Rhodium-catalyzed ortho-selective C-H halogenation of 2-arylbenzo[d]thiazoles using N-halosuccinimides as halogen sources

Article abstract of DOI:10.1016/j.tet.2015.03.004

Abstract A series Rh(III)-catalyzed ortho-selective C-H halogenation of 2-arylbenzo[d]thiazoles has been developed using N-halosuccinimides (NXS, X=Br and I) as halogen sources. ortho-Brominated and iodinated various 2-arylbenzo[d]thiazoles could be accessed in good to excellent yields and high regioselectivity under mild reaction conditions.

Full text of DOI:10.1016/j.tet.2015.03.004

Accepted Manuscript
Rhodium-catalyzed ortho-selective C-H halogenation of 2-arylbenzo[d]thiazoles using
N-halosuccinimides as halogen sources
Qiuping Ding, Xiaoli Zhou, Shouzhi Pu, Banpeng Cao
PII:
S0040-4020(15)00290-2
10.1016/j.tet.2015.03.004
TET 26486
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 15 December 2014
Revised Date: 16 February 2015
Accepted Date: 2 March 2015
Please cite this article as: Ding Q, Zhou X, Pu S, Cao B, Rhodium-catalyzed ortho-selective C-H
halogenation of 2-arylbenzo[d]thiazoles using N-halosuccinimides as halogen sources, Tetrahedron
(2015), doi: 10.1016/j.tet.2015.03.004.
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ACCEPTED MANUSCRIPT
Rhodium-catalyzed ortho-selective C-H halogenation of
2-arylbenzo[d]thiazoles using N-halosuccinimides as halogen
sources
Qiuping Ding,*a,b Xiaoli Zhou, b Shouzhi Pu*a, and Banpeng Caoa
a Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology
Normal University, Nanchang, Jiangxi 330013, P. R. China
b Key Laboratory of Functional Small Organic Molecules, Ministry of Education and
College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang,
Jiangxi 330022, P. R. China
Abstract: A series Rh(III)-catalyzed ortho-selective C-H halogenation of
2-arylbenzo[d]thiazoles has been developed using N-halosuccinimides (NXS, X = Br
and I) as halogen sources. ortho-Brominated and iodinated various
2-arylbenzo[d]thiazoles could be accessed in good to excellent yields and high
regioselectivity under mild reaction conditions.
Keywords: 2-Arylbenzo[d]thiazoles; Halogenation; N-halosuccinimides
Graphical Abstract:
H
X
N
S
N
S
[Rh], AgSbF6
NXS
R1
R1
R2
R2
X = Br, I
24 examples, up to 99% yield
* Corresponding authorꢀTel.: +86 791 83831996; fax: +86 791 83831996; E-mail: dqpjxnu@gmail.com (Q. Ding);
pushouzhi@tsinghua.org.cn (S. Pu).
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1. Introduction
Aromatic halides serve as important structural motifs extensively used as coupling
partners,1 electrophiles,2 and promising building blocks3 in organic synthesis. The
traditional methods for the synthesis of aromatic halides mainly involve electrophilic
aromatic substitution4 and directed ortho lithiation (DoL)/electrophilic substitution.5
Low yield or poor regioselectivity of the two prevalent strategies lead to urge to
develop a new straightforward protocol for the direct ortho-C-H halogenation of
arenes. In fact, transition metal-catalyzed C-H functionalization6/halogenation has
emerged over the past decade as another particularly useful and environmentally
friendly method for preparing halogenated aromatic products with high yield and
selectivity. Pd7-, Cu8-, and Au9-catalyzed C-H halogenation of arenes are
well-documented. For instance, Yu and co-workers reported the Pd-catalyzed
ortho-halogenation of arenes, using carboxylic acid7d,g and amide7e,m,n as directing
groups. Copper-based catalytic systems also have been well-demonstrated directed by
pyridine.8 In contract, the only one Rh-catalyzed C-H halogenation reaction of
benzamides, acetamides, and phenylpyridines was reported by Glorius.10 Herein, we
report Rh-catalyzed C-H halogenation of 2-arylbenzo[d]thiazoles using
N-halosuccinimides (NXS, X = Br and I) as halogen sources.
Benzothiazoles as one of numerous bioactive natural products and pharmaceuticals
have consequently attracted the continued interest of synthetic chemists for many
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years.11 Based on transition metal-catalyzed direct C-H functionalization protocol,
recently we and other groups developed the synthesis of various ortho-functionalized
2-arylbenzo[d]thiazoles, including arylation, acylation, acyloxylation, fluorination,
and amidation (Scheme 1).12 Recently, Rh-catalyzed direct C-H bond
functionalizations,13 including oxygenation, amination, arylation, alkenylation of
various organic molecules, has become a valuable synthetic method. Herein, we
report the Rh-catalyzed direct C-H bond bromination and iodination of
2-arylbenzo[d]thiazoles using N-halosuccinimides as halogen sources with excellent
regioselectivity and reactivity.
Scheme 1. Direct C-H functionalization of 2-arylbenzo[d]thiazoles.
Our initial investigations focused on the [RhCp*Cl2]2-catalyzed bromination of
2-(2-chlorophenyl)-6-methylbenzo[d]thiazole 1a under various conditions using
N-bromosuccinimide (NBS) as the bromination reagent. Without additive, the desired
brominated product 2a was obtained only in moderate yield 43% (Table 1, entry 1). In
order to improve the conversion, AgSbF6 as a commonly used additive was examined.
Delightedly, we found that the addition of AgSbF6 (40 mol %) in the reaction system
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dramatically increased the yield 79% of desired product 2a (Table 1, entry 2).
However, only inferior results were displayed when other additives were used, such as
Ag2CO3, AgNO3, AgOAc, and AgOTf. Gratifyingly, lowering the amount of the
Rh-catalyst improved the efficiency of this catalytic system significantly (Table 1,
entries 2-4). Product 2a was obtained in 95% yield upon decreasing the loading of the
Rh(III) catalyst to 1 mol% (Table 1, entry 4). Definitely, a control reaction showed
that omission of the Rh(III) catalyst resulted in complete inactivity of this catalytic
system. Notably, it was found the amount of additive AgSbF6 slightly affects the
outcome of the reaction (Table 1, entries 6-9). Decreasing the amount of AgSbF6 led
to the decrease of both the reaction activity and efficiency. An excellent conversion
was observed in 1 h in the presence of 40 mol% AgSbF6. However, when the reaction
was carried out with 4 mol% AgSbF6, only 79% yield of product 2a and 15%
substrate 1a were obtained in more than 24 h (Table 1, entry 9). Among various
solvents examined, DCE provided the best results, whereas 1,4-dioxane gave inferior
results, while toluene, CH3CN, and DMF failed to yield the desired product (Table 1,
entries 10-13).
Table 1. Optimization of ortho-bromination reaction conditionsa.
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entry [RhCp*Cl2]2
AgSbF6
-
solvent
DCE
yield (%)b
43
1
2
3
[RhCp*Cl2]2 (4%)
AgSbF6
AgSbF6
AgSbF6
DCE
DCE
DCE
79
88
95
[RhCp*Cl2]2 (4%)
[RhCp*Cl2]2 (2.5%)
4
5
[RhCp*Cl2]2 (1%)
-
AgSbF6
AgSbF6
(20%)
AgSbF6
(10%)
AgSbF6
(8%)
AgSbF6
(4%)
DCE
DCE
n.r.
86
[RhCp*Cl2]2 (1%)
6
7
8
9
DCE
DCE
DCE
85
83
79
[RhCp*Cl2]2 (1%)
[RhCp*Cl2]2 (1%)
[RhCp*Cl2]2 (1%)
AgSbF6
1,4-dioxane 57
10 [RhCp*Cl2]2 (1%)
11 [RhCp*Cl2]2 (1%)
12 [RhCp*Cl2]2 (1%)
13 [RhCp*Cl2]2 (1%)
AgSbF6
AgSbF6
AgSbF6
toluene
CH3CN
DMF
n.r.
n.r.
n.r.
a Reaction conditions: 2-(2-chlorophenyl)-6-methylbenzo[d]thiazole 1a (0.2 mmol),
NBS (1.1 equiv, 0.22 mmol), [RhCp*Cl2]2 (1-4 mol%), AgSbF6 (40 mol%), 80 oC,
solvent (2 mL). b Isolated yield based on 1a, n.r. = no reaction.
2. Results and Discussion
In order to investigate the reaction scope of the protocol, subsequently we
examined the generality of Rh-catalyzed ortho-bromination of substituted
2-arylbenzo[d]thiazoles 2 under optimized conditions {[RhCp*Cl2]2 (1 mol%),
AgSbF6 (40 mol%), DCE, 80 oC} (Table 2).
A
wide range of
2-arylbenzo[d]thiazole derivatives were smoothly transformed into the
corresponding ortho-brominated products in good to excellent yields. Substrates
bearing
electron-donating
groups
(such
as
methyl,
amino,
and
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N,N-dimethylamino) or electron-withdrawing groups (such as F and Cl) as well as
those ortho-, meta- and para-substituted derivatives were well tolerated. For
instance, 2-arylbenzo[d]thiazoles 2 containing halogen (F, Cl) and methyl
substituents on the ortho-position of 2-aryl ring undergo the C-H bond
bromination process smoothly under the optimized conditions to give the
corresponding products in 64-96% yields (2a-h). To those substrates 1i-k with a
methyl group at the meta-position of 2-aryl ring undergo the bromination reaction
efficiently to give one regioisomeric mono-brominated products 2i-k at the less
sterically hindered position in good yields (80-91%). Replacing methyl by chlorine
as a substituent at the meta-position led to a mixture of mono- and di-brominated
compounds under standard conditions, but gave only high yields (96% and 93%)
of di-brominated products (2l and 2m) when 2.1 equiv NBS was used. To those
substrates without substituents at the 2-phenyl ring also afforded almost
quantitative di-bromonated products (2n and 2o) in the presence of 2.1 equiv NBS.
For the substrates 1p-q bearing electron-donating groups (N,N-dimethylamino and
amino, respectively), the desired mono-brominated products 2p-q were isolated in
moderate yield. Unfortunately, the functional group R2 couldn’t tolerate the very
strong electron-withdrawing group (such as nitro, 1r). Interesting, for substrates 1s
and 1t, the bromination reaction was not a ligand-directed ortho-C-H activation
process under the standard conditions, but compounds 3s and 3t were obtained in
high yields via electrophilic aromatic substitution at the para-position to the
nitrogen atom in the benzo ring of benzothiazole moiety. To the substrates 1f and
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1m with a methyl at the para-position, the electrophilic substitution reaction could
not be carried out under the standard conditions, and only the C-H activated
products 2f and 2m were observed. Although we could not explain the exact
mechanism, we can conclude from the results that C-H activation may be prior to
electrophilic substitution when the ortho-position of 2-aryl was not be occupied by
substitutents (such as 1i, 1l, and 1p-q).
Table 2. ortho-Bromination of various 2-arylbenzo[d]thiazoles 1a,b
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R2
R2
[RhCp*Cl2]2 (1 mol%)
AgSbF6 (40 mol%)
N
N
S
R1
R1
NBS
(1.1 equiv.)
S
DCE 80 C
Br
1
2
Cl
N
Cl
Cl
Br
N
S
N
S
Cl
F
F
S
H3C
Br
Br
2c 84%
2b 96%
2a 95%
F
H3C
H3C
N
S
N
S
N
S
H3C
Cl
Br
Br
Br
2e 64%
2f 86%
2d 88%
CH3
F
F
N
S
N
S
N
S
F
Cl
Br
Br
Br
2g 91%
2i 80%
2h 89%
Br
Cl
CH3
CH3
N
S
N
N
S
S
Cl
F
Br
Br
2j 91%
Br
2k 89%
2l 96% (2.1 equiv. NBS)
Br
N
Br
Cl
Br
N
S
N
S
S
Cl
H3C
Br
Br
Br
2o 97% (2.1 equiv. NBS)
2m 93% (2.1 equiv. NBS)
2n 99% (2.1 equiv. NBS)
O2N
N
CH3
N
N
S
NH2
N
CH3
S
S
Br
Br
Br
2q 41%
2r trace
2p 69%
Cl
H3C
N
S
N
S
Br
Br
3s 99%
3t 92%
To further exemplify the synthetic utility of this protocol, the ortho-iodination
reaction of 2-arylbenzo[d]thiazoles by using NIS as the iodination reagent was
evaluated. Several 2-arylbenzo[d]thiazoles were studied as found in Table 3. In
general, the iodination reaction occurred smoothly, leading to the desired products
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in good to excellent yields. The substrates 2-arylbenzo[d]thiazoles 1p-r bearing
2-Me, 2-Cl, and 2-F substituents on the aryl ring reacted with NIS to give target
products 4p-r in 99%, 93%, and 86% yields, respectively. Surprisingly, without
any electrophilic aromatic substitution product was detected. The detail reason is
ambiguous.
Interesting,
when
meta-substituted
substrate,
2-(m-tolyl)benzo[d]thiazole 1i was used, provided only the mono-iodinated
product 4i at the less sterically hindered position in good yield 81%. In a similar
vein, steric hindrance showed non-ignorable influence on ortho-iodination activity.
Table 3. ortho-Iodination of 2-arylbenzo[d]thiazoles 1.
Based on previous works,7-10 the plausible mechanism for the ortho-halogenation
of 1 with N-halosuccinimides (NXS, X = Br and I) is illustrated in Scheme 1.
Firstly, [RhCp*Cl2]2 is dissociated into unsaturated monomeric complexes
RhCp*Cl2, then RhCp*(SbF6)2 species may be formed in the presence of AgSbF6.
Secondly, involves C-H bond activation through coordination at the ortho-position
of the substrate leading to a five-membered rhodacycle intermediate I. Thirdly,
rhodacycle I was oxidized into Rh(V) intermediate II by N-halosuccinimides.
Finally, involves the formation of C-X (X = Br, I) bond via reductive elimination
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leading to the halogenated product along with regeneration of the Rh(III) catalyst
(pathway a). Although we can not deny the transformation may undergo a
nucleophlic addition type reaction (pathway b).
RhCp*Cl2
[RhCp*Cl2]2
AgSbF6
AgCl
N
S
RhCp*(SbF6)2
Reductive
elimination
1
C-H Activation
X
N
Pathway
b
S
2 or 4
Cp*
N
SbF6
(III)
Rh
O
O
N(V)
Rh
Cp*
N
SbF6
S
pathway a
X
S
I
II
Oxidative
addition
NXS
Scheme 2. Proposed catalytic cycle.
Scheme 2. Proposed catalytic cycle.
Conclusion
In summary, an ortho-selective C-H bromination and iodination of
2-arybenzo[d]thiazoles have been developed using only 1% loading of Rh(III) catalyst
and commercially available halogenation reagents (NXS). ortho-Brominated and
iodinated various 2-arylbenzo[d]thiazoles could be accessed in good to excellent
yields and high regioselectivity under mild reaction conditions. Further extension the
application and mechanism of this protocol is currently underway in our laboratory.
Experimental
General
procedure
for
Rh-catalyzed
ortho-C-H
halogenation
of
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2-arylbenzo[d]thiazoles: In a sealed tube, AgSbF6 (40 mmol%) was added to a
solution of 2-arylbenzo[d]thiazole (0.2 mmol), [RhCp*Cl2]2 (1 mmol%) and NBS
(0.22 mmol, 1.1 equiv) in 1,2-dichloroethane (DCE) (2 mL). The resulting mixture
o
was stirred at 80 C for 1-3 h (monitored by TLC). After being cooling to room
temperature, evaporation of the solvent under reduced pressure followed purification
by silica gel chromatography using petroleum ether/ethyl acetate (20:1) as eluent to
provide the destination products 2-4.
2-(2-bromo-6-chlorophenyl)-6-methylbenzo[d]thiazole (2a):
Isolated (Rf = 0.27, EtOAc-petroleum ether = 1:20 v/v) as a colorless oil (63 mg, 95%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.53 (s, 3H), 7.29 (t, J = 8.2 Hz, 1H), 7.36 (d,
J = 8.0 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.76 (s, 1H), 8.04
(d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 21.6, 121.3, 123.4, 124.8, 127.9,
128.7, 131.3, 131.6, 134.2, 135.5, 136.0, 136.5, 151.0, 162.6; IR (KBr) ν/cm−1: 3051,
2924, 2853, 1579, 1554, 1427, 1085, 702, 683; HRMS (ESI): m/z [M + H]+ calcd for
C14H9BrClNS: 337.9328; found: 337.9329.
2-(2-bromo-6-chlorophenyl)-6-chlorobenzo[d]thiazole (2b):
Isolated (Rf = 0.32, EtOAc/petroleum ether = 1:20) as a yellow oil (69 mg, 96%
1
yield); H NMR (400 MHz, CDCl3) δ = 7.32 (t, J = 8.2 Hz, 1H), 7.49 (d, J = 8.0 Hz,
1H), 7.52 (d, J = 8.8 Hz, 1H), 7.63 (d, J = 8.0 Hz, 1H), 7.95 (s, 1H), 8.08 (d, J = 8.8
13
Hz, 1H); C NMR (100 MHz, CDCl3) δ = 120.8, 124.1, 124.2, 126.6, 126.7, 128.2,
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130.9, 131.4, 133.1, 134.9, 137.0, 150.9, 163.7; IR (KBr) ν/cm−1: 3054, 1592, 1554,
1427, 1081, 695; HRMS (ESI): m/z [M + H]+ calcd for C13H6BrCl2NS: 357.8861;
found: 357.8876.
2-(2-bromo-6-chlorophenyl)-6-fluorobenzo[d]thiazole (2c):
Isolated (Rf = 0.32, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (56 mg, 84%
yield); 1H NMR (400 MHz, CDCl3) δ = 7.28 (dd, J = 8.8 Hz, 1H), 7.31 (d, J = 8.0 Hz,
13
1H), 7.48 (d, J = 7.6 Hz, 1H), 7.63 (t, J = 8.0 Hz, 1H), 8.11 (s, 1H); C NMR (100
MHz, CDCl3) δ = 107.7 (d, 2JCF = 27.2 Hz), 115.0 (d, 2JCF = 24.8 Hz), 124.7, 125.0 (d,
3
3JCF = 9.5 Hz), 128.8, 131.4, 131.9, 133.7, 135.5, 137.3 (d, JCF = 11.4 Hz), 149.5,
160.8 (d, 1JCF = 245 Hz); IR (KBr) ν/cm−1: 3068, 1610, 1565, 1456, 1224, 1086, 703,
678; HRMS (ESI): m/z [M + H]+ calcd for C13H6BrClFNS: 341.9157; found:
341.9153.
2-(2-bromo-6-methylphenyl)-6-chlorobenzo[d]thiazole (2d):
Isolated (Rf = 0.28, EtOAc-petroleum ether = 1:20 v/v) as a brown oil (59 mg, 88%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.22 (s, 3H), 7.25 (d, J = 6.4 Hz, 2H), 7.51 (td,
J = 8.6 Hz, 1H), 7.53 (d, J = 6.4 Hz, 1H), 7.93 (s, 1H), 8.04 (d, J = 8.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ = 19.5, 120.2, 122.5, 123.4, 125.9, 128.1, 129.3, 130.1,
130.5, 133.1, 136.5, 139.0, 150.6, 165.6; IR (KBr) ν/cm−1: 3060, 2960, 2854, 1683,
1592, 1445, 1083, 700, 681; HRMS (ESI): m/z [M + H]+ calcd for C14H9BrClNS:
337.9328; found: 337.9394.
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6-fluoro-2-(o-tolyl)benzo[d]thiazole (2e):
Isolated (Rf = 0.29, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (40 mg, 64%
1
yield); H NMR (400 MHz, CDCl3) δ = 2.23 (s, 3H), 7.25-7.35 (m, 3H), 7.52 (d, J =
8.0 Hz, 1H), 7.63 (d, J = 8.0 Hz, 1H), 8.08 (s, 1H); 13C NMR (100 MHz, CDCl3) δ =
3
19.6, 106.6 (d, 2JCF = 26.6 Hz), 113.7 (d, 2JCF = 24.8 Hz), 122.6, 123.6 (d, JCF = 9.3
1
Hz), 128.1, 129.3, 130.0, 133.2, 139.0, 148.7, 159.6 (d, JCF = 245 Hz), 164.8; IR
(KBr) ν/cm−1: 3066, 2958, 2854, 1610, 1565, 1455, 1253, 705, 685; HRMS (ESI): m/z
[M + H]+ calcd for C14H9BrFNS: 321.9703; found: 321.9696.
2-(2-bromo-6-fluorophenyl)-6-methylbenzo[d]thiazole (2f):
Isolated (Rf = 0.29, EtOAc-petroleum ether = 1:20 v/v) as a brown oil (54 mg, 86%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.53 (s, 3H), 7.18 (t, J = 8.6 Hz, 1H), 7.32 (d,
J = 8.4 Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.75 (s, 1H), 8.04
(d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 21.5, 115.0 (d, 2JCF = 22.0 Hz),
121.1, 123.4, 124.3, 127.8, 128.8, 132.0 (d, 3JCF = 9.0 Hz), 135.9, 136.6, 151.2, 158.7,
160.7 (d, 1JCF = 253 Hz); IR (KBr) ν/cm−1: 3055, 2953, 2853, 1607, 1567, 1447, 1251,
703, 686; HRMS (ESI): m/z [M + H]+ calcd for C14H9BrFNS: 321.9703; found:
321.9699.
2-(2-bromo-6-fluorophenyl)-6-chlorobenzo[d]thiazole (2g):
Isolated (Rf = 0.32, EtOAc-petroleum ether = 1:20 v/v) as a milky solid (61 mg, 91%
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yield), mp: 108-110 oC; 1H NMR (400 MHz, CDCl3) δ = 7.19 (t, J = 8.8 Hz, 1H), 7.36
(d, J = 8.4 Hz, 1H), 7.51 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.94 (s, 1H),
13
8.07 (d, J = 8.8 Hz, 1H); C NMR (100 MHz, CDCl3) δ = 115.2 (d, 2JCF = 21.8 Hz),
121.1, 124.1, 124.7, 127.2, 128.9, 129.0, 131.9, 132.4 (d, 3JCF = 8.9 Hz), 137.5, 151.5,
160.7 (d, 1JCF = 253 Hz); IR (KBr) ν/cm−1: 3066, 1589, 1567, 1444, 1247, 1104, 695,
545; HRMS (ESI): m/z [M + H]+ calcd for C13H6BrClFNS: 341.9157; found:
341.9150.
2-(2-bromo-6-fluorophenyl)-6-fluorobenzo[d]thiazole (2h):
Isolated (Rf = 0.33, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (57 mg, 89%
yield); 1H NMR (400 MHz, CDCl3) δ = 7.18 (d, J = 8.4 Hz, 1H), 7.20 (d, J = 8.8 Hz,
1H), 7.28 (t, J = 7.2 Hz, 1H), 7.36 (d, J = 6.0 Hz, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7.64
13
2
(d, J = 8.0 Hz, 1H), 8.12 (s, 1H); C NMR (100 MHz, CDCl3) δ = 106.5 (d, JCF
=
=
2
3
3
26.7 Hz), 114.2 (d, JCF = 23.4 Hz), 123.1, 123.9 (d, JCF = 9.4 Hz), 127.9 (d, JCF
3.6 Hz), 131.3 (d, 3JCF = 9.1 Hz), 136.3, 148.6, 158.5, 159.7 (d, 1JCF = 245 Hz), 159.8
(d, 1JCF = 245 Hz); IR (KBr) ν/cm−1: 3073, 1698, 1566, 1489, 1252, 704, 683; HRMS
(ESI): m/z [M + H]+ calcd for C13H6BrF2NS: 325.9452; found: 325.9454.
2-(2-bromo-5-methylphenyl)benzo[d]thiazole (2i): Isolated (Rf
=
0.29,
EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (48 mg, 80% yield); 1H NMR (400
MHz, CDCl3) δ = 2.28 (s, 3H), 7.03 (d, J = 7.6 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 7.42
(t, J = 7.6 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.73 (s, 1H), 7.83 (d, J = 7.6 Hz, 1H),
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8.04 (d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 20.8, 118.7, 121.4, 123.5,
125.4, 126.2, 132.2, 132.6, 133.8, 134.0, 136.1, 137.7, 152.7, 165.8; IR (KBr) ν/cm−1:
3058, 2954, 2850, 1591, 1484, 1459, 708, 693; HRMS (ESI): m/z [M + H]+ calcd for
C14H10BrNS: 303.9797; found: 303.9790.
2-(2-bromo-5-methylphenyl)-6-chlorobenzo[d]thiazole (2j):
Isolated (Rf = 0.28, EtOAc-petroleum ether = 1:20 v/v) as a white flake (61 mg, 91%
o
1
yield), mp: 124-126 C; H NMR (400 MHz, CDCl3) δ = 2.27 (s, 3H), 7.03 (s, 1H),
7.37 (s, 1H), 7.49 (s, 1H), 7.78 (s, 2H), 7.92 (s, 1H); 13C NMR (100 MHz, CDCl3) δ =
20.8, 118.6, 120.9, 124.2, 127.1, 131.3, 132.4, 132.6, 133.5, 133.9, 137.2, 137.7,
151.1, 166.2; IR (KBr) ν/cm−1: 3077, 2956, 2850, 1591, 1483, 1467, 1107, 706, 698;
HRMS (ESI): m/z [M + H]+ calcd for C14H9BrClNS: 337.9328; found: 337.9329.
2-(2-bromo-5-methylphenyl)-6-fluorobenzo[d]thiazole (2k):
Isolated (Rf = 0.29, EtOAc-petroleum ether = 1:20 v/v) as a flavescent solid (56 mg,
89% yield), mp: 98-100 oC; 1H NMR (400 MHz, CDCl3) δ = 2.30 (s, 3H), 7.05 (d, J =
8.0 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.74 (s, 1H), 7.99 (s,
13
2
2
1H); C NMR (100 MHz, CDCl3) δ = 20.8, 107.4 (d, JCF = 26.5 Hz), 115.0 (d, JCF
= 24.7 Hz), 118.6, 124.3, 132.3, 132.5, 133.7, 133.9, 137.1 (d, 3JCF = 11.1 Hz), 137.7,
1
149.3, 160.5 (d, JCF = 245 Hz), 165.5; IR (KBr) ν/cm−1: 3059, 2955, 2853, 1683,
1598, 1461, 1230, 706, 518. HRMS (ESI): m/z [M + H]+ calcd for C14H9BrClNO:
321.9703; found: 321.9703.
15

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2-(2,6-dibromo-3-chlorophenyl)benzo[d]thiazole (2l):
Isolated (Rf = 0.33, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (76 mg, 96%
1
yield); H NMR (400 MHz, CDCl3) δ = 7.47 (d, J = 8.8 Hz, 1H), 7.50 (t, J = 7.6 Hz,
1H), 7.57 (t, J = 7.4 Hz, 1H), 7.62 (d, J = 8.8 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.17
(d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 99.9, 118.1, 121.7, 122.2, 124.1,
125.3, 126.0, 126.4, 132.2, 132.3, 135.0, 136.2, 137.8, 152.6; IR (KBr) ν/cm−1: 3056,
1555, 1494, 1417, 1080, 707, 680; HRMS (ESI): m/z [M + H]+ calcd for
C13H6Br2ClNS: 401.8356; found: 401.8354.
2-(2,6-dibromo-3-chlorophenyl)-6-methylbenzo[d]thiazole (2m):
Isolated (Rf = 0.32, EtOAc-petroleum ether = 1:20 v/v) as a white solid (77 mg, 93%
yield), mp: 107-109 oC; 1H NMR (400 MHz, CDCl3) δ = 2.53 (s, 3H), 7.37 (d, J = 8.8
Hz, 1H), 7.45 (d, J = 8.8 Hz, 1H), 7.60 (d, J = 8.8 Hz, 1H), 7.76 (s. 1H), 8.04 (d, J =
8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 21.6, 121.4, 122.4, 123.6, 125.4, 128.0,
132.1, 132.3, 134.9, 136.2, 136.4, 137.9, 150.8, 164.1; IR (KBr) ν/cm−1: 3067, 2956,
2851, 1602, 1590, 1444, 1104, 696, 677; HRMS (ESI): m/z [M + H]+ calcd for
C14H8Br2ClNS: 415.8513; found: 415.8519.
2-(2,6-dibromophenyl)benzo[d]thiazole (2n):
Isolated (Rf = 0.33, EtOAc-petroleum ether = 1:20 v/v) as a brown oil (73 mg, 99%
1
yield); H NMR (400 MHz, CDCl3) δ = 7.22 (t, J = 8.0 Hz, 1H), 7.49 (t, J = 7.8 Hz,
16

ACCEPTED MANUSCRIPT
1H), 7.56 (t, J = 7.8 Hz, 1H), 7.67 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 7.6 Hz, 1H), 8.18
(d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 121.7, 124.0, 124.5, 125.8,
126.3, 131.9, 132.1, 135.8, 136.3, 152.8, 165.3; IR (KBr) ν/cm−1: 3060, 1592, 1550,
1458, 726, 690; HRMS (ESI): m/z [M + H]+ calcd for C13H7Br2NS: 367.8746; found:
367.8750.
6-chloro-2-(2,6-dibromophenyl)benzo[d]thiazole (2o):
Isolated (Rf = 0.35, EtOAc-petroleum ether = 1:20 v/v) as a pink solid (67 mg, 97%
o
1
yield), mp: 126-128 C; H NMR (400 MHz, CDCl3) δ = 7.45 (d, J = 8.4 Hz, 1H),
7.49 (d, J = 7.2 Hz, 1H), 7.56 (t, J = 7.2 Hz, 1H), 7.60 (d, J = 8.8 Hz, 1H), 7.97 (d, J =
8.0 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ = 121.3, 124.4,
124.8, 127.1, 131.9, 132.0, 132.2, 135.4, 137.5, 151.3, 165.8; IR (KBr) ν/cm−1: 3068,
1591, 1508, 1434, 1093, 707, 674; HRMS (ESI): m/z [M + H]+ calcd for
C13H6Br2ClNS: 401.8276; found: 401.8240.
4-(benzo[d]thiazol-2-yl)-3-bromo-N,N-dimethylaniline (2p):
Isolated (Rf = 0.57, EtOAc–petroleum ether = 1:10) as a colorless oil (45 mg, 69%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.89 (s, 6H), 7.10 (d, J = 8.4 Hz, 1H), 7.36 (t,
J = 7.6 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.87 (d, J = 7.6 Hz, 1H), 7.93 (d, J = 8.4 Hz,
13
1H), 8.03 (d, J = 8.4 Hz, 1H), 8.30 (s, 1H); C NMR (100 MHz, CDCl3) δ = 43.7,
118.2, 120.1, 121.5, 123.0, 125.0, 126.3, 127.3, 128.6, 133.0, 134.9, 154.1, 166.2; IR
(KBr) ν/cm−1: 3435, 3056, 2939, 2830, 1597, 1477, 1326, 701, 657; HRMS (ESI): m/z
17

ACCEPTED MANUSCRIPT
[M + H]+ calcd for C15H13BrN2S 333.0063; found: 333.0069.
4-(benzo[d]thiazol-2-yl)-3-bromoaniline (2q):
Isolated (Rf = 0.30, EtOAc–petroleum ether = 1:10) as a colorless oil (25 mg, 41%
yield); 1H NMR (400 MHz, CDCl3) δ = 4.43 (s, 2H), 6.80 (d, J = 8.4 Hz, 1H), 7.33 (t,
J = 8.2 Hz, 1H), 7.45 (t, J = 8.2 Hz, 1H), 7.80 (dd, J = 8.4 Hz, 1H), 7.85 (d, J = 7.6
Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 8.19 (s, 1H); 13C NMR (100 MHz, CDCl3) δ =
109.1, 115.1, 121.4, 122.7, 124.7, 125.0, 126.2, 127.9, 131.7, 134.6, 146.5, 154.1,
166.8; IR (KBr) ν/cm−1: 3437, 3028, 1642, 1594, 1467, 703, 577; HRMS (ESI): m/z
[M + H]+ calcd for C13H9BrN2S 304.9750; found: 304.9759.
2-(2-bromo-6-methylphenyl)benzo[d]thiazole (3s):
Isolated (Rf = 0.32, EtOAc-petroleum ether = 1:20 v/v) as a brown oil (60 mg, 99%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.23 (s, 3H), 7.24 (d, J = 7.2 Hz, 1H), 7.24 (s,
1H), 7.45 (t, J = 7.6 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.54 (t, J = 8.2 Hz, 1H), 7.95
13
(d, J = 8.0 Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ = 20.6,
121.6, 123.6, 123.7, 125.5, 126.1, 129.1, 130.2, 130.9, 136.3, 140.1, 153.1; IR (KBr)
ν/cm−1: 3059, 2954, 2853, 1593, 1561, 1447, 699; HRMS (ESI): m/z [M + H]+ calcd
for C14H10BrNS: 303.9797; found: 303.9797.
6-bromo-2-(2-chlorophenyl)benzo[d]thiazole (3t):
Isolated (Rf = 0.31, EtOAc-petroleum ether = 1:20 v/v) as a colorless oil (59 mg, 92%
18

ACCEPTED MANUSCRIPT
1
yield); H NMR (400 MHz, CDCl3) δ = 7.32 (t, J = 7.6 Hz, 1H), 7.49 (d, J = 8.0 Hz,
2H), 7.63 (d, J = 8.0 Hz, 1H), 7.65 (t, J = 8.8 Hz, 1H), 8.02 (d, J = 8.8 Hz, 1H), 8.11
(s, 1H); 13C NMR (100 MHz, CDCl3) δ = 118.5, 123.2, 123.6, 124.1, 127.8, 128.8,
130.4, 130.9, 132.6, 134.4, 136.9, 150.7, 163.2; HRMS (ESI): m/z [M + H]+ calcd for
C13H7BrClNS: 323.9251; found: 323.9275.
2-(2-iodo-6-methylphenyl)benzo[d]thiazole (4p):
Isolated (Rf = 0.38, EtOAc-petroleum ether = 1:20 v/v) as a white solid (70 mg, 99%
yield), mp: 113-115 oC; 1H NMR (400 MHz, CDCl3) δ = 2.16 (s, 3H), 7.18 (t, J = 7.8
Hz, 1H), 7.19 (d, J = 7.6 Hz, 1H), 7.38 (t, J = 7.6 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H),
7.72 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 8.07 (d, J = 8.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ = 20.6, 121.6, 123.6, 123.7, 125.5, 126.1, 129.1, 130.2, 130.9,
136.3, 140.1, 153.1, 166.1; IR (KBr) ν/cm−1: 3053, 2953, 2850, 1685, 1586, 1454, 705,
587; HRMS (ESI): m/z [M + H]+ calcd for C14H10INS: 351.9659; found: 351..9646.
2-(2-chloro-6-iodophenyl)benzo[d]thiazole (4q):
Isolated (Rf = 0.37, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (69 mg, 93%
1
yield); H NMR (400 MHz, CDCl3) δ = 7.10 (t, J = 8.0 Hz, 1H), 7.47 (t, J = 7.6 Hz,
1H), 7.49 (d, J = 8.4 Hz, 1H), 7.55 (t, J = 7.2 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.96
13
(d, J = 8.0 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ = 99.1,
121.7, 124.0, 125.8, 126.3, 129.5, 132.1, 134.3, 136.3, 137.6, 137.7, 152.7, 166.4; IR
(KBr) ν/cm−1: 3059, 1647, 1593, 1423, 1083, 707, 544; HRMS (ESI): m/z [M + H]+
19

ACCEPTED MANUSCRIPT
calcd for C13H7ClINS: 371.9032; found: 371.9027.
2-(2-fluoro-6-iodophenyl)benzo[d]thiazole (4r):
Isolated (Rf = 0.37, EtOAc-petroleum ether = 1:20 v/v) as a yellow solid (58 mg, 86%
yield), mp: 102-104 oC; 1H NMR (400 MHz, CDCl3) δ = 7.18 (t, J = 6.4 Hz, 1H), 7.19
(d, J = 8.4 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 7.78 (d, J = 6 .4
13
Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 8.18 (d, J = 8.4 Hz, 1H); C NMR (100 MHz,
CDCl3) δ = 98.6, 115.9 (d, 2JCF = 22. 0Hz), 121.6, 124.0, 125.8, 126.3, 127.5 (d, 2JCF
3
1
= 16.8 Hz), 132.7 (d, JCF = 8.6 Hz), 135.2, 136.4, 152.9, 159.9 (d, JCF = 253 Hz),
162.5; IR (KBr) ν/cm−1: 3058, 1689, 1598, 1445, 1248, 708, 543; HRMS (ESI): m/z
[M + H]+ calcd for C13H7FINS: 355.9408; found: 355.9401.
2-(2-iodo-5-methylphenyl)benzo[d]thiazole (4i):
Isolated (Rf = 0.40, EtOAc-petroleum ether = 1:20 v/v) as a yellow oil (56 mg, 81%
yield); 1H NMR (400 MHz, CDCl3) δ = 2.35 (s, 3H), 6.97 (dd, J = 8.4 Hz, 1H), 7.42 (t,
J = 7.6 Hz, 1H), 7.52 (t, J = 8.2 Hz, 1H), 7.54 (s, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.92
13
(d, J = 7.2 Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl3) δ = 20.8,
92.1, 121.5, 123.6, 125.4, 126.2, 132.2, 132.3, 136.1, 138.2, 138.4, 140.4, 153.0,
168.0; IR (KBr) ν/cm−1: 3058, 2953, 2853, 1592, 1498, 1456, 708, 527; HRMS (ESI):
m/z [M + H]+ calcd for C14H9INS: 351.9659; found: 351.9671.
Acknowledgments
20

ACCEPTED MANUSCRIPT
Financial Supported from National Natural Science Foundation of China (21262016),
China Postdoctoral Science foundation (2013M531556, 2014T70617), and Natural
Science Foundation of Jiangxi Province of China (20133ACB20008,
20132BAB203006) is gratefully acknowledged.
Supplementary data
Supplementary data related to this article can be found at http://dx.doi.org/10.1016/
References and Notes
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Rhodium-Catalyzed ortho-selective C-H halogenation of
2-arylbenzo[d]thiazoles using N-halosuccinimides as halogen sources
Qiuping Ding,*a,b Xiaoli Zhou, b Shouzhi Pu*a, and Banpeng Caoa
a Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology
Normal University, Nanchang, Jiangxi 330013, P. R. China
b Key Laboratory of Functional Small Organic Molecules, Ministry of Education and
College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang,
Jiangxi 330022, P. R. China
Supporting Information
1. NMR spectra of all compounds 2-4. P2-P24
* Corresponding author：Tel.: +86 791 83831996; fax: +86 791 83831996; E-mail: dqpjxnu@gmail.com (Q. Ding);
pushouzhi@tsinghua.org.cn (S. Pu).
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