Ir-catalyzed C–S coupling of quinones with sulfonyl chloride

Article abstract of DOI:10.1007/s13738-016-0897-8

Abstract: A concise, efficient method to sulfonyl quinones and sulfonyl-1,4-diols through Ir-catalyzed C–S coupling of quinones with sulfonyl chloride has been developed. Thus, this methodology proves its value as a versatile synthetic tool for a broad ra

Full text of DOI:10.1007/s13738-016-0897-8

J IRAN CHEM SOC
DOI 10.1007/s13738-016-0897-8
ORIGINAL PAPER
Ir‑catalyzed C–S coupling of quinones with sulfonyl chloride
Long Wang1,2 · Yi‑Bi Xie1 · Quan‑Li Yang2 · Ming‑Guo Liu2 · Kai‑Bo Zheng1 ·
Yu‑lin Hu1 · Nian‑Yu Huang1,2
Received: 25 November 2015 / Accepted: 3 June 2016
© Iranian Chemical Society 2016
Abstract A concise, efficient method to sulfonyl quinones
and sulfonyl-1,4-diols through Ir-catalyzed C–S coupling
of quinones with sulfonyl chloride has been developed.
Thus, this methodology proves its value as a versatile syn-
thetic tool for a broad range of sulfonyl quinones, produc-
ing good to excellent yields.
products.1 Among these transformations, direct C–N, C–O,
and C–S cross-coupling constitutes a powerful and efficient
means of introducing a variety of substituents with diverse
functional groups onto the heterocyclic scaffold.2 Com-
pared to methods developed for C–N and C–O coupling,
transition metal-catalyzed C–S coupling remains relatively
rare [26–29], because catalyst poisoning by sulfur species
has been one of the serious limiting factors in this area [1,
7]. According to the literature, it has been reported that
even very low concentrations of these sulfur species can
rapidly, irreversibly deactivate the catalyst [30, 31]. Nowa-
days, scientists have paid great efforts to this area [32–41].
Several kinds of transition metals have proved to be effec-
tive for this transformation [42–48].
Graphical Abstract
Keywords Ir-catalyzed · C–S coupling · Quinones ·
Sulfonyl chloride
Sulfonyl-substituted quinones were important building
blocks and convenient precursors for numerous biologi-
cally significant natural products and pharmaceuticals [49–
51]. The direct C–S coupling was a nice method to the syn-
thesis of these sulfonyl quinones (Scheme 1) [52, 53], since
quinones were the very common materials. However, most
of the transition metal-catalyzed couplings of quinones
mainly focus on partners such as boron reagents,3 indoles
[61–64], and anilines [65, 66–79].
Introduction
Transition metal-catalyzed carbon–heteroatom bond forma-
tion is a very useful reaction because it provides a conveni-
ent access to numerous medicines and pharmaceutical
Recently, Wang et al. reported the Rh-catalyzed C–C
coupling and Pd-catalyzed C–S coupling quinones. How-
ever, the yield is low to moderate and usually needs
harsh terms [80–82]. Herein, we develop the Ir-catalyzed
C–H functionalization of quinones with sulfonyl chloride
through C–S coupling in moderate to good yields.
Electronic supplementary material The online version of this
article (doi:10.1007/s13738-016-0897-8) contains supplementary
material, which is available to authorized users.
* Ming-Guo Liu
longwwwang@163.com
* Nian-Yu Huang
442974924@qq.com
1
1
College of Materials and Chemical Engineering, China Three
Gorges University, Yichang 443002, Hubei, China
For some reviews, see [1–8].
2
For some reviews and examples for C–S(N, O) cross-coupling, see
2
[9–25].
3
College of Biology and Pharmacy, China Three Gorges
University, Yichang 443002, Hubei, China
For the coupling of quinones with boron reagents, see [54–60].
1 3

J IRAN CHEM SOC
Table 1 Screening of reaction conditions
Entry
Catalyst
Base
Solvent
Yield [%]
1
[Cp*IrCl2]2
IrCl3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
KHCO3
NaOH
tBuONa
Na2CO3
K2CO3
K2CO3
K2CO3
K2CO3
DCE
55
<5
23
16
<5
12
<5
10
34
22
33
41
73
81
66
<5
2
DCE
3
[(COD)IrCl]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2
[Cp*IrCl2]2/AgSbF6
[Cp*IrCl2]2/CuCl
–
DCE
Scheme 1 C–S coupling reaction from quinones and naphthoqui-
nones
4
DMF
Benzene
THF
5
6
7
Toluene
Dioxane
DCE
First, various iridium catalysts were selected in order to test
the reaction. Based on our experiments in this area, we set up
the reaction of quinone with TsCl in the presence of Na2CO3
using the DCE solvent system under an air atmosphere. The
result showed that 2-(toluene-4-sulfonyl)-[1,4]benzoquinone
(3a) was obtained with 55 % yield (Table 1, entry 1). Other
iridium catalysts gave significantly lower yields. Next, the
screening of reaction conditions was carried forward to a high
yield, and the results are shown in Table 1. When [Cp*IrCl2]2
was used as a catalyst, K2CO3 was used as the base and
AgSbF6 as the additive in the DCE to give 81 % of the product
(Table 1, entry 14). The solvent experiment showed this reac-
tion to be highly solvent-dependent, and DCE gave the best
result. Blank inspection showed that the reaction could not
occur without an iridium catalyst (Table 1, entry 16).
8
9
10
11
12
13
14
15
16
DCE
DCE
DCE
DCE
DCE
DCE
DCE
Conditions: 1a (0.5 mmol, 1.0 equiv.), 2a (1.5 equiv.), [Ir] (5 mol%),
base (1.5 equiv.), solvent, 12 h, reflux
Isolated yields based on 1a
Having established the optimal conditions of [Cp*IrCl2]2
(5 %), K2CO3 as the base, and AgSbF6 as the additive in
DCE, various substrates were applied to the standard con-
ditions in order to determine the scope and limitations of
the present methodology. Generally, all the substrates
reacted successfully to generate the desired products. The
results are summarized in Table 2. The results showed that
substrates with electron-donating groups such as Me, OMe,
and tBu could achieve high yields.
Next, we evaluated the reactivity of this transforma-
tion with benzoquinone substrates and sulfonyl chloride
(Table 2). As illustrated in Table 2, full conversions were
achieved with all the substrates. In the majority of cases,
the corresponding aryl-substituted sulfonyl quinones were
separated in good to excellent yields. However, in the case
of substrates with a strong electron-withdrawing group, this
methodology produced a disappointing result.
biosynthesis [50–52, 83]. Reynolds et al. [84] conducted a
detailed study on activity tests of quinone derivatives against
FabHs. Two typical models were shown in Scheme 2, and
compound A could be easily synthesized with 77 % yield
with this methodology (Table 2, 3i). Consequently, 2-tosylb-
enzene-1,4-diol (B) was obtained only by one more step
reduction under conditions of sodium borohydride in good
yield with Wang’s method [80–82] (Scheme 3).
A possible mechanism for the Ir-catalyzed C–S bond for-
mation reaction can be proposed (Scheme 4). (1) The oxi-
dation addition of Ir(I) with sulfonyl chloride to get species
5; (2) followed with carboiridation, whereby intermediate 6
was formed; (3) intermediate 6 released the Ir(III) 7 via β-H
elimination to produce the coupling product 3; (4) the reduc-
tive elimination of Ir(III) 7 to regenerate the Ir(I) 4, which
enters a new catalytic cycle.
In summary, a concise, efficient method to sulfonyl qui-
nones and sulfonyl-1,4-diols through Ir-catalyzed C–S cou-
pling of quinones with sulfonyl chloride has been devel-
oped. Accordingly, this methodology proves its value as a
2-Tosylbenzene-1,4-diol and naphthalene-1,4 diol/qui-
nones are potent inhibitors of β-Ketoacyl-ACP-synthase III
(FabH) [49], a key condensing enzyme for bacterial fatty acid
1 3

J IRAN CHEM SOC
Table 2 Substrate expansion of quinones
Scheme 3 Synthesis of the tosylbenzene-1,4-diol inhibitor
5 mol%), AgSbF6 (34.4 mg, 20 mol%), and K2CO3 (37.4 mg,
1.5 equiv.) in DCE (2.0 mL) was stirred at 90 °C under air
for 12 h. Upon completion, the reaction mixture was evapo-
rated to give the residue. The residue was then purified by
column chromatography on silica gel (ethyl acetate/petro-
leum ether = 1:10) to provide the corresponding product.
2‑(Toluene‑4‑sulfonyl)‑[1,4]benzoquinone (3a)
1
Light yellow solid (81 %). H NMR (400 MHz, CDCl3) δ
7.32 (d, J = 8.0 Hz, 2H), 7.25–7.14 (m, 2H), 6.85–6.67 (m,
3H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.7 (s),
186.8 (s), 145.8 (s), 140.6 (s), 137.0 (s), 136.2 (s), 132.0
(s), 129.8 (s), 129.3 (s), 129.2 (s), 21.4 (s). Anal. Calcd for
C13H10O4S: C, 59.53; H, 3.84; O, 24.40; S, 12.23. Found:
C, 59.37; H, 3.93; O, 24.27; S, 12.41.
Conditions: 1a (0.5 mmol, 1.0 equiv.), 2 (1.5 equiv.), [Cp*IrCl2]2
(5 mol%), AgSbF6 (20 mol%), K2CO3 (1.5 equiv.), DCE (3 mL),
12 h, reflux
Isolated yields based on 1a
2‑(4‑Methoxy‑benzenesulfonyl)‑[1,4]benzoquinone (3b)
1
Light yellow solid (87 %). H NMR (400 MHz, CDCl3) δ
7.48 (d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 6.87–
6.75 (m, 3H), 3.86 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 187.7 (s), 187.1 (s), 161.4 (s), 145.2 (s), 137.0 (s), 136.2
(s), 131.1 (s), 130.9 (s), 125.0 (s), 114.1 (s), 55.4 (s). Anal.
Calcd for C13H10O5S: C, 56.11; H, 3.62; O, 28.75; S, 11.52.
Found: C, 56.24; H, 3.55; O, 28.89; S, 11.42.
Scheme 2 Two typical FabH inhibitors
2‑(2,5‑Dimethoxy‑benzenesulfonyl)‑[1,4]benzoquinone
(3c)
versatile synthetic tool for a broad range of sulfonyl qui-
nones, producing good to excellent yields.
1
Light yellow solid (83 %). H NMR (400 MHz, CDCl3) δ
6.98–6.92 (m, 1H), 6.92–6.84 (m, 2H), 6.83–6.77 (m, 2H),
6.73 (d, J = 2.8 Hz, 1H), 3.78 (s, 3H), 3.73 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 187.7 (s), 185.5 (s), 153.4 (s),
151.3 (s), 145.8 (s), 137.1 (s), 136.1 (s), 134.4 (s), 123.2
(s), 116.1 (s), 116.0 (s), 112.5 (s), 56.3 (s), 55.8 (s). Anal.
Calcd for C14H12O6S: C, 54.54; H, 3.92; O, 31.14; S, 10.40.
Found: C, 54.66; H, 3.83; O, 31.23; S, 10.26.
General procedure for the synthesis
of pyrazol‑chromeno[2,3‑d]pyrimidine‑ones
(3a–3n)
A mixture of 1,4-quinone(1a) (54.0 mg, 0.50 mmol),
TsCl(2a) (145.0 mg, 0.75 mmol), [Cp*IrCl2]2 (19.9 mg,
1 3

J IRAN CHEM SOC
Scheme 4 A possible mecha-
nism for the Ir-catalyzed C–S
coupling reaction
reductive
ArSO2Cl
elimination
Ir(I)
O
O
4
oxidation
addition
Ir(III)
SO2Ar
7
3
ArSO2Ir(III)Cl
β−Η elimination
5
O
O
O
Ir(III)
SO2Ar
carboiridation
H
O
1
6
2‑(4‑tert‑Butyl‑benzenesulfonyl)‑[1,4]benzoquinone
(3d)
2‑(4‑Isopropyl‑benzenesulfonyl)‑[1,4]benzoquinone (3g)
1
Light yellow solid (81 %). H NMR (400 MHz, CDCl3) δ
1
Light yellow solid (71 %). H NMR (400 MHz, CDCl3) δ
7.43 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.93–
6.75 (m, 3H), 3.01–2.91 (m, 1H), 1.28 (d, J = 7.8 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 187.7 (s), 186.9 (s),
151.4 (s), 145.9 (s), 137.1 (s), 136.2 (s), 132.1 (s), 130.1
(s), 129.3 (s), 126.7 (s), 34.0 (s), 23.8 (s). Anal. Calcd for
C15H14O4S: C, 62.05; H, 4.86; O, 22.04; S, 11.04. Found:
C, 62.17; H, 4.76; O, 22.13; S, 10.86.
7.52–7.43 (m, 4H), 6.89–6.83 (m, 3H), 1.35 (s, 9H). 13C
NMR (100 MHz, CDCl3) δ 187.7 (s), 186.9 (s), 153.6 (s),
145.7 (s), 137.0 (s), 136.2 (s), 132.1 (s), 129.7 (s), 129.0
(s), 125.6 (s), 34.8 (s), 31.1 (s). Anal. Calcd for C16H16O4S:
C, 63.14; H, 5.30; O, 21.03; S, 10.54. Found: C, 63.22; H,
5.23; O, 21.10; S, 10.46.
2‑Benzenesulfonyl‑[1,4]benzoquinone (3e)
2‑Benzenesulfonyl‑[1,4]naphthoquinone (3h)
1
1
Light yellow solid (77 %). H NMR (400 MHz, CDCl3)
Light yellow solid (86 %). H NMR (400 MHz, CDCl3) δ
δ 7.39–7.14 (m, 5H), 6.83–6.76 (m, 3H). 13C NMR
(100 MHz, CDCl3) δ 187.5 (s), 186.6 (s), 145.6 (s), 140.4
(s), 136.8 (s), 136.0 (s), 131.8 (s), 129.6 (s), 129.1 (s), 129.0
(s). Anal. Calcd for C12H8O4S: C, 58.06; H, 3.25; O, 25.78;
S, 12.92. Found: C, 58.21; H, 3.13; O, 25.92; S, 12.77.
8.16–7.97 (m, 2H), 7.77–7.64 (m, 2H), 7.46–6.96 (m, 6H).
13C NMR (100 MHz, CDCl3) δ 185.0 (s), 184.4 (s), 147.8
(s), 140.2 (s), 134.4 (s), 133.6 (s), 133.5 (s), 132.3 (s), 131.9
(s), 130.3 (s), 129.2 (s), 129.0 (s), 126.8 (s), 125.7 (s). Anal.
Calcd for C16H10O4S: C, 64.42; H, 3.38; O, 21.45; S, 10.75.
Found: C, 64.53; H, 3.24; O, 21.56; S, 10.53.
2‑(4‑Propyl‑benzenesulfonyl)‑[1,4]benzoquinone (3f)
2‑(Toluene‑4‑sulfonyl)‑[1,4]naphthoquinone (3i)
1
Light yellow solid (86 %). H NMR (400 MHz, CDCl3) δ
1
7.34 (d, J = 8.4 Hz, 2H), 7.19 (t, J = 4.0 Hz, 2H), 6.81–
6.73 (m, 3H), 2.56 (t, J = 7.9 Hz, 2H), 1.66–1.53 (m, 2H),
0.90 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
187.7 (s), 186.9 (s), 145.8 (s), 145.3 (s), 137.0 (s), 136.2
(s), 132.0 (s), 130.0 (s), 129.2 (s), 128.7 (s), 37.8 (s), 24.3
(s), 13.8 (s). Anal. Calcd for C15H14O4S: C, 62.05; H, 4.86;
O, 22.04; S, 11.04. Found: C, 62.13; H, 4.79; O, 22.13; S,
10.88.
Light yellow solid (77 %). H NMR (400 MHz, CDCl3) δ
8.23–8.07 (m, 2H), 7.83–7.72 (m, 2H), 7.49 (d, J = 8.0 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 7.07 (s, 1H), 2.42 (s, 3H). 13
C
NMR (100 MHz, CDCl3) δ 185.2 (s), 184.6 (s), 148.0 (s),
140.4 (s), 134.6 (s), 133.8 (s), 133.7 (s), 132.5 (s), 132.1 (s),
130.5 (s), 129.4 (s), 129.2 (s), 127.0 (s), 125.9 (s), 21.4 (s).
Anal. Calcd for C17H12O4S: C, 65.37; H, 3.87; O, 20.49; S,
10.27. Found: C, 65.50; H, 3.69; O, 20.62; S, 10.05.
1 3

J IRAN CHEM SOC
2‑(2,5‑Dimethoxy‑benzenesulfonyl)‑[1,4]
naphthoquinone (3j)
2‑(4‑Propyl‑benzenesulfonyl)‑[1,4]naphthoquinone (3n)
1
Light yellow solid (81 %). H NMR (400 MHz, CDCl3) δ
1
Light yellow solid (83 %). H NMR (400 MHz, CDCl3)
8.22–8.08 (m, 2H), 7.82–7.73 (m, 2H), 7.51 (d, J = 8.4 Hz,
2H), 7.29 (d, J = 8.0 Hz, 2H), 7.08 (s, 1H), 2.65 (t,
J = 7.6 Hz, 2H), 1.75–1.62 (m, 2H), 0.98 (t, J = 7.2 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 185.2 (s), 184.6
(s), 148.0 (s), 145.2 (s), 134.6 (s), 133.8 (s), 133.7 (s),
132.5 (s), 132.1 (s), 130.7 (s), 129.4 (s), 128.6 (s), 127.0
(s), 125.9 (s), 37.9 (s), 24.3 (s), 13.8 (s). Anal. Calcd for
C19H16O4S: C, 67.04; H, 4.74; O, 18.80; S, 9.42. Found: C,
67.20; H, 4.66; O, 18.87; S, 9.33.
δ 8.19–8.08 (m, 2H), 7.80–7.72 (m, 2H), 7.02 (s, 1H),
6.98–6.90 (m, 2H), 6.82 (d, J = 2.8 Hz, 1H), 3.80 (s,
3H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 185.2
(s), 183.4 (s), 153.4 (s), 151.4 (s), 147.9 (s), 136.8 (s),
133.8 (s), 133.6 (s), 132.5 (s), 132.1 (s), 127.0 (s), 126.0
(s), 124.0 (s), 116.1 (s), 115.8 (s), 112.5 (s), 56.3 (s),
55.8 (s). Anal. Calcd for C18H14O6S: C, 60.33; H, 3.94;
O, 26.79; S, 8.95. Found: C, 60.55; H, 3.87; O, 26.85; S,
8.84.
2‑(4‑Methoxy‑benzenesulfonyl)‑[1,4]naphthoquinone
(3k)
General procedure for the synthesis
of pyrazol‑chromeno[2,3‑d]pyrimidine‑ones (B)
1
Light yellow solid (87 %). H NMR (400 MHz, CDCl3)
The substrate 3a (0.1 mmol) was dissolved in dry MeOH
(2.0 mL), and NaBH4 (0.4 mmol) was added by stirring
for at least 0.5 h. The reaction mixture was stirred at room
temperature for about 1 h. The reaction was terminated by
careful dropwise addition of water. The layers were sepa-
rated, the organic phase was washed with H2O, and the
combined aqueous layers were evaporated to dryness. The
residue was separated by column chromatography on silica
gel (ethyl acetate/petroleum ether = 1:5) to give light yel-
low solids.
δ 8.22–8.08 (m, 2H), 7.81–7.74 (m, 2H), 7.59 (d,
J = 8.8 Hz,, 2H), 7.05 (s, 1H), 7.00 (d, J = 8.8 Hz, 2H),
3.88 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 185.2 (s),
184.8 (s), 161.3 (s), 147.4 (s), 133.7 (s), 133.7 (s), 132.1
(s), 131.1 (s), 127.0 (s), 125.9 (s), 125.7 (s), 114.0 (s),
55.4 (s). Anal. Calcd for C17H12O5S: C, 62.19; H, 3.68;
O, 24.36; S, 9.77. Found: C, 62.33; H, 3.66; O, 24.40; S,
9.62.
2‑(4‑Isopropyl‑benzenesulfonyl)‑[1,4]naphthoquinone
(3l)
2‑(Toluene‑4‑sulfonyl)‑benzene‑1,4‑diol (B)
1
1
Light yellow solid (86 %). H NMR (400 MHz, CDCl3) δ
Light yellow solid (90 %). H NMR (400 MHz, CDCl3) δ
8.25–8.06 (m, 2H), 7.83–7.72 (m, 2H), 7.53 (d, J = 8.0 Hz,
2H), 7.34 (d, J = 8.4 Hz, 2H), 7.07 (s, 1H), 3.03–2.93
(m, 1H), 1.29 (d, J = 6.8 Hz, 6H). 13C NMR (100 MHz,
CDCl3) δ 185.2 (s), 184.6 (s), 151.3 (s), 148.0 (s), 134.6
(s), 133.8 (s), 133.7 (s), 132.6 (s), 132.1 (s), 130.8 (s),
129.5 (s), 127.7 (s), 127.2 (s), 127.0 (s), 126.7 (s), 125.9
(s), 34.1 (s), 23.8 (s). Anal. Calcd for C19H16O4S: C, 67.04;
H, 4.74; O, 18.80; S, 9.42. Found: C, 67.13; H, 4.62; O,
18.95; S, 9.39.
7.34 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 6.88–
6.81 (m, 1H), 6.76–6.68 (m, 2H), 4.92 (s, 1H), 4.75 (s, 1H),
2.40 (s, 3H).
Acknowledgments We gratefully acknowledge the financial support
of this work by the Youth Talent Development Foundation of China
Three Gorges University, Research Foundation for Advanced Talents
of China Three Gorges University and the National Natural Science
Foundation of China (21506115).
2‑(4‑tert‑Butyl‑benzenesulfonyl)‑[1,4]naphthoquinone
(3m)
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1
Light yellow solid (71 %). H NMR (400 MHz, CDCl3) δ
8.23–8.08 (m, 2H), 7.81–7.74 (m, 2H), 7.57–7.45 (m, 4H),
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J IRAN CHEM SOC
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