2, rt
F
F
R
F
F
2
R
1
2
3
4
4
TBHP
TBHP
TBHP
TBHP
90
90
90
90
56
36
< 5
25
1
O
5
O
Ar = mesityl
Ar
Ar
Ar
Ar
4
KI
N
N
N
N
N
N
N
N
B
B
B
B
Pd(OAc)
2
F
F
F F
O
O
O
O
F
F
F F
O
O
MeO
H
H
Ph
Ph
O
O
5a
5b
23%
5c
5d
45%
OMe
5
Cu(OAc)
------
2
TBHP
90
32
25%
41%
Scheme 4. One-pot synthesis of BODIPYs 5 from BODIPY 1a and 1,3-dioxolane 2a
and its derivatives 2b, 2d and 2e.
6
7
8
9
TBHP
TBHP
TBHP
90
90
90
90
90
90
90
90
80
100
15
33c
53d
NR
NR
18
33e
52f
45
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Bu
4
NI
4
NI
4
NI
4
NI
4
NI
4
NI
4
NI
4
NI
4
NI
Next, we evaluated a number of Lewis acids for hydrolysis of
the dioxolane functional group on BODIPY 3a. Trifluoroacetic
acid (TFA) was found to be able to convert 3a to -
formylBODIPY 4a in 90% yield at room temperature (Scheme
2 2 8
K S O
1
1
1
1
1
1
0
1
2
3
4
5
DDQ
DTBP
TBHP
TBHP
TBHP
TBHP
2
3 2
). Other reagents including HCl aqueous solution and BF .Et O
were also effective in this deprotection reaction (details in ESI).
A one-pot reaction for synthesis of 4a from BODIPY 1a was
then developed without the isolation of 3a (Scheme 2), from
53
a
Reaction conditions: 1a (0.1 mmol), 3 mL of solvent (1,3-dioxolane serves both which 4a was obtained with 6 equiv of TFA in 48% yield. The
b
as reagent and solvent), catalyst (0.02 mmol), oxidant (4 equiv), 8 h. Isolated
regiochemistry of 4a was confirmed by XRD structure
c
d
e
f
yield. 10 mol% catalyst. 30 mol% catalyst. 3 equiv TBHP. 5 equiv TBHP. TBHP
tert-butyl hydroperoxide (70% in aqueous solution), DTBP = di-tert-butyl
peroxide. NR = no reaction.
determination (Fig. 1).
=
2
| J. Name., 2012, 00, 1-3
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ARTICLE
o
To test the versatility of this one-pot reaction, meso- rings in the crystal structure of 4b is only 2.7 , indicating an
View Article Online
DOI: 10.1039/C9OB00927B
phenylBODIPY 1b and meso-2,6-dichlorophenylBODIPY 1c almost planar BODIPY core. Slight distortions were found in 4a
reacted with 1,3-dioxolane 2a, which, after in situ and 5c with those dihedral angles of 9.8o and 19.3 ,
deprotection, provided the -formylated products 4b and 4c in respectively. The dihedral angles between the meso-aryl group
o
o
o
o
o
4
3 and 38% yields, respectively (Scheme 3a). Next, 2- and the BODIPY core are around 76 , 55 , 80 and 83 for 4a,
substitued 1,3-dioxolane derivatives 2b-f (Fig. S1, ESI) were 4b, 5c and 7, respectively. The dihedral angle of the two
o
applied to obtain acylated BODIPYs, which showed higher BODIPY core planes in dimer 7 is 61.9 , whereas each BODIPY
yields than that of 1,3-dioxolane 2a: BODIPYs 4d-h with alkyl- core also has an almost planar plane with the dihedral angle of
o
o
or aryl-substituted carbonyl groups at the -position were the two pyrrole rings of 6.1 and 12.1 , respectively.
obtained in 40-55% yields (Scheme 3a). Unsymmetric BODIPY Fundamental spectroscopic properties of these newly
d was also suitable for this reaction, giving 4i in 34% yield synthesized BODIPYs were investigated in dichloromethane
1
using 1,3-dioxolane 2a (Scheme 3b). By simply extending the and are summarized in Table 2. In comparison with BODIPYs 1,
max
reaction time to 16
h
followed by hydrolysis in BODIPYs 4 generally led to red shifts of the absorption (abs
)
max
dichloromethane in the presence of TFA, the corresponding and fluorescence emission (em ) maxima of approximately
3
,5-diacylation products were major products and 5a-d were 15-20 nm, wheras disubstituted BODIPYs 5 provided additional
regioselectively produced from 1a in 23-45% yields, red shifts of about 10-30 nm. Most BODIPYs 4 and 5 showed
respectively (Scheme 4). intense fluorescence emission. However, electron-rich 4-
Finally, using 4a as an example, further transformation of methoxybenzoyl substituted BODIPYs 4g and 5d were weakly
the resultant dyes was demonstrated (Scheme 5). BODIPY 4a fluorescent. Diethylamine substituted BODIPY 6 displayed
smoothly reacted with diethylamine in DMF at room broad absorption bands with absmax around 470 nm (Fig. S2,
max
temperature for 2 h to give BODIPY 6 in 64% yield through ESI), which is about 50 nm blue-shifted compared with abs
oxidative nucleophilic hydrogen substitution at the 5-position of starting BODIPY 4a. With the increase of the polarity of the
1
2b
max
of the BODIPY core (Scheme 5a). A novel -meso directedly solvent from cyclohexane to methanol, the em values of 6
linked BODIPY dimer 7 was also synthesized in 78% overall were significantly blue-shifted from 560 nm (in cyclohexane) to
yield from the acid-catalyzed condensation of BODIPY 4a with 519 nm (in methanol) and the fluorescence quantum yields
1
5
pyrrole (to give intermediate 8), followed by DDQ oxidation were reduced from 0.18 (in cyclohexane) to 0.002 (in
and subsequent difluoroboration (Scheme 5b, Fig. 1d).
methanol) (Table S2, ESI). The spectroscopic features of 6 are
Ar
similar to our previously reported 3-aminoBODIPY
derivatives.
(
a)
Ar
1
6
DMF, rt
N
H
N
N
N
N
B
Ar = mesityl
Ar
B
2 h
2
.1 equiv
N
F
F
O
Table 2. Photophysical properties of BODIPYs in CH Cl at room
F
F
a
O
64%
2
2
H
4
H
6
a
temperature
(b)
Ar
H
N
Ar
max
max
em
max
b
c
dyes
λ
abs
λ

abs
1
Stokes shift
[cm ]
DDQ
Et3N
N
N
N
N
B
[M– cm ]
–1
a
–1
N
N
B
[nm]
500
505
519
518
[nm]
522
522
536
538
B
TFA
F F
F
F
F
F
O
CH2Cl2
BF3.OEt2
N
F
HN
N
1a
3a
4a
54100
0.74
0.81
0.68
0.25
840
610
610
820
H
B
4a
8
NH
7
7
8% overall yield
F
68700
52700
Scheme 5. Synthesis of BODIPYs 6 and 7.
4
b
51700
4
c
530
514
514
515
514
514
501
548
537
526
525
470
514
551
533
532
534
535
532
549
563
555
559
554
535
606
58500
49600
56500
49600
49200
50500
39000
77800
47700
42200
50300
42100
75400
0.44
0.48
0.36
0.51
0.03
0.45
0.09
0.40
0.37
0.14
0.02
0.004
0.005
720
650
660
690
960
690
1750
490
4
4
d
e
4
f
4
g
4
h
4
i
5
5
a
b
600
5
c
1120
1000
2580
2950
5
d
6
7
Figure 1. Top and front views of XRD structures of BODIPY 4a (a), 4b (b), 5c (c)
and 7 (d). C, light gray; N, blue; B, dark yellow; F, bright green, O, red. Hydrogen
atoms have been removed for clarity.
a
Molar absorption coefficient values rounded to the nearest 100 M–1 cm–1. b
Fluorescence quantum yields determined using fluorescein ( = 0.90 in 0.1 N
Crystals of 3-formylBODIPYs 4a and 4b, 3,5-diacylated
NaOH aqueous solution) as reference, excited at 480 nm. Standard errors are less
BODIPY 5c and BODIPY dimer 7 (Figure 1) suitable for XRD than 10%.
Stokes shift values rounded to nearest 10 cm–1
.
c
analysis were obtained. As usual, B atoms all have slightly
distorted tetrahedron geometry with the B−N distances within
Orthogonal BODIPY dimers have been demonstrated to be
1
.53−1.57 Å (Table S1, ESI). The dihedral angle of two pyrrole good photosensitizers because of their intrinsic intramolecular
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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charge transfer character through the spin-orbit charge- spectrum of the test sample in various solvents with
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1
7,17-19
DOI: 10.1039/C9OB00927B
transfer intersystem crossing (SOCT-ISC) mechanism.
fluorescein (Φr = 0.90 in 0.1 N NaOH aqueous solution) as
1
9
With dimer 7 in hand, we first measured its photophysical reference. Non-degassed, spectroscopic grade solvents and
max
properties. Dimer 7 has a typical abs
at 514 nm, and a 10 mm optical path length quartz cuvettes were used. Dilute
max
dramatically red-shifted, but very weak emission with em at solutions (0.01 < A(ex) < 0.05) were used to minimize the
6
06 nm (Fig. S18, ESI). The extremely low fluorescent quantum inner-filter effects. Quantum yields x were determined
2
0
yield of 0.005 in dichloromethane inspired us to further study according to equation (1):
its singlet oxygen generation properties. As shown in Fig. 2, the


A (
)
)
2
r
ex
ex
photooxidation of 1,3-diphenylisobenzofuran (DPBF, a singlet
oxygen trap molecule) was monitored at 60 s intervals in the
presence of dimer 7. The calculated singlet oxygen quantum
yield for dimer 7 in toluene is 0.15 using Rose Bengal as
reference.
Fx 110
nx
x   


r
A (
2
x
Fr
nr
110
(1)
where the subscripts x and r refer respectively to the BODIPY
sample x and reference (standard) fluorophore r with known
quantum yield r in a specific solvent; F stands for the
spectrally corrected, integrated fluorescence spectra; A(ex)
denotes the absorbance at the used excitation wavelength ex
and n represents the refractive index of the solvent (in
principle at the average emission wavelength).
1
1
0
0
0
.6
.2
.8
.4
.0
0.5
(
b)
time (s)
0
(a)
60
0
0
0
0
0
.4
.3
.2
.1
.0
120
180
240
360
420
Crystallography
Crystals of BODIPYs 4a, 4b, 5c and 7 suitable for X-ray analysis
3
00
400
500
600
0
60
120 180 240 300 360
Time (s)
wavelength (nm)
were obtained via the slow diffusion of petroleum ether into
irradiation in the presence of BODIPY dimer 7 (1 × 10 M) in toluene (recorded at their dichloromethane solutions. The vial containing this
-
5
Figure 2. (a) Changes in the absorption spectrum of DPBF (5 × 10 M) upon
-5
6
0 s intervals). (b) Plot of change in absorbance of DPBF at 416 nm vs irradiation
time (irr = 532 nm) in the presence of BODIPY dimer 7 in toluene.
solution was placed, loosely capped, to promote the
crystallization. A suitable crystal was chosen and mounted on a
glass fiber using grease. Data were collected using a
diffractometer
equipped
with
a
graphite
crystal
Conclusions
monochromator situated in the incident beam for data
In conclusion, we have developed an efficient protocol for the collection at room temperature. Cell parameters were
C−H formylation and acylation of BODIPY dyes using dioxolane retrieved using SMART21 software and refined using SAINT on
derivatives as aldehyde equivalent. Importantly, this reaction all observed reflections. The determination of unit cell
is devoid of precious metals and regioselectively occurs at the parameters and data collections were performed with Mo Kα

-positions of the BODIPY core via a radical pathway.
radiation (λ) at 0.71073 Å. Data reduction was performed
2
2
using the SAINT software, which corrects for Lp and decay.
The structure was solved by the direct method using the
SHELXS-974 program and refined by least squares method on
Experimental
2
23
24
F , SHELXL-97, incorporated in SHELXTL V5.10. CCDC-
811936 (4a), CCDC-1811937 (4b), CCDC-1811938 (5c) and
General experimental method
1
Reagents and solvents were used as received from Energy
Chemicals (Shanghai, China). All reactions were performed in
oven-dried or flame-dried glassware and were monitored by
TLC using 0.25 mm silica gel plates with UV indicator (60F-254).
CCDC-1815587 (7) 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.
1
13
H and C NMR spectra were recorded on a 300, 400 or 500
Synthesis and Characterization
MHz NMR spectrometer at room temperature. Chemical shifts
BODIPYs 1a-d were synthesized according to literature
1
(δ) are given in ppm relative to CDCl
3
(7.26 ppm for H and 77
9
d,11d
procedures.
Compounds 2-f were prepared from the aldol
1
3
1
ppm for C) or d6-DMSO (2.54 ppm for H and 39.9 ppm for
condensation reaction of aldehyde and ethylene glycol by
1
3
C) or to internal TMS (δ = 0 ppm) as internal standard. Data
2
5
following literature procedures.
Synthesis of 3a. BODIPY 1a (78 mg, 0.25 mmol), Bu
mg, 0.05 mmol) and the oxidant tert-butyl hydroperoxide
TBHP, 0.12 mL, 1.25 mmol) were dissolved in 2 mL 1,3-
are reported as follows: chemical shift, multiplicity, coupling
constants and integration. High-resolution mass spectra
4
NI (18
(HRMS) were obtained using APCI-TOF in positive mode.
(
Photophysical Measurements
UV-visible absorption and fluorescence emission spectra were
recorded on commercial spectrophotometers (Shimadzu UV-
dioxolane 2a, which serves both as reagent and solvent. The
o
reaction mixture was stirred at 90 C for 8 h. Upon completion,
the reaction mixture was cooled to room temperature and was
poured into dichloromethane (100 mL), washed three times
with water (100 mL), dried over Na SO , filtered, and
2 4
2
450 and Edinburgh FS5 spectrometers). All measurements
were made at 25 oC, using 5  10 mm cuvettes. Relative
fluorescence quantum efficiencies of BODIPY derivatives were
obtained by comparing the areas under the corrected emission
evaporated to dryness. The crude product was purified by
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 5 of 7
Organic & Biomolecular Chemistry
Journal Name
column chromatographically (silica; petroleum ether/ethyl MHz, CDCl
ARTICLE
3
) δ 10.36 (s, 1H), 8.27 (s, 1H), 7.53-7.45 (m, 3H),
View Article Online
DOI: 10.1039/C9OB00927B
acetate; 10:1-5:1, v/v) to provide 3a in 55% yield (52 mg). mp 7.06 (d, J = 4.3 Hz, 1H), 6.94 (d, J = 4.2 Hz, 1H), 6.73 (d, J = 4.1
o
1
13
6
3 3
8.1-70.5 C. H NMR (300 MHz, CDCl )  7.92 (s, 1H), 6.94 (s, Hz, 1H), 6.60 (d, J = 4.2 Hz, 1H); C NMR (126 MHz, CDCl ) δ
2
H), 6.67 (s, 1H), 6.63 (d, J = 3.5 Hz, 1H), 6.57 (d, J = 3.6 Hz, 1H), 183.85, 151.87, 148.35, 142.42, 140.72, 137.52, 134.94, 133.56,
6
2
1
1
.48 (s, 1H), 6.38 (s, 1H), 4.20 – 4.07 (m, 4H), 2.35 (s, 3H), 131.73, 130.54, 128.37, 126.97, 122.59, 118.63. HRMS calcd.
.09 (s, 6H); 13C NMR (126 MHz, d
-DMSO)  157.02, 147.89, for C16
46.81, 139.44, 136.35, 135.54, 135.37, 131.38, 130.81, 129.94,
29.07, 120.93, 118.13, 97.11, 66.08, 21.58, 20.33. HRMS calcd. from 1a and 2b. mp 91.6-93.4 C. H NMR (300 MHz, CDCl
H
10BCl
F
N
O [M+H] : 365.0226, found 365.0229.
+
6
2
2
2
4d (R = Me, Ar = mesityl) was prepared in 40% yield (35 mg)
) δ
8.16 (s, 1H), 6.97 (s, 2H), 6.92 (s, 1H), 6.85 (s, 1H), 6.63 (s, 1H),
o
1
3
+
+
2 2 2
for C21H21BF N O Na [M+Na] 405.1556, found 405.1557.
1
3
Synthesis of 4a from 3a. To a solution of 3a (38 mg, 0.1 6.55 (s, 1H), 2.70 (s, 3H), 2.37 (s, 3H), 2.09 (s, 6H); C NMR
mmol) in dichloromethane (3 mL) was added trifluoroacetic (126 MHz, CDCl ) δ 190.78, 150.17, 149.58, 149.23, 149.13,
acid (TFA, 68 mg, 0.6 mmol). The reaction mixture was stirred 139.26, 137.15, 136.18, 132.75, 129.38, 128.28, 127.26, 121.84,
3
at room temperature for 1 h. Upon completion, the reaction 121.31, 28.94, 21.07, 19.95. HRMS calcd. for C20
mixture was poured into dichloromethane (30 mL), washed [M+H] : 353.1631, found 353.1635.
2 2
H20BF N O
+
three times with water (50 mL), dried over Na
and evaporated to dryness. The crude product was purified by from 1a and 2c. mp 148.4-150.2 C. H NMR (300 MHz, CDCl
2
SO
4
, filtered,
4e (R = Bu, Ar = mesityl) was prepared in 48% yield (47 mg)
o
1
3
)
column chromatographically (silica; petroleum ether/ethyl δ 8.15 (s, 1H), 6.97 (s, 2H), 6.88 (d, J = 4.1 Hz, 1H), 6.82 (d, J =
acetate; 15:1-9:1 v/v) to provide 4a in 90% yield (30 mg). mp 4.3 Hz, 1H), 6.61 (d, J = 3.6 Hz, 1H), 6.55 (d, J = 4.1 Hz, 1H), 3.00
o
1
1
(
65.7-167.6 C. H NMR (500 MHz, CDCl
3
) δ 10.37 (s, 1H), 8.21 (t, J = 7.3 Hz, 2H), 2.37 (s, 3H), 2.09 (s, 6H), 1.78-1.73 (m, 2H),
1
3
s, 1H), 7.02 (d, J = 4.2 Hz, 1H), 6.98 (s, 2H), 6.92 (d, J = 4.4 Hz, 1.44-1.39 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H); C NMR (126 MHz,
1
2
1
1
C
H), 6.67 (d, J = 4.4 Hz, 1H), 6.57 (d, J = 4.2 Hz, 1H), 2.37 (s, 3H), CDCl
3
) δ 193.76, 150.56, 149.84, 149.63, 139.65, 137.73,
.10 (s, 6H); 13C NMR (126 MHz, CDCl
3
) δ 184.55, 150.86, 137.44, 136.65, 133.08, 129.88, 128.71, 127.81, 122.22, 121.04,
50.29, 148.26, 139.94, 138.20, 137.42, 136.57, 134.19, 129.43, 41.12, 26.57, 22.75, 21.55, 20.44, 14.37. HRMS calcd. for
+
28.84, 127.65, 122.38, 118.76, 21.54, 20.46. HRMS calcd. for
C
23
H
26BF
2 2
N
O [M+H] : 395.2101, found 395.2107.
+
19 2 2
H18BF N O [M+H] : 339.1475, found 339.1477.
4f (R = Ph, Ar = mesityl) was prepared in 50% yield (53 mg)
o
1
3
General Procedure for the One-pot Synthesis of 4a-h. We from 1a and 2d. mp 154.8-156.5 C. H NMR (400 MHz, CDCl )
are using 4a (R = H, Ar = mesityl) as an example to show the δ 8.14 (s, 1H), 7.95–7.93 (m, 2H), 7.62–7.58 (m, 1H), 7.50–7.46
general procedure for the preparation of 3-formylBODIPYs 4a- (m, 2H), 6.99 (s, 2H), 6.85 (d, J = 4.3 Hz, 1H), 6.64 (d, J = 4.2 Hz,
1
3
c and 3-acylBODIPYs 4d-h: BODIPY 1a (78 mg, 0.25 mmol), 1H), 6.62–6.59 (m, 2H), 2.38 (s, 3H), 2.14 (s, 6H); C NMR (126
Bu NI (18 mg, 0.05 mmol) and the oxidant TBHP (0.12 mL, 1.25 MHz, CDCl ) δ 187.45, 171.30, 149.91, 139.21, 137.78, 136.24,
4
3
mmol) were dissolved in 2a (2 mL). The reaction mixture was 133.69, 132.979, 132.76, 130.13, 129.92, 129.22, 128.43,
o
stirred at 90 C for 8 h and then was cooled to room 128.27, 128.22, 126.97, 121.94, 121.53, 21.08, 20.03. HRMS
+
temperature. After addition of 6 equiv of TFA, the reaction calcd. for C25
mixture was stirred at room temperature for 1 h. Upon
completion, the reaction mixture was poured into yield (54 mg) from 1a and 2e. mp 143.2-145.8 C. H NMR (400
dichloromethane (100 mL), washed three times with water MHz, CDCl ) δ 8.07 (s, 1H), 7.96 (d, J = 8.9 Hz, 2H), 6.98 (s, 2H),
100 mL), dried over Na SO , filtered, and evaporated to 6.96 (d, J = 9.0 Hz, 2H), 6.82 (d, J = 4.3 Hz, 1H), 6.63–6.60 (m,
dryness. The crude product was purified by column 2H), 6.57 (d, J = 4.1 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.14 (s,
H21BFN
2
O [M-F] : 395.1729, found 395.1725.
4g (R = 4-methoxyphenyl, Ar = mesityl) was prepared in 55%
o
1
3
(
2
4
1
3
chromatographically (silica; petroleum ether/ethyl acetate; 6H); C NMR (126 MHz, CDCl
3
) δ 187.03, 164.24, 149.23,
1
1
7
6
2
1
1
C
5:1-9:1 v/v) to provide 4a in 48% yield (40 mg). mp 165.7- 139.58, 137.41, 136.72, 132.88, 132.71, 130.81, 129.93, 128.70,
o
1
67.6 C. H NMR (500 MHz, CDCl
3
)  10.37 (s, 1H), 8.21 (s, 1H), 127.97, 121.32, 114.15, 114.01, 55.92, 21.54, 20.49. HRMS
+
.02 (d, J = 4.2 Hz, 1H), 6.98 (s, 2H), 6.92 (d, J = 4.4 Hz, 1H), calcd. for C26
.67 (d, J = 4.4 Hz, 1H), 6.57 (d, J = 4.2 Hz, 1H), 2.37 (s, 3H),
.10 (s, 6H); 13C NMR (126 MHz, CDCl
)  184.55, 150.86, yield (52 mg) from 1a and 2f. mp 163.1-165.4 C. H NMR (300
50.29, 148.26, 139.94, 138.20, 137.42, 136.57, 134.19, 129.43, MHz, CDCl ) δ 8.15 (s, 1H), 7.88 (d, J = 8.4 Hz, 2H), 7.46 (d, J =
28.84, 127.65, 122.38, 118.76, 21.54, 20.46. HRMS calcd. for 8.3 Hz, 2H), 6.99 (s, 2H), 6.87 (s, 1H), 6.63-6.60 (m, 3H), 2.38 (s,
H24BF N O
2 2 2
[M+H] : 445.1893, found 445.1896.
4h (R = 4-chlorophenyl, Ar = mesityl) was prepared in 47%
o
1
3
3
+
13
19 2 2
H18BF N O [M+H] : 339.1475, found 339.1477.
3
3H), 2.13 (s, 6H); C NMR (126 MHz, CDCl ) δ 186.66, 150.73,
4
b (R = H, Ar = Ph) was prepared in 43% yield (31 mg) from 149.65, 148.59, 139.90, 139.75, 138.09, 137.37, 136.67, 136.62,
o
1
1
1
b and 2a. mp 153.4-155.2 C. H NMR (300 MHz, CDCl3)  133.47, 131.71, 129.75, 129.25, 129.04, 128.76, 127.29, 122.24,
0.39 (s, 1H), 8.23 (s, 1H), 7.67–7.57 (m, 5H), 7.16 (d, J = 4.3 21.53, 20.47. HRMS calcd. for C25
+
H21BClF N
2 2
O [M+H] :
Hz, 1H), 7.10 (d, J = 4.2 Hz, 1H), 6.86 (d, J = 4.1 Hz, 1H), 6.75 (d, 449.1398, found 449.1397.
J = 4.2 Hz, 1H); 13C NMR (126 MHz, CDCl
)  184.29, 150.03, Synthesis of 4i. BODIPY 1d (62 mg, 0.25 mmol), Bu
49.11, 147.62, 136.97, 136.62, 135.21, 133.12, 131.44, 130.57, mg, 0.05 mmol) and the oxidant TBHP (0.12 mL, 1.25 mmol)
3
4
NI (18
1
1
28.87, 128.69, 121.82, 118.21. HRMS calcd. for C16
2 2
H12BF N O
were dissolved in 2a (2 mL). The reaction mixture was stirred
at 90 C for 8 h and then was cooled to room temperature.
+
o
[
M+H] : 297.1005, found 297.1008.
4
c (R = H, Ar = 2,6-dichlorophenyl) was prepared in 38% After addition of 6 equiv of TFA, the reaction mixture was
o
1
yield (34 mg) from 1c and 2a. mp 146.7-148.9 C. H NMR (400 stirred at room temperature for 1 h. Upon completion, the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Organic & Biomolecular Chemistry
Page 6 of 7
ARTICLE
Journal Name
reaction mixture was poured into dichloromethane (100 mL),
washed three times with water (100 mL), dried over Na SO
Synthesis of BODIPY 6. To a solution of 3-formylBODIPY 4a
(0.1 mmol, 33 mg) in N,N-dimethylformamide (DMF, 3 mL) was
View Article Online
DOI: 10.1039/C9OB00927B
2
4
,
filtered, and evaporated to dryness. The crude product was added diethylamine (0.21 mmol, 2.1 equiv). The mixture was
purified by column chromatographically (silica; petroleum stirred at room temperature for the 2 h under air. Upon
ether/ethyl acetate; 15:1-9:1 v/v) to provide 4i in 34% yield (25 completion, the reaction mixture was poured into
o
1
mg). mp 163.7-165.6 C. H NMR (300 MHz, CDCl
1
3
)  10.03 (s, dichloromethane (30 mL), washed three times with water (50
SO , filtered, and evaporated to dryness.
product was purified by column
3
126 MHz, CDCl )  187.23, 170.19, 143.97, 140.26, 137.57, chromatographically (silica; petroleum ether/dichloromethane;
H), 7.81 (s, 1H), 7.44 (s, 1H), 6.80 (s, 1H), 2.64 (s, 3H), 2.44 (q, mL), dried over Na
J = 7.6 Hz, 2H), 2.26 (s, 3H), 1.11 (t, J = 7.6 Hz, 3H); C NMR The
2
4
1
3
crude
(
o
1
9
2
33.72, 131.21, 130.96, 122.43, 117.83, 17.34, 13.97, 13.88, 2:1 v/v) to provide 6 in 64% yield (26 mg). mp 212.6-213.4 C.
.72. HRMS calcd. for C14
+
1
H15BFN
2
O [M-F] : 277.1318, found
3
H NMR (500 MHz, CDCl )  10.20 (s, 1H), 7.04 (d, J = 3.8 Hz,
77.1319.
1H), 6.93 (s, 2H), 6.71 (d, J = 5.2 Hz, 1H), 6.36 (d, J = 5.3 Hz, 1H),
General Procedure for the One-pot Synthesis of 5a-d. We 5.98 (d, J = 3.8 Hz, 1H), 3.91 (s, 4H), 2.34 (s, 3H), 2.08 (s, 6H),
1
3
are using 5a (R = H, Ar = mesityl) as an example to show the 1.42 (t, J = 7.1 Hz, 6H). C NMR (126 MHz, CDCl
3
)  183.66,
general procedure for the preparation of 3,5-diformylBODIPY 163.02, 140.51, 138.25, 138.20, 137.40, 136.22, 135.47, 130.20,
5
Bu
a and 3,5-diacylBODIPYs 5b-d: BODIPY 1a (78 mg, 0.25 mmol), 128.19, 127.36, 117.92, 117.41, 115.35, 47.32, 21.12, 20.06,
NI (18 mg, 0.05 mmol) and the oxidant TBHP (0.12 mL, 1.25 13.77. HRMS calcd. for C23H26BFN O [M-F] 390.2147, found
4 3
+
+
mmol) were dissolved in 2a (2 mL). The reaction mixture was 390.2149.
o
stirred at 90 C for 16 h and was cooled to room temperature.
Synthesis of BODIPY 7. To a mixture of 4a (33 mg, 0.1 mmol)
After the addition of 6 equiv of TFA, the reaction mixture was and pyrrole (1 mL, 16 mmol) was added TFA (0.02 mL, 0.2
stirred at room temperature for 1 h. Upon completion, the mmol). The reaction mixture was stirred at room temperature
reaction mixture was then poured into dichloromethane (100 for 5 min and was quenched by adding 30 mL aqueous solution
mL), washed three times with water (100 mL), dried over of NaOH (0.2 M). The reaction mixture was extracted with
Na
product was purified by column chromatographically (silica; (50 mL), dried over anhydrous Na
petroleum ether/ethyl acetate; 10:1-5:1 v/v) to provide 5a in evaporated to dryness. The residue was purified through
2
SO
4
, filtered, and evaporated to dryness. The crude CH
2
Cl
2
(30 mL) and the organic layer was washed with water
2
SO filtered, and
4
,
o
1
2
5% yield (22 mg). mp 158.7-160.9 C. H NMR (300 MHz, column chromatography (silica, CH
CDCl )  10.47 (s, 2H), 7.11 (d, J = 4.2 Hz, 2H), 7.00 (s, 2H), 6.83 dipyrromethane intermediate 8, which was dissolved in 20 mL
d, J = 3.9 Hz, 2H), 2.38 (s, 3H), 2.11 (s, 6H); C NMR (126 MHz, CH
CDCl3)  184.00, 154.60, 151.55, 140.19, 138.56, 136.06, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 40 mg, 0.2
2
Cl
2
)
to afford
3
1
3
(
2 2
Cl and directly used for the subsequent oxidation with
1
C
31.47, 128.78, 128.67, 120.34, 21.17, 120.15. HRMS calcd. for mmol) at room temperature for 1 h. The resultant mixture was
+
+
20 2 2 2
H17BF N O Na [M+Na] 389.1243, found 389.1246.
further treated with triethylamine (1 mL, 7.2 mmol) for 20 min,
5
b (R = Me, Ar = mesityl) was prepared in 23% yield (20 mg) and was complexed with boron trifluoride etherate (3 mL, 23.9
o
1
from 1a and 2b. mp 83.5-85.7 C. H NMR (500 MHz, CDCl
3
)  mmol) for 2 h at room temperature. The solvent was removed
6
2

1
C
.98 (s, 2H), 6.94 (d, J = 4.4 Hz, 2H), 6.72 (d, J = 4.4 Hz, 2H), under vacuum and the residue was purified by column
1
3
3
.82 (s, 6H), 2.37 (s, 3H), 2.09 (s, 6H). C NMR (126 MHz, CDCl ) chromatography on silica gel (ethyl acetate/petroleum ether =
192.53, 154.02, 153.15, 139.68, 138.09, 136.00, 130.54, 1:5, v/v) to give 7 as a red solid in 78% yield (40 mg). mp 233.4-
o
1
29.46, 128.46, 122.85, 29.68, 21.15, 20.06. HRMS calcd. for 235.2 C. H NMR (300 MHz, CDCl
H21BFN O [M-F] 375.1674, found 375.1678.
22 2 2
3
)  7.95 (s, 2H), 7.93 (s, 1H),
7.01 (s, 4H), 6.82 (d, J = 3.8 Hz, 1H), 6.74 (d, J = 3.6 Hz, 1H),
c (R = Ph, Ar = mesityl) was prepared in 41% yield (53 mg) 6.59 (d, J = 3.7 Hz, 1H), 6.52 (d, J = 3.6 Hz, 3H), 2.39 (s, 3H),
+
+
5
o
1
13
from 1a and 2d. mp 149.3-151.8 C. H NMR (300 MHz, CDCl
3
)
3
2.17 (s, 6H); C NMR (126 MHz, CDCl )  148.46, 147.59,

7
2
1
1
7.91 (d, J = 7.1 Hz, 4H), 7.61-7.56 (m, 2H), 7.48-7.43 (m, 4H), 146.66, 145.34, 139.33, 136.54, 136.41, 136.29, 136.21, 135.15,
.02 (s, 2H), 6.80 (d, J = 3.8 Hz, 2H), 6.63 (d, J = 3.8 Hz, 2H), 132.15, 131.82, 129.35, 128.45, 128.39, 121.83, 120.53, 118.51,
.39 (s, 3H), 2.20 (s, 6H); C NMR (101 MHz, CDCl )  187.99, 21.18, 20.07. HRMS calcd. For C27H B F N [M-F] 481.1977,
3 22 2 3 4
1
3
+
+
54.22, 151.23, 139.53, 137.31, 136.38, 136.35, 133.91, 130.30, found 481.1979.
30.22, 129.44, 129.06, 128.46, 121.80, 21.21, 20.26. HRMS
+
calcd. for C32
H26BF N O
2 2 2
[M+H] : 519.2050, found 519.2059.
5
d (R = 4-methoxyphenyl, Ar = mesityl) was prepared in 45% Conflicts of interest
o 1
yield (65 mg) ) from 1a and 2e. mp 133.7-135.9 C. H NMR
300 MHz, d -DMSO)  7.76 (d, J = 8.5 Hz, 4H), 7.11 (d, J = 9.7
Hz, 4H), 7.07 (s, 2H), 6.89 (d, J = 4.0 Hz, 2H), 6.82 (d, J = 3.9 Hz,
There are no conflicts to declare.
(
6
1
3
2
H), 3.85 (s, 6H), 2.37 (s, 3H), 2.16 (s, 6H); C NMR (126 MHz,
CDCl )  186.85, 164.29, 154.67, 139.37, 136.37, 132.71,
32.25, 130.09, 129.38, 128.39, 122.65, 121.08, 113.94, 113.74,
3
Acknowledgements
1
5
5
+
+
This work is supported by the Nature Science Foundation of
China (Grants Nos. 21672007, 21672007 and 21872002) and
Anhui Province (Grants No 1508085J07).
2 4
5.55, 21.18, 20.22. HRMS calcd. for C34H29BFN O [M-F]
59.2199, found 559.2198.
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 7 of 7
Organic & Biomolecular Chemistry
Journal Name
ARTICLE
Lett., 2016, 18, 736; (d) Y. Yu, L. Jiao, J. Wang, H. Wang, C. YVuie,wE.AHrtiacoleaOnndlinNe.
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