Iodine-catalyzed synthesis of N,N'-chelate organoboron aminoquinolate

Article abstract of DOI:10.1021/acs.joc.0c01649

We disclose a novel method for the synthesis of fluorescent N,N'-chelate organoboron compounds in high efficiency by treatment of aminoquinolates with NaBAr4/ R'COOH in the presence of an iodine catalyst. These compounds display high air and thermal stability. A possible catalytic mechanism based on the results of control experiments has been proposed. Fluorescence quantum yield of 3b is up to 0.79 in dichloromethane.

Full text of DOI:10.1021/acs.joc.0c01649

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Article
Iodine-Catalyzed Synthesis of N, N'-Chelate Organoboron Aminoquinolate
Tianbao Yang, Xin Cao, Xing-Xing Zhang, Yifeng Ou, Chaktong Au, Shuang-feng Yin, and Renhua Qiu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01649 • Publication Date (Web): 15 Sep 2020
Downloaded from pubs.acs.org on September 15, 2020
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Page 1 of 14
The Journal of Organic Chemistry
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Iodine-Catalyzed Synthesis of N, N-Chelate Organoboron
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‡
†
Tianbao Yang, Xin Cao, Xing-Xing Zhang, Yifeng Ou, Chak-Tong Au, Shuang-Feng Yin,
Renhua Qiu
*,†
†State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center
of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082,
China
‡College of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, Hunan, China
Supporting Information Placeholder
R1
R
Advantages:
NaBAr4
N
42 examples, yields up to 96%
Wide functional group tolerance
Transiton metals free
N
B
Ar
R1
R
Ar
Cheap and air-stable boron reagent
Iodine in catalyst amount
Novel organoboron aminoquinolate
N
O
I2 (5.0 mol%)
NH
RCOOH
O
R1
R = Rf, Me, Ph
NaBAr4
RCOOH
N
O
R
N
B
O
Ar
R
O
ABSTRACT: We disclose a novel method for the synthesis of fluorescent N,N-chelate organoboron compounds in high
efficiency by treatment of aminoquinolates with NaBAr /R'COOH in the presence of an iodine catalyst. These compounds
4
display high air and thermal stability. A possible catalytic mechanism based on the results of control experiments has been
proposed. Fluorescence quantum yield of 3b is up to 0.79 in dichloromethane.
INTRODUCTION
Scheme 1. Synthesis of N,N-chelate organoboron
fluorescents
N,N-chelate organoboron fluorescents have wide
1
applications in areas such as luminescent materials,
Previous work
2
3
4
fluorescent dyes, photosensitizers, molecular switches,
(a) No catalyst
N
R
R
5
6
photodynamic therapy, molecular probes, and cell
imaging. For example (Figure 1), boron dipyrromethene
B
R = F, Ph
yield up to 65%
N
N
BPh3 or BF3
or
7
+
N
N
Br
Br
Ph
N
Ph
derivatives have been successfully applied in
yield up to 50%
2 examples
B
Ar
B
B
B
Ar
8
Ph
Ph
N
photodynamic therapy and as fluorescence probe (A1),
N
(b) Base-promoted
while 2,2-(pyridine2,6-diyl)diphenolate derivatives (A2),
Ar1
N
Ar2
K3PO4 3.0 eq
with great thermally activated delayed fluorescence, in
Ar1
N
Ar2
N
+
Ar3B(OH)2
9.0 eq
N
yield up to 79%
1,4-dioxane,
110 °C, 20 h
9
B
Ar3 4 examples
organic light-emitting devices (OLEDs). Moreover,
Ar3
(c) Transitional metal
R1
R1
2
BPh (aq) polymer (A3), which is a class of fluorescent
Mn (3.0 eq)
p-tosyl chloride (2.5 eq)
main-chain type organoboron aminoquinolate polymers
+
Ar BF3K
5.0 eq
with efficient energy transfer and well π-extended linker
N
N
Ar yield up to 96%
7 examples
Na2CO3 (0.5 eq)
10
R
NH
CH CN 1.5 mL
R
N
B
units, plays a role in light harvesting antenna. Very
3
1
30 C, 24 h
Ar
O
O
recently, the aminoquinolate diarylboron complexes were
This work
11
synthesized and utilized as photocatalysts (A4).
(
d) Metal-free Catalysis
O
folic acid
R1
R1
R
O
O
I2 (5.0 mol%)
N
N
N
N
N
N
B
B
R
NH
NaBAr4
2
N
3
N
B
Ar
Ph
1
I
I
Ph
Ar
N
N
O
O
B
R = Rf, Me, Ph
Ar
B
F
F
NaBAr
RCOOH
(5
NaBAr4 =
Ar Na
Ar
R1
R1
Ph
I
5

R
Ar
2
COOH
mol%)
N
B
A3
A4
4
R1
R1
=
O
O
3
mol%)
(5.0
O
O
I 2
F
n
N
A1
A2
O
R
N
B
O
yield up to 96%
42 examples
R
Ar
O
Figure 1. N,N-chelate organoboron fluorescents
4
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To fulfil the ever increasing demand of N,N-chelate to extend the substrate scope, and 3n3t were generated in
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organoboron in material chemistry, efficient production is
required. There are two kinds of synthetic methods
moderate to good yields (67%82%). The substrate with an
electron-donating group at the para-position of aryl group
in sodium tetraarylborate still gave 82% yield of 3q.
12
13
(
Scheme 1). In Scheme 1a, BF
3
,
BPh
3
or complex
14
2 2
ArB Ph Br
2
reacts with N, N-bidendate ligand without
Furthermore, the substrate with
a large electron-
the need of a catalyst to yield the desired four-coordinate
organoboron with moderate efficiency (30–60%). In
Scheme 1b, the base-promoted one-pot synthesis of four-
withdrawing group C still gave 67% yield of 3t. The
6 5
F
above results indicate that the electronic property of BAr
2
had little effect on 3n3t yields.
Table 1. Optimization of Reaction Conditionsa.
1
5
coordinate organoboron is also an efficient route, but
nine equivalents of aryl boronic acids were required.
Therefore, the development of a highly efficient method
for the synthesis of such kind of molecular framework is
still meaningful. Very recently, Xu’s group studied the use
of transition metal (Mn powder, 3.0 equiv.) in the synthesis
of aminoquinolate diarylboron complexes successfully
0
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N
N
B
Cat. (5.0 mol%)
+
4
Ph BNa
F3C
N
Solvent, N2, Temp., 8 h
F3C NH
O
O
1a
2a
3a
o
Yield(%)(3a)b
Entry
[Cat]
Sol.(1 mL)
Temp.( C)
1
2
3
4
CuBr2
toluene
toluene
toluene
toluene
150
150
150
150
38
trace
42
1
1
(
Scheme 1c). Herein, in continuation of our study on
.
Cu(OAc)2 H2O
1
6
aminoquinoline synthesis, we disclose a new protocol to
afford N,N-chelate organoboron with fluorescence
properties by treatment of aminoquinolates with
CuBr
CuCl
43
5c
toluene
toluene
toluene
150
150
150
70
53
74
CuBr2
CuBr2
CuBr2
6d
NaBAr
4
/R'COOH in the presence of an iodine catalyst
7e
8f
(
Scheme 1d).
CuBr2
I2
toluene
150
82
9g
toluene
toluene
NMP
150
150
150
90
90
65
RESULTS AND DISCUSSION
10
I2
11
I2
Initially, 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide (1a)
and sodium tetraphenylborate (2a) were selected as
substrates for the optimization of reaction conditions
1
2
I2
DMF
150
60
13
14
15
I2
I2
I2
DMSO
toluene
toluene
150
100
140
NR
37
79
(
Table 1). When the reaction was carried out in the
16h
toluene
150
NR
2
I2
presence of catalytic amount of CuBr
2
(0.05 equiv.), (κ -
a1a (0.1 mmol), 2a (0.2 mmol), Cat. (0.005 mmol), solvent
(N,N)-8-trifluoroacetyl aminoquinolate) diphenylborane
3a was generated in 38% yield as the only product (entry 1,
the structure of 3a has been confirmed by X-ray analysis,
b
c
(
2
1.0 mL), N
equiv. of K
2
; isolated yield; 2 equiv. of AgNO
3
was added;
d
e
2
S
2
O
8
was added; 2 equiv. of PhI(OAc)
2
was
f
g
h
1
7
added; 2 equiv. of KIO
3 2 2
was added; 1 equiv. of I ; O .
see Supporting information, SI). Over Cu(OAc)2•H
yield is in trace amount, whereas over CuCl and CuBr the
yield is around 43% (entries 24). Adding AgNO , K
PhI(OAc) or I together with CuBr would increase the 3a
yield to 53%~90% (entries 59). It was found that the use
of I alone can give a 3a yield of up to 90% (entry 10). The
2
O, the
Scheme 2. Substrates scope in the synthesis of 3a.
3
2 2 8
S O ,
R1
R1
R2
I2 (5.0 mol%)
toluene, N2, 150 oC, 8 h
2
2
2
+
Ar4BNa
N
N
R2 NH
N
B
Ar
2
O
Ar
O
1
2
3a3t
results of solvent screening reveal that toluene is the most
suitable for the reaction (entries 1215). Lowering of
reaction temperature from 150 C to 120 C would decrease
R1
R1
O
N
N
N
N
the yield of 3a (entries 1415). There is no reaction when O
2
F3C
N
F3C
N
B
F3C
N
B
F3C
N
B
B
is present (entries 16).
O
O
O
O
With the standard reaction conditions in hand, we
investigated the substrate scope with respect to quinoline
derivatives (Scheme 2). The reaction displayed good
tolerance towards a wide range of functional groups such
as Cl (3b, 76%), Br (3c, 82%), thienyl (3g, 96%), methyl (3h,
78%), and methoxy (3i, 80%) that are attached to the
quinoline ring. Notably, substrates with electron
withdrawing groups gave higher yields (3d3f, 8692%)
than did substrates with electron-donating groups (3h3i,
a, R1 = H, 90%
3d, R1 = Ph, 90%
3
3
3h, 78%
3i, 80%
b, R1 = Cl, 76%
3e, R1 = 4-ClPh, 92%
3f, R1 = 4-AcPh,86%
R1 = Br, 82%
3c
,
3
g, R1 = 2-thiophene, 96%
N
N
N
N
N
B
F
R4
R2
N
B
F3C
F3C
N
B
F
B
F C
R
N
3
3
O
F
O
O
O
F
F
F
R4
F
F
3
R
j, R2 = Me, 47%
3n, R3 = Me, 72%
3r, R4 = Cl, 76%
3s, R4 = OMe, 74%
F
3
3
F
3
7880%). Replacing the CF group of 1a by a methyl group
k, R2 = C2F5, 75%
3o, R3 = OMe, 78%
3p, R3 = iPr, 69%
3t, 67%
3l, R2 = C F , 63%
would result in lower yield (3j, 47%). Comparing with
3
7
3m, R2 = C6F5, 81% 3q, R3 = tBu,82%
1
0
previous report , the yield of 3j was less than 43% by
treating air-sensitive triarylborane (BPh with N-
quinolin-8-yl)acetamide. Replacing CF group with C
or C resulted in medium yields (3k3m, 6381%).
Various sodium tetraarylborate derivatives 2 were screened
a1 (0.1 mmol), 2 (0.2 mmol), I
mL), N , 150 C, 8 h, isolated yield of 3.
2
(0.005 mmol), toluene (1.0
3
)
2
(
C
3
2 5
F ,
3
F
7
6 5
F
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Surprisingly, in the synthesis of 3a, 1a in the presence of
a tiny amount of CF COOH resulted in the formation of
reacted with 2a to generate those active species. BPh
reacted with 1a to give a trace amount of desired 3a
(Scheme 4b), suggesting BPh might not be a possible
3
1
2
3
4
5
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7
8
9
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1
1
1
1
1
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5
5
5
5
6
3
novel boron compound 4a. We investigated the scope of
3
f
quinoline derivatives [(8-A Q)BAr(X)] (4) by a slightly
intermediate. In addition, when radical scavenger
TEMPO/BHT/BQ was employed in the reaction system,
the reaction was almost completely quenched (Scheme
4c), indicating that the present protocol involves a radical
pathway. These results may suggest the intermediacy of
phenyl radical Ph• in the transformation, in which
diphenyl could be found (Scheme 4a). In addition, benzene
was detected by GC-MS (see SI). We also chose compound
3a as starting material to react with trifluoroacetic acid
modified synthetic protocol using 1 equivalent of 2 and 2
equivalents of acyl acid 5 (Scheme 3). The reaction showed
good tolerance towards a wide range of functional groups
attached to quinoline such as Cl (4b, 82%), Br (4c, 82%),
thienyl (4e, 71%), methyl (4f, 89%), and methoxy (4g,
65%). Notably, substrates attached with an electron-
donating group showed higher yields (4d, 93%) than did
those with an electron-withdrawing group (4b, 82%; 4c,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
2%). Replacing trifluoromethyl with methyl or phenyl
3
(CF COOH) for the direct production of 4a (yield 65%)
could result in the desired products (4h, 78%; 4i, 76%).
Various sodium tetraarylborate derivatives 2 were also
screened (4j, 81%; 4k, 80%). The fact that the substrate
with electron-donating propionic acid only gave 50% yield
(Scheme 4d). The reaction could be quenched by TEMPO
2
(Scheme 4e), and in the absence of I did not proceed
(Scheme 4f).
Scheme 4. Control experiments and mechanism.
of
4l,
while
that
with
electron-withdrawing
(
a)Without 1a
I2
.0 eq. 2.0 eq.
pentafluorobenzonic acid gave 89% yield of 4v signifies
toluene
+
2a
BPh3
+
Ph-Ph
considerable electronic effect on the yields of [(8-
N2, 150 °C, 8 h GC-MS detected
1
42%
f
A Q)BAr(X)] (4j4v). The structure of 4t has been
1
8
(b) BPh3 instead of 2a
BPh3
2.0 eq.
confirmed by X-ray analysis, see SI.
toluene
1
a
+
3a
trace
Scheme 3. Substrates scope in the synthesis of 4a.
N , 150 °C, 8 h
2
1.0 eq.
(
c) TEMPO/BHT/BQ
I2 (5.0 mol%)
TEMPO/BHT/BQ (2.0 eq.)
R1
R1
N
N
1a
+
2a
3a
trace
R2
I2 (5.0 mol%)
R2
toluene, N , 150 °C, 8 h
NH + Ar BNa + R'COOH
N
B
1.0 eq.
2.0 eq.
2
4
O
toluene, N2, 150 °C, 2 h
Ar
O
O
R'
1
2
5
(d) 3a can form 4a
O
4a4v
I2 (5.0 mol%)
3a
+
CF COOH
4a
65%
R1
3
toluene, N , 150 °C, 8 h
1.0 eq.
2.0 eq.
2
O
N
B O
N
B O
N
B O
N
(e) TEMPO addition
I2 (5.0 mol%)
R2
N
B O
O
O
F3C
N
O
O
F3C
N
F3C
N
TEMPO (2.0 eq.)
3a
1.0 eq.
+
CF COOH
2.0 eq.
4a
ND
CF3
O
CF3
CF3
O
CF3
3
O
O
toluene, N , 150 °C, 8 h
2
4
a, R1 = H, 89%
4h, R2 = Me, 78%
4i, R2 = Ph, 76%
(f)
without I2 catalyst
1
4g, 65%
4b, R = Cl, 82%
4f, 89%
toluene, N , 150 °C, 8 h
1
2
4c, R = Br, 82%
3a
1.0 eq.
+
CF COOH
2.0 eq.
4a
trace
1a
85%
3
+
1
4d, R = 4-ClPh, 93%
4
e, R1 = 2-thiophene, 71%
(g) proposed mechanism
N

2
O
N
I2
N
F3C
N
B
O
2I
or
BPh4
A
O
O
F3C
N
B
O
-2 NaI
F3C
N
B
O
R4
O
O
R5
4
-
+
O
CF3
RCOOH
Ph
1
Ph Na
l, R4 = Et, 50%
4
4
4
4
m, R4
nPr, 52%
PhH
=
4q, R5 = H, 85%
4r, R5 = 2,4-dimethyl,73%
4s, R5 = 2,3-dimethyl, 73%
R3
3
Ph
+
PhH
RCOO
2
n, R4 = Bu, 82%
o, R4 = CCl3, 83%
t
or
4j, R3 = Me, 81%
HI
k, R3 = Bu, 80%
t
4
4p, R4 = 1-dodecene, 45%
On the basis of the above results and literature
1
0
precedents, a plausible mechanism is proposed (Scheme
4g). As a first step, iodine radical is generated by high
temperature homolytic cleavage. Addition of 2 with iodine
N
N
O
N
O
F
O
F3C
N
B
O
F3C
N
B O
F3C
N
B
O
Br
O
F
O
O
O
O
F
1
9
F
radical affords intermediate radical A (•BPh ) , which
4
F
MeO
reacts with 1 to form 3 together with a phenyl radical.
4t, 63%
4u, 72%
4v, 89%
1.81 g, 3.25 mmol, 65%)b
Combination of the phenyl radical with 2 regenerates
(
1
9
-
+
a1 (0.1 mmol), 2 (0.1 mmol), 5 (0.2 mmol), I
toluene (1.0 mL), N , 150 C, 2 h, isolated yield of 4. 5 mmol-
•BPh4 and Ph Na . With the involvement of phenyl radical
2
(5.0 mol%),
b
or iodine radical, the reaction of 3 with CF COOH forms 4.
3
2
scale, 12 h (1.81 g, 3.25 mmol, 65%).
In the whole process, a catalytic amount of iodine is good
enough.
To understand the synthesis mechanism of 3 and 4, we
With two series of BN complexes (3a3t, 20 examples,
performed a series of control experiments (Scheme 4). I
reacted with 2a to give BPh (GC-MS analysis, air-sensitive)
and biphenyl (42%) (Scheme 4a), confirming I first
2
4a4v, 22 examples) in hand, we proceeded to characterize
3
their physical and chemical properties. (i) Air-stability:
2
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The organoboron aminoquinolates 3 and 4 exhibited good of the compounds (3c, 3d, 3f, 3g, 0.38, 0.24, 0.33, 0.31)
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1
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1
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5
5
5
5
5
6
air-stability, both of them were found stable in open air for
four years at room temperature. (ii) Solubility: They can be
well dissolved in solvents such as toluene, dimethyl
sulfoxide, N,N-dimethylformamide, tetrahydrofuran,
dichloromethane, chloroform, acetone, and acetonitrile.
(iii) Fluorescent ability: They show a wide-range green,
blue or yellow fluorescence emission (Figure 2).
decreased but 3b and 3e displayed better (0.79, 0.55).
Compound 3t with more fluorine atoms also exhibited
excellent quantum yield (0.75). As
a whole, the
fluorescence quantum yield of 4a4v was similar to that of
3a3t (Figure 2 and Table 2). We used different carboxylic
acid to synthesize 4l4v, and found good quantum yield
(
4v, 0.67). The products utilized as photocatalysts and
Lewis acid catalysts are still under investigation in our lab.
CONCLUSIONS
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
In summary, we have developed a highly efficient method
for the synthesis of two kinds of BN quenched
f
organoboron aminoquinolate [(8-A Q)BAr
2
]
and [(8-
f
A Q)BAr(X)] by treatment of aminoquinolates with
NaBAr4/R'COOH using iodine as catalyst. This protocol
has wide substrate scope. The produced compounds
display high air and thermal stability as well as fluorescent
ability. Fluorescence quantum yield of 3b is up to 0.79 in
dichloromethane.
EXPERIMENTAL SECTION
2
All reactions were carried out under N atmosphere using
Figure 2. Fluorescence spectra of (ab) 3 and (cd) 4 [used
solutions in DCM], Al(q) as reference.
3
standard Schlenk techniques unless stated otherwise. The
glassware was dried in an oven (110 °C) and heated under
reduced pressure before use. The thin layer
1
0
Table 2. UV absorption and fluorescence propertiesa
chromatography
(TLC)
analysis
and
column
chromatography were performed using silica gel (200300)
with distilled solvents. NMR spectra were recorded on a
Bruker Advance 400 spectrometer operating at 400 MHz
Compd max (nm) em (nm)  (%)
Compd max (nm) em (nm)  (%)
3
a
374
390
474
506
49
79
3k
3l
372
369
445
482
40
17
3b
1
13
1
13
(
H NMR) and 101 MHz ( C NMR) in CDCl
NMR chemical shifts were reported in ppm relative to
internal references of CDCl at 7.26 ppm and carbon
resonance in chloroform-d at 77.00 ppm, respectively. The
3
. All H and C
3
3
3
c
d
e
388
387
499
505
38
24
3m
3n
3o
3p
372
372
450
469
55
24
392
385
507
500
55
33
371
378
442
444
13
32
3
3f
1
3
g
h
397
366
399
527
441
495
31
19
37
3q
3r
3s
3t
372
372
374
466
471
465
30
24
21
following abbreviations are used to describe peak patterns
where appropriate: singlet (s), doublet (d), triplet (t),
multiplet (m), broad resonances (br). Unless noted
otherwise, the materials obtained from commercial
suppliers were used without further purification. All
solvents were distilled. The UV absorption data was tested
by SHIMADZU UV 2600 at room temperature. The data of
the fluorescence emission was tested by HITACHI FV4600
at room temperature.
3
3
i
3j
399
518
18
377
479
75
4
a
365
380
479
502
38
26
4l
369
359
478
476
46
20
4b
4m
4n
4o
4p
4q
4
4
4
c
d
e
384
390
502
515
20
25
369
369
479
477
45
43
397
357
440
471
13
36
366
362
473
477
34
37
4f
4
g
h
368
398
391
483
513
439
32
28
31
4r
4s
4t
368
369
369
477
481
477
21
41
44
4
Typical
Experimental
Procedure
for
the
4
i
4
j
370
370
390
493
441
513
50
16
17
4u
4v
369
372
473
487
40
67
Preparation of Starting Materials N-trifluoroacetyl
aminoquinolines Derivatives (1)
4k
ref.10
Alq3
N-trifluoroacetyl aminoquinolines derivatives were
20
prepared according to the literatures. Trifluoroacetic
aThe UV absorption was controlled between 0.025 and 0.050
for fluorescence quantum yield. The data of fluorescence
emission was excited at maximum absorption wavelength.
anhydride or trifluoroacetyl chloride (11.0 mmol) was
added dropwise into a solution of 8-aminoquinoline (1.44
g, 10.0 mmol) and Et
mL) at 0 C. The mixture was stirred overnight at room
temperature. Then the mixture was diluted with CH Cl
(10.0 mL), and washed successively with water, saturated
aqueous NaHCO , and brine. The organic layer was dried
over MgSO and concentrated under reduced pressure.
The residue was purified by flash column chromatography
3 2 2
N (1.7 mL, 12.0 mmol) in CH Cl (15.0
The UV absorption wavelengths of 42 compounds
ranged from 366 nm to 399 nm. The fluorescence emission
of them are from 441 nm to 518 nm. The fluorescence
quantum yield of 3a is 0.49. However, with an group
including chlorine, bromine, phenyl, chlorophenyl,
phenylacetyl, thienyl, 3b3g) was attached on the C5
2
2
3
(
4
position of quinoline ring, the fluorescence quantum yield
ACS Paragon Plus Environment

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The Journal of Organic Chemistry
on silica gel and eluted with EtOAc/Hexane (1:10, v/v) to
afford the corresponding 8-aminoquinolinyl amides 1.
General Procedure for N-(5-halogen-)-2,2,2-
at 100 °C for 12 h. Then, the mixture was concentrated
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
under reduced pressure. The residue was purified by flash
chromatography (silica gel, petroleum ether/ethyl
acetate=5:1, v/v) to afford 5-(Substrates)quinoline-8-
amine, which reacted with fluoroanhydride to get the
related products. At last, using previous method, there is
the formation of the target amine.
trifluoro-8-quinolinylacetamide Generation
N-(5-halogen-)-2,2,2-trifluoro-8-quinolinylacetamide
1
6d
was prepared according to the literatures. To a 10.0 mL
screw capped vial equipped with a magnetic stirring bar
was added N-(quinolin-8-yl)pivalamide (1) (0.2 mmol), N-
halogensuccinimide (NXS, X = Cl, Br, 0.22 mmol) and DMF
General Procedure for Sodium Tetraarylborates
production
Sodium tetraarylborates were prepared according to the
(
1.0 mL) under N
the reaction mixture was placed in an oil bath preheated to
0 °C and vigorously stirred for 1 h. Subsequently the
2
atmosphere. To halogenate quinolone,
21
literature with some modifications. The synthesis of
sodium tetra-p-tolylborate was chosen as representative
reaction. A mixture of sodium tetrafluoroborate (1.47 g, 13.4
mmol) and magnesium turnings (2.16 g, 88.7 mmol) were
placed in an oven-dried sealed tube. The tube was filled
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
reaction mixture was cooled down to room temperature,
filtered through a plug of celite and then washed with
saturated brine and extracted by ethyl acetate (3  5.0 mL).
The solvents were removed under reduced pressure and
the crude reaction mixture was purified by
chromatography on silica gel using PE/EtOAc(20:1 v/v) as
eluent to obtain the desired products.
To a solution of halogenated quinoline (0.2 mmol, 67.2
mg) in EtOH (1.0 mL) was added NaOH (2.0 mmol, 80.0
mg). The mixture was heated at 100 C for 12 h. Then, the
mixture was concentrated under reduced pressure. The
residue was purified by flash chromatography (silica gel,
petroleum ether/ethyl acetate=5/1, v/v) to afford 5-
(halogen)quinoline-8-amine.
2
with N by the standard Schlenk technique. To this
mixture, 30.0 mL of THF and iodine (10.0 mg) were added
and the mixture was stirred for 1 min. Finally, p-
bromotoluene (10.0 mL, 80.2 mmol) was added and the
suspension was stirred for 12 h at room temperature. After
1
2 h, the solution became gray and white precipitates were
formed. Then the reaction mixture was added to aqueous
Na2CO , stirred for 30 min, and then extracted with ethyl
acetate/diethyl ether (1:1; 3  30 mL). The organic layer was
dried over MgSO , filtered, and concentrated under
reduced pressure with a rotary evaporator. The crude
residue was purified by precipitation using
3
4
Then trifluoroacetic anhydride (1.1 mmol) was added
dropwise to a solution of 5-(halogen)quinoline-8-amine
chloroform/hexane (1:4) to afford an off-white powder of
sodium tetra-p-anisylborate (4.54 g, 11.4 mmol, 85%).
General Procedure for the Synthesis of Products 34.
To a 10.0 mL screw capped vial equipped with a magnetic
stirring bar was added aminoquinolines derivatives (1) (0.1
mmol), sodium tetraphenylborate derivatives (2) (0.10.2
(
3 2 2
1.0 mmol) and Et N (170 µL, 1.2 mmol) in CH Cl (15.0 mL)
at 0 °C. The mixture was stirred overnight at room
temperature. Afterward the mixture was diluted with
CH
saturated aqueous NaHCO
was dried over MgSO and concentrated under reduced
2
Cl
2
(10.0 mL), and washed successively with water,
3
, and brine. The organic layer
mmol), I
2
(0.005 mmol), (or adding 2 equivalents of acid
4
for the synthesis of 4) and toluene (1.0 mL) under N
2
pressure. The residue was purified by flash column
chromatography on silica gel and eluted with
EtOAc/Hexane (1:10, v/v) to afford the corresponding 8-
aminoquinolinyl amides.
General Procedure for N-(5-Substrates-quinolin-8-
yl)-2,2,2-Trifluoroacetamide formation
atmosphere. The reaction mixture was placed in an oil bath
preheated to 150 C, and vigorously stirred for 8 h.
Afterward it was cooled to ambient temperature, filtered
through a plug of celite and then washed with ethyl acetate
(3  5.0 mL). The solvents were removed under reduced
pressure and the crude reaction mixture was purified by
chromatography on silica gel (PE/EtOAc, 10:1 v/v as an
eluent) to obtain the desired products 3.
2
,2,2-Trifluoro-N-(5-Substrates-)8-quinolinylacetamide
1
6d
was prepared according to the literatures. To a 10.0 mL
screw capped vial equipped with a magnetic stirring bar
was added brominated quinoline (3.0 mmol). Then the
reaction mixture was added with boronic acid derivatives
2
Procedure for the synthesis of ( -(N,N)-8-
trifluoroacetyaminoquinolate)-5-methoxyl-2-bromop
henylacetateborane (4t) in scale of 1 gram. To a 50.0 mL
screw capped vial equipped with a magnetic stirring bar
was added 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide (1a)
(
6.0 mmol), sodium carbonate (6.0 mmol), Pd(PPh
mmol), and DMSO (5.0 mL) under N atmosphere. The as-
resulted mixture was placed in an oil bath preheated to 140
C and vigorously stirred for 12 h. Subsequently it was
3 4
) (0.15
2
(
1
5 mmol, 1.2 g), sodium tetraphenylborate (2a) (5 mmol,
.71 g), 2-bromo-5-methoxybenzoic acid (10 mmol, 2.31 g),
(0.25 mmol, 63.3 mg) and toluene (10.0 mL) under N
2
°
cooled down to room temperature, filtered through a plug
of celite and then washed with saturated brine and
extracted by ethyl acetate (3  5.0 mL). The solvents were
removed under reduced pressure and the crude reaction
mixture was purified by chromatography on silica gel using
PE/EtOAc (20:1, v/v) as eluent to obtain the desired
product.
I
2
atmosphere. The reaction mixture was placed in an oil bath
preheated to 150 C, and vigorously stirred for 12 h.
Afterward it was cooled to ambient temperature, filtered
through a plug of celite and then washed with ethyl acetate
(
3  5.0 mL). The solvents were removed under reduced
pressure and the crude reaction mixture was purified by
chromatography on silica gel (PE/EtOAc, 10:1 v/v as an
eluent) to obtain the desired products (4t, 1.81 g, 65%).
To
a
solution of N-(5-(Substrates)quinoline-8-
yl)pivalamide (0.2 mmol, 67.2 mg) in EtOH (1.0 mL), was
added NaOH (2.0 mmol, 80.0 mg). The mixture was heated
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 14
Procedure for UV-vis absorption and fluorescence
-82.53 (s, 3F), -122.43 (s, 2F), -122.14 (d, J = 216.8 Hz, 2F).
MS (EI): m/z=290.1.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
quantum yield of 3a4v. We first used 1.0 mol/L 3a4v
in DMF to test UV absorption, but the extent of absorption
was too low. Finally, we found 40.0 mol/L 3a4v in DMF
suitable for graphic purpose. The data was tested by
SHIMADZU UV 2600 at room temperature (SI, Figure
S29). We chose compound 4t as sample to screen serval
solvents, such as 1,4-dioxane, DCM, DMF, DMSO, CH3CN,
THF, Toluene in 5 mol/L. We found that DCM is the best
solvent for the fluorescence emission. The data of the
fluorescence emission was tested by HITACHI FV4600 at
room temperature (SI, Figure S30). We controlled 3a4v to
test the UV absorption between 0.025 and 0.050 in DCM
for fluorescence quantum yield by SHIMADZU UV 2600 at
room temperature. Next, we tested the data of fluorescence
emission when excited at their maximum absorption
wavelength by HITACHI FV 4600 (SI, Table S3, S4).
N-(quinolin-8-yl)-2,2,3,3,4,4,4-heptafluorobutanamide
16b
(1e). The amide was obtained as yellow oil, 2.7 g, 79%
1
yield. EtOAc/petroleum ether = 1:20, R
(400 MHz, CDCl ) δ 10.84 (s, 1H), 8.81 (dd, J = 4.2, 1.4 Hz,
1H), 8.67 (d, J = 7.6 Hz, 1H), 8.15 (dd, J = 8.3, 1.4 Hz, 1H),
f
= 0.46. H NMR
3
1
3
1
7.687.56 (m, 1H), 7.567.44 (m, 2H). C H NMR (101
MHz, CDCl ) δ 155.5, 155.2, 154.9, 149.0, 138.4, 136.4, 132.1,
3
129.9, 127.9, 127.1, 123.9, 122.2, 119.3, 119.0, 118.7, 117.6, 116.5,
116.1, 115.8, 113.6, 113.3, 111.5, 111.2, 110.9, 109.0, 108.8, 108.6,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
9
108.5, 108.2, 108.2, 107.9, 106.2, 105.9, 105.5. F NMR (376
MHz, CDCl ) δ -80.45 (t, J = 8.8 Hz, 2F), -120.16 (q, J = 8.8
3
Hz, 3F), -126.66 (s, 2F). MS (EI): m/z=340.0.
N-(quinolin-8-yl)-2,3,4,5,6-pentafluorobenzamide (1f).23
The amide was obtained as white solid, 2.7 g, 80% yield.
mp:134.5135.2 C. EtOAc/petroleum ether = 1:20, R = 0.45.
f
2
2
Calculation formula of quantum yield was adopted as the
1
3
H NMR (400 MHz, CDCl ) δ 10.43 (s, 1H), 8.908.80 (m,
2
푠
퐴푐푎푙
· 퐴
푛
2H), 8.24 (d, J = 8.1 Hz, 1H), 7.65 (m, 2H), 7.52 (dd, J = 8.2,
following: 퐹=
퐹,푐푎푙푆푐푎푙
·

푛푐푎푙2
13
1
4.3 Hz, 1H). C H NMR (101 MHz, CDCl ) δ 155.3, 148.5,
3
1
45.6, 143.1, 141.2, 138.9, 138.1, 136.4, 133.5, 127.8, 127.2, 122.9,
N-(quinolin-8-yl)-2,2,2-trifluoroacetamide (1a).16b The
amide was obtained as white solid, 2.2 g, 90% yield.
19
121.9, 117.2, 111.9. F NMR (376 MHz, CDCl
3
) δ -140.03 (d, J
= 15.9 Hz, 2F), -150.38 (t, J = 20.7 Hz, 1F), -156.59-163.62 (m,
2F). MS (EI): m/z=338.1.
N-(5-chloroquinolin-8-yl)-2,2,2-trifluoroacetamide (1g).
The amide was obtained as white solid, 227.4 mg, 83% yield.
mp:82.483.1 C. EtOAc/petroleum ether = 1:20, R
f
= 0.50.
1
3
H NMR (400 MHz, CDCl ) δ 10.69 (s, 1H), 8.81 (d, J = 4.1
Hz, 1H), 8.65 (d, J = 7.6 Hz, 1H), 8.16 (d, J = 8.3 Hz, 1H), 7.60
3
1
(
d, J = 8.3 Hz, 1H), 7.567.45 (m, 2H). 1 C H NMR (101
mp:131.5132.5 C. EtOAc/petroleum ether = 1:20, R
f
= 0.43.
MHz, CDCl ) δ 154.6, 148.9, 138.4, 136.4, 132.0, 127.9, 127.0,
3
1
3
H NMR (400 MHz, CDCl ) δ 10.60 (s, 1H), 8.85 (d, J = 3.7
1
9
1
23.8, 122.2, 117.5, 115.8 (q, J = 288.4 Hz). F NMR (376 MHz,
13
1
Hz, 1H), 8.54(t, J = 9.8 2H), 7.607.42 (m, 2H). C H NMR
3
CDCl ) δ -75.72 (s, 3F). MS (EI): m/z=240.0.
N-(2-methylquinolin-8-yl)-2,2,2-trifluoroacetamide (1b).
(
101 MHz, CDCl
3
) δ 155.3 (q, J = 37.8 Hz), 149.4, 138.7, 133.4,
19
1
31.1, 126.8, 126.8, 125.8, 122.8, 117.3, 115.7 (q, J = 288.3 Hz). F
1
6b
The amide was obtained as white solid, 2.5 g, 98% yield.
NMR (376 MHz, CDCl
m/z=274.0, HRMS m/z (EI) calcd for [C11
3
) δ -75.74 (s, 3F). MS (EI):
ClF O]:
mp:83.484.3 C. EtOAc/petroleum ether = 1:20, R
f
= 0.48.
H
6
3 2
N
1
H NMR (400 MHz, CDCl
3
) δ 10.80 (s, 1H), 8.64 (d, J = 7.6
274.0121 found 274.0125.
Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.49
t, J = 7.9 Hz, 1H), 7.36 (d, J = 8.4 Hz, 1H), 2.75 (s, 3H).
N-(5-bromoquinolin-8-yl)-2,2,2-trifluoroacetamide (1h).
The amide was obtained as white solid, 222.5 mg, 70%
(
24
13
1
C H NMR (101 MHz, CDCl
3
) δ 158.2, 154.8, 154.5, 137.7,
yield. mp:122.5123.4 C. EtOAc/petroleum ether = 1:20, R
f
1
36.4, 131.3, 126.0, 123.5, 123.0, 117.4, 115.9 (q, J = 288.5 Hz).
1
=
=
0.43. H NMR (400 MHz, CDCl
3
) δ 10.65 (s, 1H), 8.85 (d, J
19
3
F NMR (376 MHz, CDCl ) δ -75.79(s, 3F). MS (EI):
2.5 Hz, 1H), 8.53 (t, J = 7.9 Hz, 2H), 7.79 (d, J = 8.3 Hz, 1H),
m/z=254.1.
13
1
3
7.60 (dd, J = 8.4, 4.1 Hz, 1H). C H NMR (101 MHz, CDCl )
N-(6-methoxyquinolin-8-yl)-2,2,2-trifluoroacetamide (1c).
The amide was obtained as faint yellow solid, 2.1 g, 81%
δ 154.7 (q, J = 37.7 Hz), 149.4, 138.9, 136.1, 131.8, 130.5, 127.2,
16b
19
1
23.2, 115.4 (q, J = 288.4 Hz), 117.1, 116.9, 116.6. F NMR (376
yield. mp:127.3128.6 C. EtOAc/petroleum ether = 1:20, R
f
3
MHz, CDCl ) δ -75.72 (s, 3F). MS (EI): m/z=317.9.
1
=
(
8
3
0.48. H NMR (400 MHz, CDCl ) δ 10.64 (s, 1H), 8.968.52
N-(5-phenylquinolin-8-yl)-2,2,2-trifluoroacetamide (1i).
The amide was obtained as white solid, 2.9 g, 92% yield.
m, 1H), 8.37 (s, 1H), 8.04 (d, J = 8.3 Hz, 1H), 7.43 (dd, J =
16b
13
1
.1, 4.2 Hz, 1H), 6.87 (s, 1H), 3.92 (s, 3H). C H NMR (101
mp:107.8109.3 C. EtOAc/petroleum ether = 1:20, R
f
= 0.41.
) δ 10.85 (s, 1H), 8.87 (d, J = 3.8
Hz, 1H), 8.76 (d, J = 7.9 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H),
MHz, CDCl
3
) δ 158.0, 154.9, 154.6, 146.3, 135.0, 134.8, 132.8,
1
H NMR (400 MHz, CDCl
3
19
1
28.9, 122.6, 115.7 (q, J = 288.4 Hz), 110.5, 101.7. F NMR (376
3
MHz, CDCl ) δ -75.76(s, 3F). MS (EI): m/z=269.1.
13
1
7
.607.40 (m, 7H). C H NMR (101 MHz, CDCl
3
) δ 154.8
N-(quinolin-8-yl)-2,2,3,3,3-pentafluoropropenamide (1d).
(
q, J = 37.3 Hz), 148.7, 138.6, 138.5, 136.7, 135.0, 131.3, 130.0,
16b
The amide was obtained as yellow oil, 2.6 g, 91% yield.
19
1
28.6, 127.8, 127.5, 126.3, 122.1, 115.8 (q, J = 274.5 Hz). F NMR
1
EtOAc/petroleum ether = 1:20, R
MHz, CDCl
8.788.61 (m, 1H), 8.328.09 (m, 1H), 7.697.61 (m, 1H),
f
= 0.46. H NMR (400
(
3
376 MHz, CDCl ) δ -75.65 (s, 3F). MS (EI): m/z=316.1.
3
) δ 10.88 (s, 1H), 8.84 (d, J = 3.9 Hz, 1H),
N-(5-chlorophenylquinolin-8-yl)-2,2,2-trifluoroacetamide
(
1j). The amide was obtained as white solid, 3.0 g, 85% yield.
1
3
1
3
7.607.47 (m, 2H). C H NMR (101 MHz, CDCl ) δ 155.6,
mp:150.5151.4 C. EtOAc/petroleum ether = 1:20, R
H NMR (400 MHz, CDCl ) δ 10.83 (s, 1H), 8.88 (d, J = 2.2
3
f
= 0.40.
155.4, 155.1, 149.0, 138.3, 136.4, 132.0, 127.8, 126.9, 123.8, 122.2,
119.8, 119.4, 119.1, 117.5, 116.9, 116.6, 116.3, 113.7, 109.7, 109.3,
1
Hz, 1H), 8.75 (d, J = 7.9 Hz, 1H), 8.26 (d, J = 8.5 Hz, 1H), 7.50
1
9
107.5, 107.1, 106.7, 104.4, 104.0. F NMR (376 MHz, CDCl
3
) δ
13
1
(
t, J = 8.5 Hz, 4H), 7.38 (d, J = 8.0 Hz, 2H). C H NMR (101
MHz, CDCl ) δ 148.8, 138.5, 137.0, 135.3, 135.3, 134.6, 131.7,
3
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The Journal of Organic Chemistry
31.2, 128.9, 127.6, 126.2, 122.3, 117.1. 19F NMR (376 MHz,
) δ -75.68 (s, 3F). MS (EI): m/z=350.1, HRMS m/z (EI)
calcd for [C17 O]: 350.0434 found 350.0437.
13
1
1
7.9 Hz, 1H), 7.01 (d, J = 7.8 Hz, 1H), 5.17 (s, 2H). C H NMR
(101 MHz, CDCl ) δ 147.2, 143.7, 138.4, 138.2, 133.7, 132.7, 131.3,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
CDCl
3
3
H
10ClF
3
N
2
128.5, 128.1, 127.2, 126.7, 121.4, 109.3.
27
N-(5-(thiophen-2-yl)-quinolin-8-yl)-2,2,2-trifluoroacetam
5-bromoquinolin-8-amine (1r). EtOAc/petroleum = 1:10,
= 0.45, 43.3 mg, 98% yield. H NMR (400 MHz, CDCl
1
-ide (1k). The amide was obtained as white solid, 3.0 g, 93%
R
f
3
) δ
yield. mp:121.3122.4 C. EtOAc/petroleum ether = 1:20, R
f
8.73 (d, J = 3.2 Hz, 1H), 8.38 (d, J = 8.5 Hz, 1H), 7.54 (d, J =
8.1 Hz, 1H), 7.43 (dd, J = 8.5, 4.1 Hz, 1H), 6.75 (d, J = 8.1 Hz,
1H), 5.05 (s, 2H). C H NMR (101 MHz, CDCl3) δ 147.7,
1
= 0.41. H NMR (400 MHz, CDCl
3
) δ 10.82 (s, 1H), 8.87 (d, J
1
3
1
= 3.4 Hz, 1H), 8.72 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.5 Hz,
1H), 7.58 (d, J = 7.9 Hz, 1H), 7.50 (d, J = 3.4 Hz, 2H), 7.39 (s,
144.0, 139.1, 135.4, 130.8, 127.8, 122.4, 110.1, 107.3.
1
3
1
28
1H), 7.26 (d, J = 4.3 Hz, 1H). C H NMR (101 MHz, CDCl
3
)
sodium tetra-p-tolylborate (2aa). The borate was
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
δ 154.8 (q, J = 38.4 Hz), 148.7, 139.1, 138.5, 134.9, 131.4, 129.1,
obtained as white solid, 4.5 g, 85% yield. H NMR (400 MHz,
1
9
127.4, 126.5, 126.1, 124.1, 122.2, 115.8 (q, J = 279.8 Hz). F NMR
(376 MHz, CDCl ) δ -75.67 (s, 3F). MS (EI): m/z=322.0,
D
2
O) δ 7.30 (s, 8H), 7.03 (d, J = 6.0 Hz, 8H), 2.26 (s, 12H).
1
3
1
C H NMR (101 MHz, D
2
O) δ 135.6, 134.6, 132.3, 127.3, 19.9.
3
HRMS m/z (EI) calcd for [C15
H
9 3
F N
2
OS]: 322.0388 found
MS (EI): m/z=398.2.
sodium tetrakis(4-methoxyphenyl)borate (2b).29 The
322.0386.
1
N-(5-(4-acetylphenyl)quinolin-8-yl)-2,2,2-trifluoroaceta
mide (1l). The amide was obtained as white solid, 3.2 g, 90%
borate was obtained as white solid, 5.5 g, 88% yield. H
2
NMR (400 MHz, D O) δ 7.07 (s, 12H), 6.616.59 (m, 4H),
1
3
1
yield. mp:219.5221.1 C. EtOAc/petroleum ether = 1:20, R
f
3.643.60 (m, 12H). C H NMR (101 MHz, Acetone) δ
206.2, 156.2, 137.5, 111.7, 111.7, 111.7, 111.7, 54.9. MS (EI):
m/z=462.2.
1
=
=
0.41. H NMR (400 MHz, CDCl
3
) δ 10.85 (s, 1H), 8.89 (d, J
3.0 Hz, 1H), 8.77 (d, J = 7.9 Hz, 1H), 8.27 (d, J = 8.5 Hz,
sodium tetrakis(3-methoxyphenyl)borate (2c).29 The
1
H), 8.11 (d, J = 8.0 Hz, 2H), 7.627.46 (m, 4H), 2.69 (s, 3H).
1
3
1
borate was obtained as faint yellow solid, 5.4 g, 87% yield.
C H NMR (101 MHz, CDCl
3
) δ 197.6, 148.9, 143.4, 138.4,
1
1
(
7
[
36.4, 135.4, 134.5, 132.0, 130.2, 128.7, 127.7, 126.0, 122.4, 115.7
H NMR (400 MHz, D
2
O) δ 7.07 (s, 12H), 6.616.59 (m, 4H),
1
9
13
1
q, J = 275.8 Hz), 101.4, 26.7. F NMR (376 MHz, CDCl
5.68 (s, 3F). MS (EI): m/z=358.2, HRMS m/z (EI) calcd for
]: 358.0929 found 358.0921.
3
) δ -
3.643.60 (m, 12H). C H NMR (101 MHz, D2O) δ 165.9,
157.4, 128.7, 127.7, 120.5, 108.7, 54.9. MS (EI): m/z=462.2.
2
8
C
19
H
13
F
3
N
2
O
2
sodium tetrakis(3-chlorophenyl)borate (2d). The borate
2
5
1
5
-(thiophen-3-yl)quinolin-8-amine (1m). EtOAc/petrole
was obtained as white solid, 4.0 g, 66% yield. H NMR (400
1
13
1
um ether = 1:10, R
MHz, CDCl
f
= 0.40, 38.9 mg, 86% yield. H NMR (400
2
MHz, D O) δ 7.29 (d, J = 22.2 Hz, 8H), 7.00 (s, 8H). C H
3
) δ 8.78 (d, J = 4.0 Hz, 1H), 8.33 (d, J = 8.6 Hz,
NMR (101 MHz, D
(EI): m/z=455.0.
2
O) δ 134.4, 133.6, 132.4, 128.4, 123.1. MS
1
H), 7.497.41 (m, 1H), 7.407.32 (m, 2H), 7.327.27 (m, 1H),
7
.23 (d, J = 4.8 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 5.07 (s, 2H).
sodium tetrakis(4-(tert-butyl)phenyl)borate (2e). The
1
1
3
1
borate was obtained as white solid, 6.0 g, 79% yield. H
3
C H NMR (101 MHz, CDCl ) δ 147.2, 143.5, 140.5, 138.3,
NMR (400 MHz, DMSO) δ 7.16 (s, 8H), 6.95 (d, J = 7.7 Hz,
1
34.1, 129.6, 128.0, 127.2, 125.3, 123.4, 122.6, 121.4, 109.4.
1
6d
13
1
5
-phenylquinolin-8-amine (1n).
ether = 1:10, R = 0.42, 36.5 mg, 83% yield. H NMR (400
MHz, CDCl ) δ 8.78 (d, J = 4.0 Hz, 1H), 8.23 (d, J = 8.6 Hz,
H), 7.537.28 (m, 7H), 6.99 (d, J = 7.7 Hz, 1H), 5.06 (s, 2H).
EtOAc/petroleum
8H), 1.23 (s, 36H). C H NMR (101 MHz, Acetone) δ 205.4,
1
161.8, 161.3, 160.8, 160.3, 142.6, 135.8, 121.8, 33.5, 31.3, 29.6,
f
2
9.4, 29.2, 29.0, 28.8, 28.6, 28.4. MS (EI): m/z=566.4, HRMS
3
-
m/z (ESI) calcd for [C40
H
52B] : 543.4168 found 543.4161.
1
30
1
3
1
sodium tetrakis(4-isopropylphenyl)borate (2f).
The
C H NMR (101 MHz, CDCl
3
) δ 147.2, 143.4, 140.0, 138.3,
1
borate was obtained as white solid, 3.1 g, 46% yield. H
NMR (400 MHz, DMSO) δ 7.14 (s, 8H), 6.80 (d, J = 7.5 Hz,
8H), 2.72 (dt, J = 13.6, 6.8 Hz, 4H), 1.17 (d, J = 6.8 Hz, 24H).
1
34.2, 130.2, 128.9, 128.4, 128.1, 127.0, 126.8, 121.3, 109.5.
1
-(4-(8-aminoquinolin-5-yl)phenyl)ethenone (1o). EtOA
1
c/petroleum ether = 1: 10, R
NMR (400 MHz, CDCl
Hz, 1H), 8.05 (d, J = 8.2 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H),
.367.31 (m, 2H), 6.98 (d, J = 7.8 Hz, 1H), 5.16 (s, 2H), 2.66
s, 3H). C H NMR (101 MHz, CDCl
44.2, 138.2, 135.4, 133.7, 130.2, 128.5, 128.4, 127.2, 126.5, 121.6,
09.2, 26.6, HRMS m/z (EI) calcd for [C17 O]: 262.1106
f
= 0.40, 40.3 mg, 77% yield. H
13
1
C H NMR (101 MHz, Acetone) δ 206.2, 141.4, 137.0, 123.9,
3
) δ 8.908.64 (m, 1H), 8.19 (d, J = 8.6
1
23.9, 34.5, 24.8. MS (EI): m/z=510.3.
(
2-(N,N)-8-trifluoacetylaminoquinolate)diphenylboran
7
(
1
1
1
3
1
(3a). The borane was obtained as faint yellow solid, 36.1 mg,
0% yield. mp:223.2224.3 C. EtOAc/petroleum ether =
3
) δ 197.8, 147.4, 145.1,
9
1
1
f 3
:10, R = 0.48. H NMR (400 MHz, CDCl ) δ 9.06 (d, J = 5.8
14 2
H N
Hz, 1H), 8.538.34 (m, 2H), 7.86 (t, J = 7.4 Hz, 1H), 7.66 (d,
J = 7.7 Hz, 1H), 7.56 (s, 1H), 7.48 (d, J = 5.2 Hz, 4H), 7.25 (s,
found 262.1101.
-chloroquinolin-8-amine (1p).26 EtOAc/petroleum ether
5
1
13
1
=
1:10, R
f
= 0.45, 33.8 mg, 95% yield. H NMR (400 MHz,
6H). C H NMR (101 MHz, CDCl
3
) δ 167.1, 140.8, 140.2,
3
CDCl ) δ 8.80 (d, J = 3.6 Hz, 1H), 8.47 (d, J = 8.5 Hz, 1H),
139.5, 136.7, 133.2, 132.2, 127.5, 127.3, 127.2, 122.9, 121.3, 119.9,
19
7
.49 (dd, J = 8.4, 4.4 Hz, 1H), 7.39 (d, J = 8.1 Hz, 1H), 7.26 (s,
114.2 (q, J = 287.45 Hz). F NMR (376 MHz, CDCl
3
) δ -69.19
13
1
1
H), 6.84 (d, J = 8.1 Hz, 1H), 5.01 (s, 2H). C H NMR (101
MHz, CDCl ) δ 147.8, 143.3, 138.8, 132.9, 127.2, 126.5, 122.0,
18.1, 109.5.
(s, 3F). HRMS m/z (EI) calcd for [C23
found 404.1309.
( -(N,N)-5-chloro-8-trifluoroacetylaminoquinolate)dip
henylboran (3b). The borane was obtained as yellow solid,
H16BF N O]: 404.1308,
3 2
3
2
1
5
-(4-chlorophenyl)quinolin-8-amine (1q).25 EtOAc/petrol
1
eum ether = 1:10, R
MHz, CDCl
1H), 7.48 (d, J = 8.3 Hz, 2H), 7.447.35 (m, 3H), 7.32 (d, J =
f
= 0.42, 23.9 mg, 47% yield. H NMR (400
33.3 mg, 76% yield. mp:228.5229.8 C. EtOAc/petroleum
1
3
) δ 8.83 (d, J = 3.9 Hz, 1H), 8.21 (d, J = 8.5 Hz,
ether = 1:10, R
f
= 0.46. H NMR (400 MHz, CDCl
3
) δ 9.04 (d,
J = 8.4 Hz, 1H), 8.73 (d, J = 8.4 Hz, 1H), 8.55 (d, J = 4.8 Hz,
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The Journal of Organic Chemistry
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1
1
7
H), 7.92 (d, J = 8.4 Hz, 1H), 7.69 (dd, J = 8.5, 5.2 Hz, 1H),
EtOAc/petroleum ether = 1:10, R
CDCl ) δ 9.09 (d, J = 7.7 Hz, 1H), 8.68 (d, J = 8.4 Hz, 1H),
8.49 (d, J = 4.8 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.697.47
f
= 0.40. H NMR (400 MHz,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
13
1
.577.46 (m, 4H), 7.357.27 (m, 6H). C H NMR (101
) δ 160.2 (q, J = 38.7 Hz), 145.1, 141.1, 139.9, 137.3,
37.2, 133.1, 131.4, 127.6, 127.4, 125.6, 123.7, 123.6, 121.2, 115.5 (q,
3
MHz, CDCl
1
3
13
1
(m, 6H), 7.45 (s, 1H), 7.357.20 (m, 7H). C H NMR (101
MHz, CDCl ) δ 160.1 (q, J = 37.8 Hz), 145.4, 140.3, 139.8, 138.4,
137.5, 136.9, 133.2, 131.7, 128.5, 127.5, 127.2, 126.9, 126.0, 124.2,
122.9, 121.0, 115.6 (q, J = 287.4 Hz). F NMR (376 MHz, CDCl )
3
3 2
δ -69.13 (s, 3F). HRMS m/z (EI) calcd for [C27H18BF N OS]:
19
J = 287.3 Hz). F NMR (376 MHz, CDCl
HRMS m/z (EI) calcd for [C23H15BClF N O]: 438.0918 found
438.0913.
( -(N,N)-5-bromo-8-trifluoroacetylaminoquinolate)dip
henylboran (3c). The borane was obtained as yellow solid,
39.5 mg, 82% yield. mp:237.7238.8 C. EtOAc/petroleum
3
) δ -69.18 (s, 3F).
3
3 2
1
9
2
486.1185 found 486.1189.
2
( -(N,N)-2-methyl-8-trifluoroacetylaminoquinolate)dip
henylborane (3h). The borane was obtained as faint yellow
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ether = 1:10, R
= 0.46. H NMR (400 MHz, CDCl
3
) δ 8.98 (d,
f
J = 8.3 Hz, 1H), 8.68 (d, J = 8.4 Hz, 1H), 8.53 (d, J = 4.8 Hz,
1H), 8.10 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.5, 5.3 Hz, 1H),
solid, 32.6 mg, 78% yield. mp:186.1187.8 C.
1
EtOAc/petroleum ether = 1:10, R = 0.50. H NMR (400 MHz,
f
1
3
1
7.567.44 (m, 4H), 7.347.27 (m, 6H). C H NMR (101
MHz, CDCl ) δ 160.2 (q, J = 38.6 Hz), 145.2, 141.0, 140.5, 139.4,
137.3, 134.9, 134.7, 133.1, 130.5, 127.8, 127.6, 127.3, 126.9, 123.8,
3
CDCl ) δ 9.09 (s, 1H), 8.35 (d, J = 8.4 Hz, 1H), 7.85 (t, J = 8.1
3
Hz, 1H), 7.69 (d, J = 8.3 Hz, 1H), 7.647.57 (m, 4H),
1
3
1
7.407.28 (m, 7H), 2.45 (s, 3H). C H NMR (101 MHz,
1
9
123.3, 121.6, 119.8, 118.0, 115.5 (q, J = 287.4 Hz), 112.7, 111.3. F
NMR (376 MHz, CDCl ) δ -69.20 (s, 3F). HRMS m/z (EI)
O]: 482.0413 found 482.0389.
CDCl ) δ 154.6, 140.6, 139.4, 137.3, 133.6, 130.7, 127.5, 127.0,
3
1
9
3
126.1, 125.8, 120.7, 120.1, 115.6 (q, J = 287.4 Hz). F NMR (376
calcd for [C23
H
15BBrF
3
N
2
MHz, CDCl ) δ -69.11 (s, 3F). HRMS m/z (EI) calcd for
3
2
( -(N,N)-5-phenyl-8-trifluoroacetylaminoquinolate)dip
henylborane (3d). The borane was obtained as yellow solid,
[C H BF N O]: 418.1464 found 418.1453.
24
18
3
2
2
( -(N,N)-6-methoxyl-8-trifluoroacetylaminoquinolate)
diphenylborane (3i). The borane was obtained as yellow
4
3.2 mg, 90% yield. mp:195.5196.7 C. EtOAc/petroleum
1
ether = 1:10, R
f
3
= 0.48. H NMR (400 MHz, CDCl ) δ 9.14 (d,
solid, 34.7 mg, 80% yield. mp:262.0263.3 C.
1
J = 7.9 Hz, 1H), 8.59 (d, J = 8.5 Hz, 1H), 8.51 (d, J = 5.1 Hz,
EtOAc/petroleum ether = 1:10, R = 0.50. H NMR (400 MHz,
f
1
7
H), 7.87 (d, J = 8.1 Hz, 1H), 7.667.46 (m, 10H), 7.32 (t, J =
CDCl ) δ 9.07 (s, 1H), 8.59 (d, J = 8.5 Hz, 1H), 8.30 (d, J = 5.1
3
1
3
1
3
.2 Hz, 6H). C H NMR (101 MHz, CDCl ) δ 140.2, 140.0,
Hz, 1H), 7.60 (dd, J = 8.5, 5.2 Hz, 1H), 7.45 (d, J = 5.6 Hz,
1
3
1
1
1
38.6, 137.0, 137.0, 133.8, 133.3, 132.1, 129.7, 129.0, 128.4, 127.6,
4H), 7.26 (d, J = 5.9 Hz, 7H), 4.18 (s, 3H). C H NMR (101
1
9
27.2, 125.9, 122.8, 121.1, 115.7 (q, J = 287.4 Hz). F NMR (376
) δ -69.11 (s, 3F). HRMS m/z (EI) calcd for
O]: 480.1621 found 480.1627.
MHz, CDCl ) δ 160.6 (q, J = 38.7 Hz), 158.3, 138.0, 137.8, 133.1,
3
MHz, CDCl
[
3
132.8, 127.6, 127.4, 127.3, 124.1, 115.5 (q, J = 287.3 Hz), 109.0,
1
9
C
29
H
20BF
3
N
2
3
98.6. F NMR (376 MHz, CDCl ) δ -69.24 (s, 3F). HRMS
2
(
 -(N,N)-5-(p-chlorophenyl)-8-trifluoroacetylaminoqui
m/z (EI) calcd for [C24
( -(N,N)-8-acetylaminoquinolate)diphenylborane (3j).
H
18BF
3
N
2
O
2
]: 434.1413 found 434.1418.
2
nolate)diphenylborane (3e). The borane was obtained as
light yellow solid, 47.3 mg, 92% yield. mp:227.1228.7 C.
The borane was obtained as faint yellow solid,16.5 mg, 47%
1
EtOAc/petroleum ether = 1:10, R
CDCl
J = 8.1 Hz, 1H), 7.53 (dd, J = 8.3, 5.4 Hz, 1H), 7.48 (dd, J = 6.9,
f
= 0.40. H NMR (400 MHz,
yield. mp:216.8218.7 C. EtOAc/petroleum ether = 1:10, R
f
1
3
) δ 9.08 (d, J = 7.9 Hz, 1H), 8.598.34 (m, 2H), 7.79 (d,
3
= 0.49. H NMR (400 MHz, CDCl ) δ 8.96 (d, J = 7.7 Hz, 1H),
8.40 (dd, J = 19.0, 6.6 Hz, 2H), 7.80 (t, J = 8.0 Hz, 1H), 7.51
(t, J = 9.4 Hz, 6H), 7.29 (p, J = 6.4 Hz, 6H), 1.95 (s, 3H).
3
.9 Hz, 6H), 7.39 (d, J = 8.3 Hz, 2H), 7.297.17 (m, 6H).
1
3
1
13
1
3
C H NMR (101 MHz, CDCl ) δ 160.4, 145.4, 140.4, 140.3,
C H NMR (101 MHz, CDCl
3
) δ 174.3, 142.0, 139.5, 139.0,
1
1
38.2, 136.9, 135.4, 134.6, 133.2, 132.3, 132.1, 130.9, 129.3, 127.6,
137.6, 133.5, 132.6, 127.8, 127.5, 127.1, 122.4, 118.7, 117.0. HRMS
1
9
27.2, 125.8, 123.0, 120.9, 115.6 (q, J = 287.6 Hz). F NMR (376
) δ -69.06 (s, 3F). HRMS m/z (EI) calcd for
O]: 514.1231 found 514.1244.
m/z (EI) calcd for [C23
( -(N,N)-8-pentafluoropropylaminoquinolate)diphenyl
borane (3k). The borane was obtained as faint yellow solid,
H
19BN
2
O]: 350.1590 found 350.1597.
2
MHz, CDCl
[
3
C
29
H
3 2
19BClF N
2
(
 -(N,N)-5-(p-phenylacetyl)-8-trifluoroacetylaminoqui
34.1 mg, 75% yield. mp:172.4173.8 C. EtOAc/petroleum
1
nolate)diphenylborane (3f). The borane was obtained as
ether = 1:10, R
f
= 0.45. H NMR (400 MHz, CDCl
3
) δ 9.14 (d,
light yellow solid, 44.9 mg, 86% yield. mp:215.5216.8 C.
J = 7.5 Hz, 1H), 8.50 (dd, J = 18.1, 6.6 Hz, 2H), 7.92 (t, J = 8.0
1
EtOAc/petroleum ether = 1:10, R
CDCl
d, J = 8.2 Hz, 2H), 7.87 (d, J = 8.1 Hz, 1H), 7.59 (dd, J = 8.3,
f
= 0.40. H NMR (400 MHz,
Hz, 1H), 7.73 (d, J = 8.3 Hz, 1H), 7.647.60 (m, 1H), 7.55 (d,
1
3
1
3
) δ 9.12 (d, J = 8.0 Hz, 1H), 8.52 (t, J = 6.2 Hz, 2H), 8.13
J = 6.3 Hz, 4H), 7.33 (d, J = 6.6 Hz, 6H). C H NMR (101
MHz, CDCl ) δ 162.1, 161.9, 140.8, 140.2, 139.4, 136.6, 133.1,
132.1, 127.6, 127.3, 127.1, 122.9, 121.5, 120.1. F NMR (376 MHz,
CDCl ) δ -81.60 (s, 3F), -113.82 (s, 2F). HRMS m/z (EI) calcd
(
3
1
9
4
.4 Hz, 3H), 7.537.46 (m, 4H), 7.29 (m, 6H), 2.68 (s, 3H).
1
3
1
C H NMR (101 MHz, CDCl
3
) δ 197.4, 160.4 (q, J = 38.5 Hz),
3
1
1
(
15.6 (d, J = 285.5 Hz), 141.8, 140.5, 138.1, 137.0, 136.8, 133.3,
32.4, 132.3, 129.9, 129.0, 127.6, 127.3, 125.7, 123.2, 121.0, 115.6
for [C24
H
16BF
5
N
2
O]: 454.1276 found 454.1276.
2
( -(N,N)-8-heptafluorobutanoylaminoquinolate)diphe
nylborane (3l). The borane was obtained as faint yellow
1
9
q, J = 285.5 Hz). F NMR (376 MHz, CDCl
F). HRMS m/z (EI) calcd for [C31
found 522.1710.
2-(N,N)-5-(2-thienyl)-8-trifluoroacetylaminoquinolate)
3
) δ -69.19 (s,
3
H
22BF
3
N
2
O
2
]: 522.1726
solid, 31.8 mg, 63% yield. mp:245.1246.7 C.
1
EtOAc/petroleum ether = 1:10, R
CDCl
J = 8.1 Hz, 1H), 7.71 (d, J = 8.3 Hz, 1H), 7.60 (dd, J = 8.0, 5.5
f
= 0.40. H NMR (400 MHz,
(
3
) δ 9.13 (d, J = 7.8 Hz, 1H), 8.558.38 (m, 2H), 7.90 (t,
diphenylborane (3g). The borane was obtained as light
yellow solid, 46.7 mg, 96% yield. mp:193.2194.2 C.
13
1
Hz, 1H), 7.51 (d, J = 7.0 Hz, 4H), 7.397.19 (m, 6H). C H
ACS Paragon Plus Environment

Page 9 of 14
The Journal of Organic Chemistry
2
NMR (101 MHz, CDCl
40.2, 139.4, 136.6, 133.0, 132.1, 127.6, 127.3, 127.1, 122.9, 121.6,
120.1, 119.3, 119.0, 118.7, 116.5, 116.1, 115.8, 111.3, 108.9, 108.6,
3
) δ 162.3, 162.0, 161.8, 145.7, 140.9,
( -(N,N)-8-trifluoroacetylaminoquinolate)di(p-tert-but
tylphenyl)borane (3q). The borane was obtained as faint
yellow solid, 42.3 mg, 82% yield. mp:229.6230.9 C.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
19
1
1
08.3, 105.9, 105.6. F NMR (376 MHz, CDCl
3
) δ -80.13 (t, J
EtOAc/petroleum ether = 1:10, R = 0.46. H NMR (400 MHz,
f
=
8.8 Hz, 3F), -110.79 (d, J = 7.8 Hz, 2F), -124.53 (s, 2F).
CDCl ) δ 9.09 (d, J = 7.5 Hz, 1H), 8.618.49 (m, 1H), 8.44 (d,
J = 8.3 Hz, 1H), 7.90 (t, J = 8.1 Hz, 1H), 7.69 (d, J = 8.3 Hz,
3
HRMS m/z (EI) calcd for [C25
504.1233.
H
16BF
7
N
2
O]: 504.1244 found
1H), 7.60 (dd, J = 8.3, 5.2 Hz, 1H), 7.44 (d, J = 8.1 Hz, 4H),
2-(N,N)-8-pentafluorobenzoylaminoquinolate)diphen
7.32 (d, J = 7.4 Hz, 5H), 1.33 (s, 18H). C H NMR (101 MHz,
CDCl ) δ 149.7, 140.3, 140.2, 139.1, 136.7, 133.0, 132.0, 127.3,
13
1
(
ylborane (3m). The borane was obtained as faint yellow
solid, 40.7 mg, 81% yield. mp:234.1235.8 C.
3
1
9
124.3, 122.8, 121.2, 119.8, 115.7 (q, J = 287.4 Hz), 34.3, 31.3. F
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
EtOAc/petroleum ether = 1:10, R
CDCl
2H), 7.88 (t, J = 8.0 Hz, 1H), 7.64 (d, J = 8.3 Hz, 1H), 7.57
(dd, J = 7.9, 5.4 Hz, 1H), 7.297.15 (m, 10H). C H NMR
(101 MHz, CDCl ) δ 161.0, 145.0, 144.0, 143.9, 142.6, 141.5, 141.0,
140.1, 139.5, 138.2, 137.4, 135.7, 133.4, 132.4, 127.5, 127.4, 122.8,
120.0, 119.3, 114.2, 99.9. F NMR (376 MHz, CDCl
(dd, J = 21.8, 6.3 Hz, 2F), -155.35 (t, J = 20.7 Hz, 1F), -
162.46-162.58 (m, 2F). HRMS m/z (EI) calcd for
= 0.41. H NMR (400 MHz,
NMR (376 MHz, CDCl ) δ -69.02 (s, 3F). HRMS m/z (EI)
f
3
3
) δ 9.05 (d, J = 7.7 Hz, 1H), 8.41 (dd, J = 16.9, 6.6 Hz,
calcd for [C H BF N O]: 516.2560 found 516.2562.
3
1
32
3
2
2
( -(N,N)-8-trifluoroacetylaminoquinolate)di(m-chlorop
henyl)borane (3r). The borane was obtained as faint yellow
solid, 35.9 mg, 76% yield. mp:176.3177.8 C.
1
3
1
3
1
EtOAc/petroleum ether = 1:10, R = 0.45. H NMR (400 MHz,
f
1
9
3
) δ -137.84
CDCl ) δ 9.05 (d, J = 6.3 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.43
3
(d, J = 5.2 Hz, 1H), 7.90 (t, J = 8.1 Hz, 1H), 7.73 (d, J = 8.3 Hz,
1H), 7.65 (dd, J = 7.2, 5.2 Hz, 1H), 7.417.31 (m, 4H), 7.247.17
1
3
1
[C28
H
16BF
5
N
2
O]: 502.1276 found 502.1256.
(m, 4H). C H NMR (101 MHz, CDCl
3
) δ 160.1, 147.5, 140.2,
2
( -(N,N)-8-trifluoroacetylaminoquinolate)di(p-methylp
henyl)borane (3n). The borane was obtained as faint yellow
solid, 31.1 mg, 72% yield. mp:234.5235.7 C.
136.5, 133.8, 132.7, 132.3, 131.2, 129.2, 127.5, 127.4, 123.1, 121.5,
1
9
120.4, 115.5 (q, J = 287.5 Hz). F NMR (376 MHz, CDCl
3
) δ -
O]:
69.06 (s, 3F). HRMS m/z (EI) calcd for [C23
H
2 3
14BCl F N
2
1
EtOAc/petroleum ether = 1:10, R
CDCl
d, J = 8.3 Hz, 1H), 7.88 (t, J = 8.1 Hz, 1H), 7.67 (d, J = 8.3 Hz,
H), 7.587.54 (m, 1H), 7.42 (d, J = 7.5 Hz, 4H), 7.13 (d, J =
f
= 0.48. H NMR (400 MHz,
472.0528 found 472.0531.
2
3
) δ 9.10 (d, J = 7.4 Hz, 1H), 8.48 (d, J = 5.2 Hz, 1H), 8.41
( -(N,N)-8-trifluoroacetylaminoquinolate)di(m-methox
ylphenyl)borane (3s). The borane was obtained as faint
(
1
yellow solid, 34.4 mg, 74% yield. mp:157.3158.5 C.
1
3
1
1
7.5 Hz, 4H), 2.34 (s, 6H). C H NMR (101 MHz, CDCl
3
) δ
60.3 (q, J = 37.5 Hz), 142.4, 140.7, 140.1, 139.3, 136.6, 133.2,
32.0, 128.3, 127.3, 122.8, 121.1, 119.9, 112.8 (q, J = 287.4 Hz),
EtOAc/petroleum ether = 1:10, R
CDCl
f
= 0.47. H NMR (400 MHz,
1
1
3
) δ 9.05 (d, J = 7.2 Hz, 1H), 8.43 (dd, J = 18.2, 6.7 Hz,
2H), 7.86 (t, J = 8.1 Hz, 1H), 7.66 (d, J = 8.3 Hz, 1H), 7.577.53
(m, 1H), 7.21 (t, J = 7.7 Hz, 2H), 7.08 (d, J = 10.2 Hz, 4H),
1
9
2
1.2. F NMR (376 MHz, CDCl
O]: 432.1621 found 432.1612.
 -(N,N)-8-trifluoroacetylaminoquinolate)di(p-methox
3
) δ -68.89 (s, 3F). HRMS m/z
1
3
1
(
EI) calcd for [C25
H
20BF
3
N
2
6.80 (d, J = 8.1 Hz, 2H), 3.74 (s, 6H). C H NMR (101 MHz,
CDCl ) δ 158.8, 147.4, 140.6, 140.3, 139.5, 136.6, 132.0, 128.59,
127.3, 125.6, 122.9, 121.2, 120.0, 119.4, 115.6 (q, J = 287.5 Hz),
2
(
3
ylphenyl)borane (3o). The borane was obtained as faint
yellow solid, 36.2 mg, 78% yield. mp:171.8173.0 C.
EtOAc/petroleum ether = 1:10, R
CDCl
1
9
111.7, 55.0. F NMR (376 MHz, CDCl
3
) δ -69.01 (s, 3F).
1
= 0.48. H NMR (400 MHz,
HRMS m/z (EI) calcd for [C25H20BF N O ]: 464.1519 found
3 2 3
f
3
) δ 9.06 (d, J = 7.2 Hz, 1H), 8.44 (t, J = 7.5 Hz, 2H),
464.1510.
2
7
7
4
.87 (t, J = 8.1 Hz, 1H), 7.67 (d, J = 8.3 Hz, 1H), 7.58 (dd, J =
.9, 5.4 Hz, 1H), 7.40 (d, J = 8.1 Hz, 4H), 6.83 (d, J = 8.2 Hz,
H), 3.77 (s, 6H). C H NMR (101 MHz, CDCl
( -(N,N)-8-trifluoroacetylaminoquinolate)di(perfluorp
henyl)borane (3t). The borane was obtained as faint yellow
1
3
1
3
) δ 160.2 (q,
solid. 39.1 mg, 67% yield. mp:212.3213.7 C.
1
J = 39.0 Hz), 158.8, 140.6, 140.1, 139.3, 137.3, 136.6, 136.5, 134.4,
EtOAc/petroleum ether = 1:10, R
CDCl
Hz, 1H), 7.90 (t, J = 8.0 Hz, 1H), 7.857.78 (m, 1H), 7.75 (d,
f
= 0.40. H NMR (400 MHz,
1
32.0, 127.3, 122.8, 121.1, 119.9, 115.7 (q, J = 287.5 Hz), 113.0,
3
) δ 9.00 (s, 1H), 8.84 (d, J = 5.2 Hz, 1H), 8.66 (d, J = 8.2
1
9
5
4.9. F NMR (376 MHz, CDCl
]: 464.1519 found 464.1507.
 -(N,N)-8-trifluoroacetylaminoquinolate)di(p-isoprop
3
) δ -69.19 (s, 3F). HRMS m/z
1
3
1
(
EI) calcd for [C25
H
20BF
3
N
2
O
3
J = 8.3 Hz, 1H). C H NMR (101 MHz, CDCl ) δ 171.2, 159.1,
3
2
(
158.7, 150.0, 147.6, 142.4, 142.4, 142.3, 142.2, 142.2, 142.1, 141.6,
140.9, 139.9, 139.8, 139.7, 139.6, 139.3, 138.7, 138.5, 138.4, 137.1,
ylphenyl)borane (3p). The borane was obtained as faint
yellow solid, 33.7 mg, 69% yield. mp:211.6212.9 C.
136.2, 136.0, 135.9, 135.8, 132.5, 127.6, 123.3, 121.8, 120.4, 119.9,
1
19
EtOAc/petroleum ether = 1:10, R
CDCl
d, J = 8.3 Hz, 1H), 7.85 (t, J = 8.1 Hz, 1H), 7.64 (d, J = 8.3 Hz,
H), 7.55 (dd, J = 7.5, 6.0 Hz, 1H), 7.39 (d, J = 7.5 Hz, 4H),
.13 (d, J = 7.4 Hz, 4H), 2.87 (dt, J = 13.7, 6.8 Hz, 2H), 1.24 (t,
f
= 0.48. H NMR (400 MHz,
117.1, 114.2, 111.4. F NMR (376 MHz, CDCl
3
) δ -71.47 (s, 3F),
3
) δ 9.05 (d, J = 7.4 Hz, 1H), 8.48 (d, J = 5.1 Hz, 1H), 8.38
-133.79 (s, 4F), -153.85 (t, J = 19.7 Hz, 2F), -162.33 (t, J = 17.9
(
1
7
Hz, 4F). HRMS m/z (EI) calcd for [C H BF N O]: 584.0366
23
6
13
2
found 584.0360.
2
( -(N,N)-8-trifluoroacetylaminoquinolate) trifluoroace
tatephenylborane (4a). The borane was obtained as faint
yellow solid, 39.1 mg, 89% yield. mp:111.2112.3 C.
1
3
1
J = 10.7 Hz, 12H). C H NMR (101 MHz, CDCl
J = 35.9 Hz), 147.4, 142.8, 140.8, 140.3, 139.2, 136.7, 133.2, 132.0,
3
) δ 160.4 (q,
1
1
27.5, 127.3, 125.5, 122.8, 121.1, 119.8, 115.7 (q, J = 287.4 Hz),
EtOAc/petroleum ether = 1:10, R = 0.46. H NMR (400 MHz,
f
19
3
3.7, 23.9, 23.9. F NMR (376 MHz, CDCl
3
) δ -69.02 (s, 3F).
CDCl ) δ 8.96 (d, J = 7.7 Hz, 1H), 8.66 (d, J = 8.3 Hz, 1H),
3
HRMS m/z (EI) calcd for [C29
88.2243.
H
28BF
3
N
2
O]: 488.2247 found
8.40 (d, J = 5.2 Hz, 1H), 7.92 (t, J = 8.1 Hz, 1H), 7.78 (d, J =
8.4 Hz, 1H), 7.73 (dd, J = 8.3, 5.3 Hz, 1H), 7.477.44 (m, 2H),
4
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 14
.317.28 (m, 3H). 13C H NMR (101 MHz, CDCl
q, J = 39.1 Hz), 157.7 (q, J = 41.4 Hz), 142.0, 140.6, 139.4, 136.5,
32.3, 130.6, 128.6, 128.0, 127.0, 123.1, 121.0, 120.5, 115.5 (q, J =
1
( -(N,N)-8-trifluoroacetyl-2-methyl-aminoquinolate)tri
2
7
(
1
2
3
) δ 159.3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
fluoroacetatephenylborane (4f). The borane was obtained
as faint yellow solid, 40.4 mg, 89% yield. mp:230.8239.5
C. EtOAc/petroleum ether = 1:10, R = 0.48. H NMR (400
19
1
87.2 Hz), 114.8 (q, J = 286.5 Hz). F NMR (376 MHz, CDCl
3
)
f
δ -70.89 (s, 3F), -76.33 (s, 3F). HRMS m/z (EI) calcd for
]: 440.0767, found 440.0771.
 -(N,N)-8-trifluoroacetyl-5-chloro-aminoquinolate) tri
MHz, CDCl ) δ 8.93 (d, J = 7.7 Hz, 1H), 8.49 (d, J = 8.4 Hz,
3
[C
19
H
11BF
6
N
2
O
3
1H), 7.80 (t, J = 8.0 Hz, 1H), 7.71 (d, J = 8.3 Hz, 1H), 7.477.41
2
13
1
(
(m, 3H), 7.28 (s, 3H), 2.54 (s, 3H). C H NMR (101 MHz,
fluoroacetatephenylborane (4b). The borane was obtained
CDCl ) δ 158.7 (q, J = 40.0 Hz), 158.3 (q, J = 42.9 Hz), 154.8,
3
as faint yellow solid, 37.9 mg, 82% yield. mp:234.2235.4 C.
141.6, 139.0, 136.9, 131.5, 131.1, 128.4, 127.7, 125.6, 125.3, 120.9,
1
19
EtOAc/petroleum ether = 1:10, R
CDCl
1H), 7.96 (d, J = 8.3 Hz, 1H), 7.907.79 (m, 1H), 7.42 (d, J =
f
= 0.45. H NMR (400 MHz,
120.4, 115.5 (q, J = 287.2 Hz), 114.9 (q, J = 286.9 Hz), 20.0. F
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
) δ 8.92 (dd, J = 18.3, 8.4 Hz, 2H), 8.45 (d, J = 5.0 Hz,
NMR (376 MHz, CDCl ) δ -70.98 (s, 3F), -76.25 (s, 3F).
3
HRMS m/z (EI) calcd for [C H BF N O ]: 454.0923, found
20
13
6
2
3
1
3
1
6.4 Hz, 2H), 7.30 (d, J = 6.1 Hz, 3H). C H NMR (101 MHz,
CDCl ) δ 159.3 (q, J = 39.3 Hz), 157.8 (q, J = 42.1 Hz), 141.4,
139.7, 138.6, 137.1, 131.7, 130.7, 128.8, 128.1, 125.4, 124.4, 123.7,
454.0918.
2
3
( -(N,N)-8-trifluoroacetyl-6-methoxyl-aminoquinolate)
trifluoroacetatephenylborane (4g). The borane was
obtained as faint yellow solid, 30.6 mg, 65% yield.
1
9
121.1, 115.4 (q, J = 287.1 Hz), 114.7 (q, J = 286.4 Hz). F NMR
(376 MHz, CDCl ) δ -71.01 (s, 3F), -76.33 (s, 3F). HRMS m/z
]: 474.0377, found 474.0372.
3
mp:145.3146.7 C. EtOAc/petroleum ether = 1:10, R = 0.48.
f
1
(EI) calcd for [C19
( -(N,N)-8-trifluoroacetyl-5-bromo-aminoquinolate) tri
fluoroacetatephenylborane (4c). The borane was obtained
H
10BClF
6
N
2
O
3
H NMR (400 MHz, CDCl ) δ 8.64 (s, 1H), 8.46 (d, J = 8.3
3
2
Hz, 1H), 8.16 (d, J = 5.1 Hz, 1H), 7.797.54 (m, 1H), 7.527.38
(m, 2H), 7.29 (d, J = 5.1 Hz, 3H), 7.00 (s, 1H), 4.02 (s, 3H).
1
3
1
as faint yellow solid, 42.5 mg, 82% yield. mp:242.7244.5 C.
C H NMR (101 MHz, CDCl ) δ 163.0, 159.4 (q, J = 39.3 Hz),
3
1
EtOAc/petroleum ether = 1:10, R
CDCl
8.43 (d, J = 4.7 Hz, 1H), 8.14 (d, J = 8.2 Hz, 1H), 7.917.75 (m,
f
= 0.46. H NMR (400 MHz,
157.6 (q, J = 41.6 Hz), 140.2, 139.7, 137.1, 133.4, 130.7, 128.6,
128.0, 127.9, 123.4, 115.4 (q, J = 287.2 Hz), 114.8 (q, J = 286.7
3
) δ 8.90 (d, J = 8.4 Hz, 1H), 8.85 (d, J = 8.1 Hz, 1H),
1
9
Hz), 98.4, 56.3. F NMR (376 MHz, CDCl ) δ -71.04 (s, 3F),
3
1
3
1
1H), 7.42 (d, J = 5.7 Hz, 2H), 7.31 (s, 3H). C H NMR (101
MHz, CDCl ) δ 159.4 (q, J = 39.5 Hz), 157.8 (q, J = 41.8 Hz),
42.0, 141.4, 139.2, 137.2, 135.3, 130.7, 128.8, 128.1, 126.8, 124.0,
-76.37 (s, 3F). HRMS m/z (EI) calcd for [C H BF N O ]:
20
13
6
2
4
3
470.0873, found 470.0877.
2
1
1
( -(N,N)-8-acetyl-aminoquinolate)trifluoroacetatephen
ylborane (4h). The borane was obtained as faint yellow
1
9
21.6, 115.4 (q, J = 286.6 Hz), 114.7 (q, J = 286.3 Hz). F NMR
(
(
376 MHz, CDCl
3
) δ -71.01 (s, 3F), -76.34 (s, 3F). HRMS m/z
]: 517.9872, found 517.9867.
solid, 30.1 mg, 78% yield. mp:152.3153.7 C.
1
EI) calcd for [C19
H
10BBrF
6
N
2
O
3
EtOAc/petroleum ether = 1:10, R = 0.50. H NMR (400 MHz,
f
2
(
 -(N,N)-8-trifluoroacetyl-5-(p-chlorophenyl)-aminoqui
CDCl ) δ 8.84 (d, J = 7.7 Hz, 1H), 8.56 (d, J = 8.2 Hz, 1H),
3
nolate)trifluoroacetatephenylborane (4d). The borane was
obtained as faint yellow solid, 51.1 mg, 93% yield.
8.41 (d, J = 5.0 Hz, 1H), 7.79 (t, J = 8.0 Hz, 1H), 7.64 (dd, J =
8.3, 5.3 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.557.49 (m, 2H),
1
3
1
mp:149.6153.2 C. EtOAc/petroleum ether = 1:10, R
f
= 0.40.
7.397.28 (m, 3H), 2.06 (s, 3H). C H NMR (101 MHz,
1
H NMR (400 MHz, CDCl
d, J = 8.4 Hz, 1H), 8.43 (d, J = 4.9 Hz, 1H), 7.88 (d, J = 7.9
Hz, 1H), 7.787.68 (m, 1H), 7.57 (d, J = 7.8 Hz, 2H), 7.47 (d,
3
) δ 9.02 (d, J = 7.9 Hz, 1H), 8.72
CDCl ) δ 173.2, 157.5 (q, J = 40.8 Hz), 141.6, 140.4, 136.9, 135.5,
3
(
133.9, 132.6, 132.5, 131.1, 128.5, 128.2, 127.9, 127.6, 127.1, 122.4,
1
9
118.7, 118.0, 114.9 (q, J = 287.0 Hz), 25.0. F NMR (376 MHz,
1
3
1
J = 7.2 Hz, 4H), 7.33 (s, 3H). C H NMR (101 MHz, CDCl
3
)
CDCl ) δ -76.15 (s, 3F). HRMS m/z (EI) calcd for
3
δ 159.3 (q, J = 39.2 Hz), 157.8 (q, J = 41.7 Hz), 140.7, 140.7,
[C H BF N O ]: 386.1050, found 386.1033.
1
9
14
3
2
3
2
1
1
39.0, 136.7, 135.0, 132.9, 132.4, 131.0, 130.7, 129.4, 128.7, 128.0,
( -(N,N)-8-phenyl-aminoquinolate)trifluoroacetatephe
nylborane (4i). The borane was obtained as faint yellow
solid, 34.0 mg, 76% yield. mp:68.870.3 C.
25.6, 123.2, 120.8, 115.4 (q, J = 287.2 Hz), 114.8 (q, J = 286.3
1
9
Hz). F NMR (376 MHz, CDCl
F). HRMS m/z (EI) calcd for [C25
found 550.0685.
2-(N,N)-8-trifluoroacetyl-5-thiophene-aminoquinolate)
3
) δ -70.98 (s, 3F), -76.36 (s,
1
3
H
14BClF
6
N
2
O
3
]: 550.0690,
EtOAc/petroleum ether = 1:10, R = 0.49. H NMR (400 MHz,
f
CDCl ) δ 8.71 (d, J = 7.6 Hz, 1H), 8.54 (d, J = 8.2 Hz, 1H), 8.31
3
(
(d, J = 4.9 Hz, 1H), 7.81 (t, J = 7.7 Hz, 1H), 7.57 (t, J = 6.8 Hz,
trifluoroacetatephenylborane (4e). The borane was
obtained as faint yellow solid, 37.1 mg, 71% yield.
2H), 7.15 (dd, J = 7.5, 4.4 Hz, 1H), 7.076.87 (m, 7H), 6.79
13
1
(
3
d, J = 7.2 Hz, 2H). C H NMR (101 MHz, CDCl ) δ 174.1,
mp:199.3200.5 C. EtOAc/petroleum ether = 1:10, R
f
= 0.40.
157.7, 141.8, 141.4, 140.8, 138.0, 137.5, 132.4, 130.9, 129.2, 127.7,
1
H NMR (400 MHz, CDCl
d, J = 8.5 Hz, 1H), 8.41 (d, J = 5.1 Hz, 1H), 7.93 (d, J = 8.0 Hz,
H), 7.73 (dd, J = 8.1, 5.4 Hz, 1H), 7.647.55 (m, 1H), 7.49 (s,
3
) δ 8.99 (d, J = 8.0 Hz, 1H), 8.88
127.3, 127.3, 127.1, 126.8, 122.5, 120.0, 118.4, 114.9 (q, J = 287.1
(
19
Hz). F NMR (376 MHz, CDCl
3
) δ -76.04 (s, 3F). HRMS m/z
1
3
(EI) calcd for [C H BF N O ]: 448.1206, found 448.1208.
24
16
3
2
3
1
3
1
2
H), 7.32 (t, J = 4.8 Hz, 4H). C H NMR (101 MHz, CDCl
3
)
( -(N,N)-8-trifluoroacetyaminoquinolate) trifluoroacet
ate-p-methyl-phenyl-borane (4j). The borane was obtained
as faint yellow solid, 36.8 mg, 81% yield. mp:207.6208.4 C.
δ 159.3 (q, J = 39.2 Hz), 157.8 (q, J = 41.5 Hz), 141.1, 140.7, 138.6,
1
1
37.2, 136.8, 132.0, 130.8, 129.2, 128.7, 128.6, 128.1, 127.3, 125.9,
24.7, 123.1, 121.0, 115.6 (q, J = 287.2 Hz), 114.9 (q, J = 286.6
1
EtOAc/petroleum ether = 1:10, R
f
= 0.48. H NMR (400 MHz,
19
Hz), 100.0. F NMR (376 MHz, CDCl
7
5
3
) δ -70.87 (s, 3F), -
S]:
CDCl ) δ 8.96 (d, J = 7.6 Hz, 1H), 8.66 (d, J = 8.2 Hz, 1H),
3
6.31 (s, 3F). HRMS m/z (EI) calcd for [C23
22.0644, found 522.0661.
6 2 3
H13BF N O
8
.40 (d, J = 5.0 Hz, 1H), 7.93 (t, J = 8.0 Hz, 1H), 7.837.61 (m,
2H), 7.32 (d, J = 7.3 Hz, 2H), 7.10 (d, J = 7.4 Hz, 2H), 2.32 (s,
ACS Paragon Plus Environment

Page 11 of 14
H). C H NMR (101 MHz, CDCl
The Journal of Organic Chemistry
1
3
1
2
3
3
) δ 157.7 (q, J = 41.3 Hz),
( -(N,N)-8-trifluoroacetyaminoquinolate) trichloroacet
ateborane (4o). The borane was obtained as faint yellow
solid, 40.5 mg, 83% yield. mp:222.6223.5 C.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
1
41.8, 140.5, 139.5, 138.3, 136.5, 132.5, 130.7, 128.7, 127.0, 123.0,
21.1, 120.3, 115.5 (q, J = 286.6 Hz), 114.8 (q, J = 286.3 Hz), 21.4.
19
1
F NMR (376 MHz, CDCl
HRMS m/z (EI) calcd for [C20
54.0918.
2-(N,N)-8-trifluoroacetyaminoquinolate) trifluoroacet
3
) δ -70.92 (s, 3F), -76.37 (s, 3F).
EtOAc/petroleum ether = 1:10, R
f
= 0.40. H NMR (400 MHz,
H
13BF
6
N
2
O
3
]: 454.0923, found
CDCl ) δ 8.99 (d, J = 7.7 Hz, 1H), 8.66 (d, J = 8.3 Hz, 1H),
3
4
8.39 (d, J = 5.0 Hz, 1H), 7.93 (t, J = 8.0 Hz, 1H), 7.837.66
(m, 2H), 7.51 (d, J = 4.7 Hz, 2H), 7.31 (d, J = 4.5 Hz, 3H).
(
13
1
ate-p-tert-butyl-phenyl-borane (4k). The borane was
C H NMR (101 MHz, CDCl ) δ 161.6, 161.2, 160.8, 141.9,
3
obtained as faint yellow solid, 40.1 mg, 80% yield.
141.6, 140.2, 139.6, 136.7, 132.4, 130.8, 130.6, 128.6, 128.0, 127.0,
1
9
mp:227.6228.4 C. EtOAc/petroleum ether = 1:10, R
f
= 0.45.
123.0, 121.2, 120.3, 66.0. F NMR (376 MHz, CDCl ) δ -70.67
3
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
H NMR (400 MHz, CDCl
3
) δ 8.96 (d, J = 7.7 Hz, 1H), 8.64
(s, 3F). HRMS m/z (EI) calcd for [C H BCl F N O ]:
1
9
11
3
3
2
3
(d, J = 8.2 Hz, 1H), 8.43 (d, J = 5.1 Hz, 1H), 7.90 (t, J = 8.1 Hz,
487.9880, found 487.9875.
2
1H), 7.807.68 (m, 2H), 7.39 (d, J = 8.0 Hz, 2H), 7.32 (d, J =
( -(N,N)-8-trifluoroacetyaminoquinolate) undecylaceta
teborane (4p). The borane was obtained as faint yellow
solid, 22.9 mg, 45% yield. mp:94.296.1 C.
1
3
1
3
8.1 Hz, 2H), 1.30 (s, 11H). C H NMR (101 MHz, CDCl ) δ
159.4 (q, J = 39.1 Hz), 157.7 (q, J = 41.4 Hz), 151.4, 141.7, 140.6,
139.5, 136.5, 132.4, 130.5, 127.0, 124.8, 123.0, 121.0, 120.3, 115.5
(q, J = 287.3 Hz), 114.8 (q, J = 286.6 Hz), 34.5, 31.2. 19F NMR
1
EtOAc/petroleum ether = 1:10, R = 0.42. H NMR (400 MHz,
f
CDCl ) δ 8.97 (d, J = 7.7 Hz, 1H), 8.57 (d, J = 8.3 Hz, 1H), 8.37
3
3
(376 MHz, CDCl ) δ -70.93 (s, 3F), -76.38 (s, 3F). HRMS
(d, J = 5.1 Hz, 1H), 7.89 (t, J = 8.1 Hz, 1H), 7.737.64 (m, 2H),
7.447.42 (m, 2H), 7.27 (d, J = 5.8 Hz, 3H), 5.82 (m, 1H),
5.02.ꢀ2 (m, 2H), 2.442.35 (m, 2H), 2.04 (dd, J = 13.2, 6.3
Hz, 2H), 1.391.28 (m, 12H). C H NMR (101 MHz, CDCl )
δ 175.2, 140.8, 140.0, 139.9, 139.2, 136.8, 132.1, 130.5, 127.9,
m/z (EI) calcd for [C23
H
19BF
6
N
2
O
3
]: 496.1393, found
496.1396.
2
13
1
( -(N,N)-8-trifluoroacetyaminoquinolate) propionicate
borane (4l). The borane was obtained as faint yellow solid,
3
2
0.1 mg, 50% yield. mp:153.1155.4 C. EtOAc/petroleum
127.7, 127.0, 122.6, 120.7, 119.9, 114.1, 36.1, 33.8, 29.3, 29.3, 29.2,
29.1, 29.0, 28.9, 24.8, 24.7. F NMR (376 MHz, CDCl ) δ -
1
19
ether = 1:10, R
f
3
= 0.49. H NMR (400 MHz, CDCl ) δ 8.94 (d,
3
J = 7.8 Hz, 1H), 8.54 (d, J = 8.3 Hz, 1H), 8.35 (d, J = 5.2 Hz,
70.74 (s, 3F). HRMS m/z (EI) calcd for [C28
510.2085, found 510.2091.
3 2 3
H30BF N O ]:
1
H), 7.85 (t, J = 8.1 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.657.58
(
m, 1H), 7.43 (d, J = 2.6 Hz, 2H), 7.25 (d, J = 1.4 Hz, 3H),
2
( -(N,N)-8-trifluoroacetyaminoquinolate) benzoatebor
ane (4q). The borane was obtained as faint yellow solid, 38.1
mg, 85% yield. mp:239.3241.8 C. EtOAc/petroleum ether
1
3
1
2
.472.41 (m, 2H), 1.08 (t, J = 7.5 Hz, 3H). C H NMR (101
) δ 175.9, 159.2 (q, J = 39.0 Hz), 140.8, 140.0,
36.7, 135.6, 133.6, 132.7, 132.0, 131.0, 130.5, 128.0, 127.0, 127.7,
MHz, CDCl
3
1
1
1
=
7
1:10, R
.6 Hz, 1H), 8.59 (d, J = 8.2 Hz, 1H), 8.41 (d, J = 4.8 Hz, 1H),
8.15 (d, J = 7.6 Hz, 2H), 7.91 (t, J = 7.9 Hz, 1H), 7.76 (d, J =
.4 Hz, 1H), 7.707.62 (m, 1H), 7.56 (t, J = 6.9 Hz, 3H), 7.45
f 3
= 0.46. H NMR (400 MHz, CDCl ) δ 9.00 (d, J =
1
9
27.0, 122.7, 120.6, 120.0, 115.7 (q, J = 287.5 Hz), 29.3, 9.0. F
) δ 70.78 (s, 3F). HRMS m/z (EI)
]: 400.1206, found 400.1213.
NMR (376 MHz, CDCl
3
calcd for [C20
H
16BF
3
N
2
O
3
8
2
13
1
(
 -(N,N)-8-trifluoroacetyaminoquinolate)-n-butylaceta
(t, J = 7.4 Hz, 2H), 7.31 (s, 3H). C H NMR (101 MHz,
teborane (4m). The borane was obtained as faint yellow
CDCl ) δ 167.3, 159.3 (q, J = 39.1 Hz), 141.0, 140.2, 140.0, 136.8,
3
solid, 21.5 mg, 52% yield. mp:166.4167.7 C.
133.0, 132.7, 132.1, 130.6, 130.1, 129.9, 128.3, 128.1, 127.9, 127.0,
122.8, 120.7, 120.2, 115.8 (q, J = 289.3 Hz). F NMR (376 MHz,
1
19
EtOAc/petroleum ether = 1:10, R
CDCl
f
= 0.48. H NMR (400 MHz,
3
) δ 8.94 (d, J = 7.8 Hz, 1H), 8.54 (d, J = 8.3 Hz, 1H),
CDCl ) δ -70.67 (s, 3F). HRMS m/z (EI) calcd for
3
8
8
.34 (d, J = 5.1 Hz, 1H), 7.85 (t, J = 8.1 Hz, 1H), 7.69 (d, J =
.4 Hz, 1H), 7.63 (dd, J = 8.2, 5.4 Hz, 1H), 7.42 (d, J = 2.5 Hz,
[C H BF N O ]: 448.1206, found 448.1201.
24
16
3
2
3
2
(
 -(N,N)-8-trifluoroacetyaminoquinolate)-2,4-dimethy
2
H), 7.25 (d, J = 1.2 Hz, 3H), 2.39 (dd, J = 17.5, 7.9 Hz, 2H),
lphenylacetateborane (4r). The borane was obtained as
faint yellow solid, 34.7 mg, 73% yield. mp:215.2216.3 C.
1
3
1
1
.631.60 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H). C H NMR (101
MHz, CDCl ) δ 175.0, 159.2 (q, J = 38.9 Hz), 141.5, 140.8, 140.0,
39.9, 136.7, 133.6, 132.0, 130.5, 127.9, 127.7, 127.0, 122.6, 120.6,
20.0, 115.7 (q, J = 287.6 Hz), 38.1, 18.2, 13.7. 19F NMR (376
) δ -70.72 (s, 3F). HRMS m/z (EI) calcd for
]: 414.1363, found 414.1352.
1
3
EtOAc/petroleum ether = 1:10, R
CDCl ) δ 8.98 (d, J = 7.7 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.39
d, J = 5.1 Hz, 1H), 8.19 (d, J = 7.9 Hz, 1H), 7.85 (t, J = 8.0 Hz,
H), 7.68 (d, J = 8.4 Hz, 1H), 7.617.57 (m, 1H), 7.52 (d, J =
.6 Hz, 2H), 7.27 (d, J = 4.6 Hz, 3H), 7.11 (d, J = 8.0 Hz, 1H),
= 0.45. H NMR (400 MHz,
f
1
1
3
(
1
4
MHz, CDCl
3
[C
21
H
3 2 3
18BF N O
2
(
 -(N,N)-8-trifluoroacetyaminoquinolate)trimethylacet
13
1
7.00 (s, 1H), 2.43 (s, 3H), 2.34 (s, 3H). C H NMR (101 MHz,
ateborane (4n). The borane was obtained as faint yellow
CDCl ) δ 167.9, 159.3 (q, J = 39.0 Hz), 142.2, 140.8, 140.6,
3
solid, 35.1 mg, 82% yield. mp:236.5237.7 C.
140.0, 139.9, 136.7, 132.4, 132.0, 131.6, 130.5, 128.5, 127.9, 127.8,
1
EtOAc/petroleum ether = 1:10, R
CDCl
.28 (s, 1H), 7.88 (d, J = 7.5 Hz, 1H), 7.69 (dd, J = 22.3, 5.2
f
= 0.45. H NMR (400 MHz,
127.1, 126.5, 122.6, 120.7, 120.1, 115.8 (q, J = 287.6 Hz), 21.9, 21.3.
3
) δ 8.98 (d, J = 7.2 Hz, 1H), 8.57 (d, J = 8.0 Hz, 1H),
19
F NMR (376 MHz, CDCl
calcd for [C26 ]: 476.1519, found 476.1514.
 -(N,N)-8-trifluoroacetyaminoquinolate)-2,3-dimethy
3
) δ -70.68 (s, 3F). HRMS m/z (EI)
8
H
3 2 3
20BF N O
13
1
Hz, 2H), 7.46 (s, 2H), 7.27 (s, 3H), 1.25 (s, 9H). C H NMR
101 MHz, CDCl ) δ 179.7, 140.9, 140.0, 139.4, 136.9, 132.1,
30.6, 129.0, 128.0, 127.8, 127.0, 122.7, 120.8, 120.0, 116.4 (q, J
2
(
(
1
=
3
phenylacetateborane (4s). The borane was obtained as faint
yellow solid, 34.7 mg, 73% yield. mp:193.6195.4 C.
EtOAc/petroleum ether = 1:10, R
19
278.9 Hz), 39.7, 27.2. F NMR (376 MHz, CDCl
3
) δ -70.59
1
f
= 0.45. H NMR (400 MHz,
(
s, 3F). HRMS m/z (EI) calcd for [C22
H
20BF
3
N
2
O
3
]: 428.1519,
CDCl ) δ 8.99 (d, J = 7.7 Hz, 1H), 8.53 (d, J = 8.2 Hz, 1H),
3
found 428.1514.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 14
8
8
.40 (d, J = 5.1 Hz, 1H), 8.00 (d, J = 7.8 Hz, 1H), 7.87 (t, J =
.1 Hz, 1H), 7.70 (d, J = 8.4 Hz, 1H), 7.62 (dd, J = 8.2, 5.5 Hz,
* E-mail: renhuaqiu1@hnu.edu.cn (R.Q.).
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Author Contributions
1H), 7.51 (d, J = 3.8 Hz, 2H), 7.28 (d, J = 6.8 Hz, 4H), 7.19 (t,
J = 7.6 Hz, 1H), 2.32 (s, 3H), 2.27 (s, 3H). C H NMR (101
MHz, CDCl ) δ 169.0, 159.3 (q, J = 38.8 Hz), 140.9, 139.9,
138.0, 137.8, 136.8, 132.9, 132.6, 132.1, 130.5, 128.5, 128.0, 127.8,
127.1, 125.1, 122.7, 120.8, 120.0, 115.8 (q, J = 287.6 Hz), 20.5,
16.6. F NMR (376 MHz, CDCl
(EI) calcd for [C26
( -(N,N)-8-trifluoroacetyaminoquinolate)-5-methoxyl-
2-bromophenylacetateborane (4t). The borane was
obtained as faint yellow solid, 35.0 mg, 63% yield.
The manuscript was written through contributions of all
13
1
+
authors. T.B. Yang and X. Cao contribute equally to this
3
work.
Notes
The authors declare no competing financial interest.
1
9
3
) δ -70.67 (s, 3F). HRMS m/z
H
20BF
3
N
2
O
3
]: 476.1519, found 476.1514.
ACKNOWLEDGMENT
2
The authors thank Prof. Nobuaki Kambe (Osaka University),
Prof. Wai-Yeung Huang (The Hong Kong Polytechnic
University) and Prof. Lin Yuan (Hunan University) for helpful
discussion. The authors thank the Natural Science Foundation
of China (Nos. 21676076, 21878071, 21971060), Hu-Xiang High
Talent of Hunan Province (2018RS3042), and Recruitment
Program for Foreign Experts of China (WQ20164300353) for
financial support.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
mp:183.5184.7 C. EtOAc/petroleum ether = 1:10, R
f
= 0.45.
1
3
H NMR (400 MHz, CDCl ) δ 9.05 (d, J = 7.7 Hz, 1H), 8.60
(dd, J = 20.9, 8.3 Hz, 2H), 7.94 (t, J = 8.1 Hz, 1H), 7.857.66
(m, 2H), 7.667.44 (m, 4H), 7.32 (dd, J = 2.9, 2.1 Hz, 3H),
6.92 (dd, J = 8.8, 2.6 Hz, 1H), 3.86 (s, 3H). C H NMR (101
MHz, CDCl ) δ 166.7, 159.2 (q, J = 38.8 Hz), 141.1, 140.4, 139.8,
136.7, 135.1, 134.6, 132.0, 130.6, 128.0, 127.8, 127.0, 122.7, 120.8,
1
3
1
3
REFERENCES
1
9
(1) Selected examples for luminescent materials: (a) Maeda, C.;
Nagahata, K.; Shirakawa, T.; Ema, T. Azahelicene-Fused BODIPY
Analogues Showing Circularly Polarized Luminescence. Angew.
Chem. Int. Ed. Engl. 2020, 59, 1-6; (b) Chi, W.; Chen, J.; Liu, W.;
Wang, C.; Qi, Q.; Qiao, Q.; Tan, T. M.; Xiong, K.; Liu, X.; Kang, K.;
Chang, Y. T.; Xu, Z.; Liu, X. A General Descriptor DeltaE Enables
the Quantitative Development of Luminescent Materials Based
on Photoinduced Electron Transfer. J. Am. Chem. Soc. 2020, 142,
1
20.2, 118.5, 116.3, 115.7 (q, J = 287.7 Hz), 111.3, 55.5. F NMR
(376 MHz, CDCl ) δ -70.56 (s, 3F). HRMS m/z (EI) calcd for
Br]: 556.0417, found 556.0423.
3
[
C
25
H
3 2 4
17BF N O
2
(
 -(N,N)-8-trifluoroacetyaminoquinolate) piperinicacet
ateborane (4u). The borane was obtained as faint yellow
solid, 35.4 mg, 72% yield. mp:163.4165.1 C.
1
EtOAc/petroleum ether = 1:10, R
CDCl ) δ 8.99 (d, J = 7.7 Hz, 1H), 8.57 (d, J = 8.3 Hz, 1H),
.40 (d, J = 5.0 Hz, 1H), 7.90 (t, J = 8.0 Hz, 1H), 7.75 (t, J =
.4 Hz, 2H), 7.667.63 (m, 1H), 7.567.53 (m, 3H), 7.30 (d, J
f
= 0.42. H NMR (400 MHz,
6777-6785; (c) Gartzia-Rivero, L.; Ray Leiva, C.; Sanchez-
3
Carnerero, E. M.; Banuelos, J.; Moreno, F.; Maroto, B. L.; Garcia-
Moreno, I.; Infantes, L.; Mendez, B.; Lopez-Arbeloa, I.; de la Moya,
S. Chiral Microneedles from an Achiral Bis(boron
dipyrromethene): Spontaneous Mirror Symmetry Breaking
Leading to a Promising Photoluminescent Organic Material.
Langmuir 2019, 35, 5021-5028; (d) Tian, D.; Qi, F.; Ma, H. L.; Wang,
X. Q.; Pan, Y.; Chen, R. F.; Shen, Z.; Liu, Z. P.; Huang, L.; Huang,
W. Domino-like multi-emissions across red and near infrared
from solid-state 2-/2,6-aryl substituted BODIPY dyes. Nat.
Commun. 2018, 9, 2688; (e) Zhao, Y.; He, S. L.; Yang, J. Y.; Sun, H.;
Shen, X. F.; Han, X. G.; Ni, Z. H. Study on TICT emission of TPE-
BODIPY derivatives mediated by methyl group on BODIPY. Opt.
Mater. 2018, 81, 102-108.
(2) Selected examples for fluorescent dyes: (a) Li, G.; Hirano, T.;
Yamada, K. Bright near-infrared chemiluminescent dyes:
Phthalhydrazides conjugated with fluorescent BODIPYs. Dyes
Pigm. 2020, 178, 108339; (b) Radunz, S.; Kraus, W.; Bischoff, F. A.;
Emmerling, F.; Tschiche, H. R.; Resch-Genger, U. Temperature-
and Structure-Dependent Optical Properties and Photophysics of
BODIPY Dyes. J. Phys. Chem. A. 2020, 124, 1787-1797; (c) Boens,
N.; Verbelen, B.; Ortiz, M. J.; Jiao, L.; Dehaen, W. Synthesis of
BODIPY dyes through postfunctionalization of the boron
dipyrromethene core. Coord. Chem. Rev. 2019, 399; (d) Li, G. L.;
Otsuka, Y.; Matsumiya, T.; Suzuki, T.; Li, J. Y.; Takahashi, M.;
Yamada, K. A Straightforward Substitution Strategy to Tune
BODIPY Dyes Spanning the Near-Infrared Region via Suzuki(-
)Miyaura Cross-Coupling. Materials 2018, 11, 1297.
8
7
1
3
1
=
4.3 Hz, 3H), 6.85 (d, J = 8.1 Hz, 1H), 6.03 (s, 2H). C H
) δ 166.6, 151.4, 147.6, 140.9, 140.2,
40.1, 136.8, 132.1, 130.6, 128.0, 127.9, 127.0, 126.3, 125.7, 122.7,
NMR (101 MHz, CDCl
3
1
1
(
1
9
20.7, 120.1, 115.7 (q, J = 287.7 Hz), 109.9, 107.9, 101.7. F NMR
376 MHz, CDCl ) δ -70.66 (s, 3F). HRMS m/z (EI) calcd
]: 492.1104, found 492.1115.
3
for [C25
H
16BF
3
N
2
O
5
2
(
 -(N,N)-8-trifluoroacetyaminoquinolate) pentafluorob
enzoateborane (4v). The borane was obtained as faint
yellow solid, 47.8 mg, 89% yield. mp:189.1190.2 C.
1
EtOAc/petroleum ether = 1:10, R
CDCl
.46 (d, J = 4.7 Hz, 1H), 7.94 (t, J = 8.0 Hz, 1H), 7.857.68
f
= 0.40. H NMR (400 MHz,
3
) δ 9.02 (d, J = 7.6 Hz, 1H), 8.65 (d, J = 8.2 Hz, 1H),
8
1
3
1
(
(
m, 2H), 7.49 (s, 2H), 7.29 (d, J = 9.5 Hz, 3H). C H NMR
101 MHz, CDCl ) δ 159.4, 159.1, 146.8, 144.3, 141.4, 140.1, 139.7,
3
1
36.6, 132.4, 130.4, 128.3, 127.9, 127.1, 122.9, 121.0, 120.2, 115.6
1
9
(
q, J = 287.1 Hz). F NMR (376 MHz, CDCl
3
) δ -70.99 (s,
3
F), -139.10 (d, J = 18.8 Hz, 2F), -149.60 (t, J = 20.9 Hz, 1F),
-
160.69 (dt, J = 20.4, 6.2 Hz, 2F). HRMS m/z (EI) calcd for
]: 538.0735, found 538.0729.
[C
24
H
11BF
8
N
2
O
3
ASSOCIATED CONTENT
Supporting Information
(3) Selected examples for photosensitizer: (a) Cao, J. J.; Zhang,
M. S.; Li, X. Q.; Yang, D. C.; Xu, G.; Liu, J. Y. A glutathione-
responsive photosensitizer with fluorescence resonance energy
The Supporting Information is available free of charge on the
ACS Publications website at DOI: xxxxxxxxxxxx.
Detailed
transfer
characteristics
for
imaging-guided
targeting
experimental
procedures,
compound
photodynamic therapy. Eur. J. Med. Chem. 2020, 193, 112203; (b)
Wang, C. J.; Qian, Y. A novel BODIPY-based photosensitizer with
pH-active singlet oxygen generation for photodynamic therapy in
lysosomes. Org. Biomol. Chem. 2019, 17, 8001-8007; (c) Wang, L.
F.; Bai, J.; Qian, Y. Synthesis of a triphenylamine BODIPY
characterization data, and NMR spectra (PDF).
AUTHOR INFORMATION
Corresponding Author
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The Journal of Organic Chemistry
photosensitizer with D–A configuration and its application in
intracellular simulated photodynamic therapy. New J. Chem. 2019,
3, 16829-16834.
4) Selected examples for molecular switch: (a) Dolati, H.; Haufe,
12685-12689; (d) Ke, M. R.; Yeung, S. L.; Ng, D. K.; Fong, W. P.; Lo,
P. C. Preparation and in vitro photodynamic activities of folate-
conjugated distyryl boron dipyrromethene based
photosensitizers. J. Med. Chem. 2013, 56, 8475-8483.
(9) Selected example for 2,2-(Pyridine2,6-diyl)diphenolate
derivatives: Li, P.; Chan, H.; Lai, S. L.; Ng, M.; Chan, M. Y.; Yam,
V. W. Four-Coordinate Boron Emitters with Tridentate Chelating
Ligand for Efficient and Stable Thermally Activated Delayed
Fluorescence Organic Light-Emitting Devices. Angew. Chem. Int.
Ed. Engl. 2019, 58, 9088-9094.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
4
(
L. C.; Denker, L.; Lorbach, A.; Grotjahn, R.; Horner, G.; Frank, R.
Two pi-Electrons Make the Difference: From BODIPY to BODIIM
Switchable Fluorescent Dyes. Chemistry 2020, 26, 1422-1428; (b)
Gautam, R.; Petritis, S. J.; Tomat, E. Redox-Switchable Cyan
Fluorescence of a BODIPY Analog Inspired by Propentdyopent
Pigments. Eur. J. Inorg. Chem. 2019, 2019, 68-72; (c) Shi, W.-J.;
Huang, Y.; Liu, W. C.; Xu, D.; Chen, S.-T.; Liu, F. G.; Hu, J. Q.;
Zheng, L. Y.; Chen, K. A BODIPY-based “OFF-ON” fluorescent
probe for fast and selective detection of hypochlorite in living
cells. Dyes Pigm. 2019, 170, 107566.
(10) Selected example for BPh (aq) polymer: Nagata, Y.; Chujo,
2
Y. Main-Chain-Type N,N-Chelate Organoboron Aminoquinolate
Polymers: Synthesis, Luminescence, and Energy Transfer
Behavior. Macromolecules 2008, 41, 3488–3492.
(11) Zu, W.; Day, C.; Wei, L.; Jia, X.; Xu, L. Dual aminoquinolate
diarylboron and nickel catalysed metallaphotoredox platform for
carbon-oxygen bond construction. Chem. Commun. 2020, 56,
8273-8276.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
5) Selected examples for photodynamic therapy: (a) Nguyen, V.
N.; Yim, Y.; Kim, S.; Ryu, B.; Swamy, K. M. K.; Kim, G.; Kwon, N.;
Kim, C. Y.; Park, S.; Yoon, J. Molecular Design of Highly Efficient
Heavy-Atom-Free Triplet BODIPY Derivatives for Photodynamic
Therapy and Bioimaging. Angew. Chem. Int. Ed. Engl. 2020, 59, 1-
(12) Selected example for unsing BF as starting material: Yang,
3
7
; (b) Pederzoli, M.; Wasif Baig, M.; Kyvala, M.; Pittner, J.; Cwiklik,
Y.; Hughes, R. P.; Aprahamian, I. Near-Infrared Light Activated
Azo-BF2 Switches. J. Am. Chem. Soc. 2014, 136, 13190-13193.
L. Photophysics of BODIPY-Based Photosensitizer for
Photodynamic Therapy: Surface Hopping and Classical Molecular
Dynamics. J. Chem. Theory. Comput. 2019, 15, 5046-5057; (c)
Gayathri, T.; Vijayalakshmi, A.; Mangalath, S.; Joseph, J.; Rao, N.
M.; Singh, S. P. Study on Liposomal Encapsulation of New Bodipy
Sensitizers for Photodynamic Therapy. ACS Med. Chem. Lett.
(13) Selected example for unsing BPh as starting material: (a)
3
Mas-Montoya, M.; Usea, L.; Espinosa Ferao, A.; Montenegro, M.
F.; Ramirez de Arellano, C.; Tarraga, A.; Rodriguez-Lopez, J. N.;
Curiel, D. Single Heteroatom Fine-Tuning of the Emissive
Properties
in
Organoboron
Complexes
with
7-
2
018, 9, 323-327; (d) Dai, X. M.; Chen, X. L.; Zhao, Y.; Yu, Y. J.; Wei,
(Azaheteroaryl)indole Systems. J. Org. Chem. 2016, 81, 3296-3302;
(b) Liu, Q. D.; Mudadu, M. S.; Schmider, H.; Thummel, R.; Tao,
Y.; Wang, S. N. Tuning the Luminescence and
Electroluminescence of Diphenylboron Complexes of 5-
Substituted 2-(2-Pyridyl)indoles. Organometallics 2002, 21, 4743–
4749.
X. S.; Zhang, X. G.; Li, C. X. A Water-Soluble Galactose-Decorated
Cationic Photodynamic Therapy Agent Based on BODIPY to
Selectively Eliminate Biofilm. Biomacromolecules 2018, 19, 141-149;
(e) Huang, L.; Li, Z. J.; Zhao, Y.; Zhang, Y. W.; Wu, S.; Zhao, J. Z.;
Han, G. Ultralow-Power Near Infrared Lamp Light Operable
Targeted Organic Nanoparticle Photodynamic Therapy. J. Am.
Chem. Soc. 2016, 138, 14586-14591.
(14) Selected example for unsing ArB Ph Br as starting material:
2
2
2
(a) Tokoro, Y.; Nagai, A.; Chujo, Y. Synthesis of highly
luminescent organoboron polymers connected by bifunctional 8-
aminoquinolate linkers. J. Polym. Sci., Part A: Polym. Chem. 2010,
48, 3693-3701; (b) Tokoro, Y.; Nagai, A.; Chujo, Y. Luminescent
chiral organoboron 8-aminoquinolate-coordination polymers.
Appl. Organomet. Chem. 2009, 24, 563-568.
(15) Selected example for base-promoted one-pot synthesis of
four-coordinate or-ganoboron: Sadu, V. S.; Bin, H. R.; Lee, D. M.;
Lee, K. I. One-pot synthesis of four-coordinate boron(III)
complexes by the ligand-promoted organic group migration
between boronic acids. Sci. Rep. 2017, 7, 242.
(
6) Selected examples for molecular probes: (a) Wu, S.; Li, Y.;
Deng, T.; Wang, X.; Hu, S.; Peng, G.; Huang, X. A.; Ling, Y.; Liu, F.
A new fluorescent probe for sensing of biothiols and screening of
acetylcholinesterase inhibitors. Org. Biomol. Chem. 2020, 18,
2468-2474; (b) Zhang, J.; Wang, N.; Ji, X.; Tao, Y.; Wang, J.; Zhao,
W. BODIPY-Based Fluorescent Probes for Biothiols. Chemistry
2
020, 26, 4172-4192; (c) Guria, S.; Ghosh, A.; Manna, K.; Pal, A.;
Adhikary, A.; Adhikari, S. Rapid detection of aspartic acid and
glutamic acid in water by BODIPY-Based fluorescent probe: Live-
cell imaging and DFT studies. Dyes Pigm. 2019, 168, 111-122.
(
7) Selected examples for cell imaging: (a) Brommel, K.; Maskri,
(16) (a) Tang, Z.; Liu, Z. L.; Tong, Z.; Xu, Z. H.; Au, C.-T.; Qiu, R.
H.; Kambe, N. Cu-Catalyzed Cross-Dehydrogenative Coupling of
Heteroaryl C(sp(2))-H and Tertiary C(sp(3))-H Bonds for the
Construction of All-Carbon Triaryl Quaternary Centers. Org. Lett.
2019, 21, 5152-5156; (b) Zhu, L. Z.; Le, L. Y.; Yan, M. P.; Au, C.-T.;
Qiu, R. H.; Kambe, N. Carbon-Carbon Bond Formation of
Trifluoroacetyl Amides with Grignard Reagents via C(O)-CF3
Bond Cleavage. J. Org. Chem. 2019, 84, 5635-5644; (c) Wang, X.;
Xie, P. P.; Qiu, R. H.; Zhu, L. Z.; Liu, T.; Li, Y.; Iwasaki, T.; Au, C.-
T.; Xu, X. H.; Xia, Y. Z.; Yin, S.-F.; Kambe, N. Nickel-catalysed
direct alkylation of thiophenes via double C(sp3)-H/C(sp2)-H
bond cleavage: the importance of KH PO . Chem. Commun. 2017,
S.; Maisuls, I.; Konken, C. P.; Rieke, M.; Petho, Z.; Strassert, C. A.;
Koch, O.; Schwab, A.; Wunsch, B. Synthesis of Small-Molecule
Fluorescent Probes for the In Vitro Imaging of Calcium-Activated
Potassium Channel KCa 3.1. Angew. Chem. Int. Ed. Engl. 2020, 59,
2-10; (b) Taniguchi, A.; Sawazaki, T.; Shimizu, Y.; Sohma, Y.;
Kanai, M. Photophysical properties and application in live cell
imaging of B,B-fluoro-perfluoroalkyl BODIPYs. Medchemcomm
2019, 10, 1121-1125; (c) Zhang, P.-L.; Wang, Z.-K.; Chen, Q.-Y.; Du,
X.; Gao, J. Biocompatible G-Quadruplex/BODIPY assembly for
cancer cell imaging and the attenuation of mitochondria. Bioorg.
Med. Chem. Lett. 2019, 29, 1943-1947.
2
4
(
8) Selected examples for boron dipyrromethene derivatives: (a)
53, 8316-8319; (d) Li, Y.; Zhu, L. Z.; Cao, X.; Au, C. T.; Qiu, R. H.;
Yin, S. F. Metal–free C5-H Bromination of Quinolines for One-pot
C−X (X=C, O, S) Bond Formations. Adv. Synth. Catal. 2017, 359,
2864–2873; (e) Wang, X.; Zhu, L. Z.; Chen, S. H.; Xu, X. H.; Au, C.-
T.; Qiu, R. H. Nickel-Catalyzed Direct C (sp3)–H Arylation of
Aliphatic Amides with Thiophenes. Org. Lett. 2015, 17, 5228–5231;
(f) Wang, X.; Qiu, R. H.; Yan, C. Y.; Reddy, V. P.; Zhu, L. Z.; Xu, X.
H.; Yin, S.-F. Nickel-Catalyzed Direct Thiolation of C(sp3)–H
Bonds in Aliphatic Amides. Org. Lett. 2015, 17, 1970–1973; (g) Zhu,
L. Z.; Qiu, R. H.; Cao, X.; Xiao, S.; Xu, X. H.; Au, C.-T.; Yin, S.-F.
Lapok, L.; Cieslar, I.; Pedzinski, T.; Stadnicka, K. M.; Nowakowska,
M. Near-Infrared Photoactive Aza-BODIPY: Thermally Robust
and Photostable Photosensitizer and Efficient Electron Donor.
Chemphyschem 2020, 21, 1-7; (b) Wang, C. J.; Qian, Y. A water
soluble carbazolyl-BODIPY photosensitizer with orthogonal D-A
structure for photodynamic therapy in living cells and zebrafish.
Biomater. Sci. 2020, 8, 830-836; (c) Wijesooriya, C. S.; Peterson, J.
A.; Shrestha, P.; Gehrmann, E. J.; Winter, A. H.; Smith, E. A. A
Photoactivatable BODIPY Probe for Localization-Based Super-
Resolution Cellular Imaging. Angew. Chem. Int. Ed. Engl. 2018, 57,
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Page 14 of 14
Copper-Mediated Remote C–H Bond Chalcogenation of
Quinolines on the C5 Position. Org. Lett. 2015, 17, 5528–5531.
17) Copies of crystallographic data (CCDC 1965554 (3a)) can be
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
(24) Shi, C.; Miao, Q.; Ma, L.; Lu, T.; Yang, D.; Chen, J.; Li, Z.
RoomTemperature CH Bromination and Iodination with
Sodium Bromide and Sodium Iodide Using N-
Fluorobenzenesulfonimide as an Oxidant. ChemistrySelect 2019,
4, 6043-6047.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
(
18) Copies of crystallographic data (CCDC 1833128 (4t)) can be
(25) Perez, C.; Barkley-Levenson, A. M.; Dick, B. L.; Glatt, P. F.;
Martinez, Y.; Siegel, D.; Momper, J. D.; Palmer, A. A.; Cohen, S. M.
Metal-Binding Pharmacophore Library Yields the Discovery of a
Glyoxalase 1 Inhibitor. J. Med. Chem. 2019, 62, 1609-1625.
(26) Qiao, L.; Cao, X.; Chai, K.; Shen, J.; Xu, J.; Zhang, P. Remote
radical halogenation of aminoquinolines with aqueous hydrogen
halide (HX) and oxone. Tetrahedron Lett. 2018, 59, 2243-2247.
(27) Yang, X.; Yang, Q. L.; Wang, X. Y.; Xu, H. H.; Mei, T. S.;
Huang, Y.; Fang, P. Copper-Catalyzed Electrochemical Selective
Bromination of 8-Aminoquinoline Amide Using NH4Br as the
Brominating Reagent. J. Org. Chem. 2020, 85, 3497-3507.
(28) Shintani, R.; Tsutsumi, Y.; Nagaosa, M.; Nishimura, T.;
Hayashi, T. Sodium Tetraarylborates as Effective Nucleophiles in
Rhodium/Diene-Catalyzed 1,4-Addition to β,β-Disubstituted α,β-
Unsaturated Ketones: Catalytic Asymmetric Construction of
Quaternary Carbon Stereocenters. J. Am. Chem. Soc. 2009, 131,
13588-13589.
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
(19) Liu, K. J.; Langan, J. R.; Salmon, G. A.; Holton, D. M.;
Edwards, P. P. Pulse radiolysis of solutions of sodium
tetraphenylborate. J. Phys. Chem. 1988, 92, 2449–2451.
(
20) Selected example for fluoroaminoquinolines derivatives:
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Whiteoak, C. J.; Planas, O.; Company, A.; Ribas, X. A First Example
of Cobalt-Catalyzed Remote CH Functionalization of 8-
Aminoquinolines Operating through a Single Electron Transfer
Mechanism. Adv. Synth. Catal. 2016, 358, 16791688.
(21) Selected example for sodium tetraarylborates production:
Zhou, W.-J.; Wang, K.-H.; Wang, J.-X.; Gao, Z.-R. Ligand-free,
atom-efficient Suzuki–Miyaura type cross-coupling reactions at
room temperature. Tetrahedron 2010, 66, 7633–7641.
(
22)Tang, Q.; Wang, N.; Zhou, F.; Deng, T.; Zhang, S.; Li, J.; Yang,
R.; Zhong, W.; Tan, W. A novel AgNP/DNA/TPdye conjugate-
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