Rhodium-catalyzed desulfination of sodium arenesulfinates and oxidative annulation with alkynes

Article abstract of DOI:10.1002/adsc.201400930

Polycyclic aromatic compounds are widely used in materials science, so it is highly desirable to develop an efficient and practical approach to them. In this paper, a novel, efficient and practical method for the rhodium(III)-catalyzed desulfination of sodium arenesulfinates and oxidative annulation with alkynes has been developed, and the corresponding polycyclic aromatic compounds with multiple substituents were prepared in moderate to good yields. The reactions proceeded through sequential rhodium(III)-catalyzed desulfination, intermolecular addition of aryl-Rh(III) complexes to dialkyl but-2-ynedioates and diarylalkynes, and intramolecular oxidative annulation via C-H activation. The present method is the first example of the oxidative annulation of arene derivatives with two different alkynes. Therefore, it should afford a useful strategy for the synthesis of polycyclic aromatic compounds.

Full text of DOI:10.1002/adsc.201400930

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DOI: 10.1002/adsc.201400930
Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates and
Oxidative Annulation with Alkynes
Hui Wang,a Yuyuan Wang,b Haijun Yang,a Chunyan Tan,b Yuyang Jiang,b
Yufen Zhao,a and Hua Fua,b,*
a
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of
Chemistry, Tsinghua University, Beijing 100084, Peopleꢀs Republic of China
Fax : (+ 86)-10-6278-1695; e-mail: fuhua@mail.tsinghua.edu.cn
Key Laboratory of Chemical Biology (Guangdong Province), Graduate School of Shenzhen, Tsinghua University,
b
Shenzhen 518057, Peopleꢀs Republic of China
Received: September 23, 2014; Revised: November 9, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400930.
Abstract: Polycyclic aromatic compounds are widely addition of aryl-Rh(III) complexes to dialkyl but-2-
used in materials science, so it is highly desirable to ynedioates and diarylalkynes, and intramolecular ox-
À
develop an efficient and practical approach to them. idative annulation via C H activation. The present
In this paper, a novel, efficient and practical method method is the first example of the oxidative annula-
for the rhodium(III)-catalyzed desulfination of tion of arene derivatives with two different alkynes.
sodium arenesulfinates and oxidative annulation Therefore, it should afford a useful strategy for the
with alkynes has been developed, and the corre- synthesis of polycyclic aromatic compounds.
sponding polycyclic aromatic compounds with multi-
ple substituents were prepared in moderate to good
yields. The reactions proceeded through sequential Keywords: annulation; C H functionalization; desul-
rhodium(III)-catalyzed desulfination, intermolecular fination; polycyclic aromatic compounds; rhodium
À
Introduction
ACHTUNGTRENNUNG
The polycyclic aromatic motif constitutes an impor- tigated.[7,8] Some research groups have made great
tant class of compounds that are widely used in mate- achievements in the rhodium(III)-catalyzed synthesis
rials science, as light emitters, semiconductors, nano- of heterocycles via heterocyclization with one equiva-
tubes, light-absorption dyes, and liquid crystals due to lent of alkynes.[7] The synthesis of polycyclic aromatic
their electro- and photochemical properties.[1] The in- compounds via oxidative annulations with two or
troduction of multiple substituents on the molecules more equivalents of alkynes has also been well devel-
usually renders these compounds more soluble and oped,[2a,8] in which the used alkynes were the same in
stable, as well as affecting the modulation and im- each reaction system (Scheme 1a, b). However, there
provement of their fluorescence and charge mobility is no report on the rhodium(III)-catalyzed oxidative
properties.[2] Various methods for the synthesis of the couplings of aromatic substrates with two different al-
polycyclic aromatic compounds have been developed kynes thus far. On the other hand, arenesulfinic acids
in the past decades,[3] in which transition metal-cata- and their salts are readily available chemicals, and
lyzed cross-coupling reactions of organometallic re- their transition metal-catalyzed desulfitative arylation
agents with organic halides are a common strategy.[4] has attracted much attention.[9] To the best of our
Unfortunately, the unavailability of the starting mate- knowledge, the transition metal-catalyzed desulfita-
rials and multistep procedures restricts the application tive coupling of arenesulfinic acids and their salts
À
of the methods. Transition metal-catalyzed direct C
with alkynes is an unexplored field. Herein, we report
H bond functionalization has emerged as a powerful the rhodium(III)-catalyzed desulfination of sodium
tool in modern organic chemistry.[5] Recently, rhod- arenesulfinates and oxidative annulation with two
ACHTUNGTRENNUNGium(III) complexes were used as efficient catalysts for identical or different alkynes (Scheme 1c).
[6]
À
direct arene C H activation. In particular, rhod-
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Scheme 1. Rhodium(III)-catalyzed synthesis of polycyclic aromatic compounds via C H functionalization.
Table 1. Optimization of the conditions for the Rh(III)-catalyzed reaction of sodium 4-methylbenzenesulfinate (1b) with di-
methyl but-2-ynedioate (2a) leading to tetramethyl 6-methylnaphthalene-1,2,3,4-tetracarboxylate (3c).[a]
Entry
Oxidant
Acid
Solvent
Temperature [oC]
Yield [%][b]
1
2
3
4
5
6
7
8
Ag2O
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
CF3COOH
t-BuCOOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
–
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
CHCl3
AcOEt
dioxane
DMF
DMSO
DCE
DCE
DCE
DCE
DCE
70
70
70
70
70
70
40
100
70
70
70
70
70
70
70
70
70
70
70
70
25
72
42
trace
0
AgOAc
Ag2CO3
Cu(OAc)2
Cu(OTf)2
PhI(OAc)2
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
–
0
31
49
27
0
37
35
33
0
9
10
11
12
13
14
15
16
17
18
19
20
0
0[c]
0[d]
9[e]
48[f]
61[g]
AgOAc
AgOAc
AgOAc
AcOH
AcOH
[a]
Reaction conditions: sodium 4-methylbenzenesulfinate (1b) (0.25 mmol), dimethyl but-2-ynedioate (2a) (0.75 mmol),
[RhCp*Cl2]2 (0.0125 mmol), oxidant (0.5 mmol), acid (0.3 mmol), solvent (2.5 mL), temperature: 40–1008C, reaction
time: 36 h.
Isolated yield.
[b]
[c]
[d]
[e]
[f]
In the absence of Rh(III) catalyst.
In the absence of oxidant.
In the absence of acid.
Using 0.5 mmol of 2a as the substrate.
Reaction time: 24 h.
[g]
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Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates
Results and Discussion
The reaction of 1 with 2’ did not work in the absence
of 2. The results showed that the annulation-initiated
In preliminary experiments, the Rh(III)-catalyzed re- addition of aryl-Rh(III) complexes (II) to dialkyl but-
action of sodium 4-methylbenzenesulfinate (1b) with 2-ynedioates (2) was followed by reaction with di-
dimethyl but-2-ynedioate (2a) was used as the model
ACHTUNGTRENaNGNU rylalkynes (2’) due to the higher reactivity of 2 than
for optimized reaction conditions. As shown in 2’ (NB: 2 were more favorable than 2’ for Michael ad-
Table 1, six oxidants were screened by using 5 mol% dition of ArRhCp*OAc (II) to alkynes in Scheme 4).
[RhCp*Cl2]2 as the catalyst, AcOH as the acid, di- The reactivity depended on electronic effects of the
chloroethane (DCE) as the solvent at 708C for 36 h substrates, and diarylalkynes containing electron-with-
(entries 1–6), and AgOAc was found to be a suitable drawing groups afforded higher yields than those con-
oxidant (entry 2). Yields decreased when the temper- taining electron-donating groups. The rhodium(III)-
ature was changed (entries 7 and 8). Other acids were catalyzed desulfination and oxidative annulation
tested (entries 9 and 10), and AcOH provided the above could tolerate various functional groups includ-
highest yield (compare entries 2, 9 and 10). The effect ing esters (entries 1–25), ethers (entries 5, 13, 19 and
À
À
of solvents was investigated (compare entries 2, 11– 23), C Cl bond (entries 6 and 7), C Br bond (en-
15), and DCE afforded the best result (entry 2). No tries 8, 14, 17–21, 24), trifluoromethyl (entries 9, 15,
target product was found in the absence of Rh(III) 16, 21–25), nitro (entry 10), and cyano (entry 11) moi-
catalyst (entry 16). Product 3c was not observed with- eties.
out addition of oxidant (entry 17). Only a 9% yield
Inspired by the nice results above, we investigated
was realized in the absence of acid (entry 18). The the rhodium(III)-catalyzed reaction of sodium thio-
yield decreased when the amount of 2a was reduced phene-2-sulfinate with dimethyl but-2-ynedioate (2a)
(entry 19) or the time was shortened (entry 20).
or diethyl but-2-ynedioate (2b) under the standard
After finding the optimal reaction conditions, we conditions, and the corresponding products 3z and 3a’
examined the scope of sodium arenesulfinates and in- were obtained in the reasonable yields (Scheme 2).
ternal alkynes in this rhodium(III)-catalyzed desulfi-
To probe the reaction mechanism, the following
nation and oxidative annulation sequence (Table 2). control experiments were performed. As shown in
When sodium arenesulfinates (1) were treated with Scheme 3, reaction of sodium 4-methylbenzenesulfin-
three equivalents of dialkyl but-2-ynedioates (2) in
ACHTUNGTRENaNGNU te (1b) with dimethyl but-2-ynedioate (2a) in the ab-
the absence of diarylalkynes (2’), naphthalene deriva- sence of [RhCp*Cl2]2 and AgOAc led to the corre-
tives containing four esters were obtained (entries 1– sponding sulfone (4) in 91% yield (Scheme 3a), and
11), and sodium arenesulfinates with electron-donat- treatment of 4 with 2a under the standard conditions
ing groups provided higher yields than those with provided 3c in only 8% yield (Scheme 3b), which
electron-withdrawing groups. When sodium arenesul- showed that 4 was not an intermediate in the rhod-
finates (1) were reacted with 1.2 equivalents of dialkyl
ACHTUNGTRENiNUGN um(III)-catalyzed desulfination and oxidative annula-
but-2-ynedioates (2) and two equiv. of diarylalkynes tion. Reactions of sodium 4-methylbenzenesulfinate
(2’), naphthalene derivatives containing two esters (1b) with two equivalents of dimethyl but-2-ynedioate
and two aryls were formed (entries 12–21). Mean- (2a) and one equivalent of diphenylacetylene (2’a)
while, traces to small amounts of naphthalene deriva- were carried out under the standard conditions, and
tives with four esters were observed, but no naphtha- products 3c and 3l were obtained in 42% and 17%
lene derivatives containing four aryls were observed. yields, respectively (see Scheme 3c). When sodium 4-
Scheme 2. Rhodium(III)-catalyzed reaction of sodium thiophene-2-sulfinate with dimethyl but-2-ynedioate (2a) or diethyl
but-2-ynedioate (2b) under the standard conditions.
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Table 2. Rhodium(III)-catalyzed desulfination and oxidative annulation.[a]
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Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates
Table 2. (Continued)
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Table 2. (Continued)
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Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates
Table 2. (Continued)
[a]
[b]
Reaction conditions: sodium arenesulfinate (1) (0.25 mmol), dialkyl but-2-ynedioate (2) (0.75 mmol for en-
tries 1–11 without addition of 2’; 0.3 mmol for entries 12–25), diarylalkyne (2’) (0.5 mmol for entries 12–25),
[RhCp*Cl2]2 (0.0125 mmol), AgOAc (0.5 mmol), AcOH (0.3 mmol), DCE (2.5 mL), temperature: 708C, reac-
tion time: 30 or 36 h.
Isolated yield.
methylbenzenesulfinate (1b) was reacted with vious reports.[2a,8,9] Treatment of sodium arenesulfinate
1.2 equivalents of 2a and 2 equivalents of 2’a, we ob- (1) with AcOH gives arenesulfinic acid (1’) with
tained 3c in 7% yield and 3l in 43% yield (see cleavage of NaOAc, and reaction of [RhCp*Cl2]2 with
entry 12 in Table 2). The results showed that yields of NaOAc leads to [RhCp*(OAc)2]2 or RhCp*(OAc)2.
3c and 3l were related to the amount of the two inter- Coordination of 1 or 1’ with the Rh catalyst provides
nal alkynes. Furthermore, reactions of sodium 4-tri- I, and desulfination of I affords the aryl-Rh(III) com-
fluoromethylbenzenesulfinate (1g) with dimethyl but- plex II.[9] When dialkyl but-2-ynedioate (2) and diaryl-
2-ynedioate (2a), bis(4-methylphenyl)acetylene (2’b)
ACHTUNGTRENaNGNU lkyne (2’) are present in the reaction system, prefer-
and bis(4-trifluoromethylphenyl)acetylene (2’c) were ential reaction of 2 with II provides III because 2 has
performed, and 2’c containing an electron-withdraw- a higher reactivity than 2’. Intramolecular transforma-
ing group displayed higher reactivity than 2’b contain- tion of III forms IV freeing AcOH, reaction of IV
ing an electron-donating group on phenyl ring (see with 2’ produces V, and reductive elimination of V
Scheme 3d).
yields the target product releasing RhCp*.[2a,8] Finally,
Therefore, a possible mechanism is proposed in oxidation of RhCp* with AgOAc regenerates catalyst
Scheme 4 according to the results above and the pre- RhCp*(OAc)2 or [RhCp*(OAc)2]2.
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Scheme 3. (a) Reaction of sodium 4-methylbenzenesulfinate (1b) with dimethyl but-2-ynedioate (2a) in the absence of
[RhCp*Cl2]2 and AgOAc. Under the standard conditions, (b) treatment of 4 with 2a; (c) reactions of sodium 4-methylbenz-
ACHTUNGTRENNUNGenesulfinate (1b) with dimethyl but-2-ynedioate (2a) and diphenylacetylene (2’a); (d) reactions of sodium 4-trifluoromethyl-
benzenesulfinate (1g) with dimethyl but-2-ynedioate (2a), bis(4-methylphenyl)acetylene (2’b) and bis(4-trifluoromethylphe-
nyl)acetylene (2’c).
Conclusions
for the oxidative annulation of arene derivatives with
two different alkynes.
We have developed a novel, efficient and practical
method for the rhodium(III)-catalyzed desulfination
of sodium arenesulfinates and oxidative annulation,
and the corresponding polycyclic aromatic compounds
with multiple substituents were prepared in moderate
to good yields. The protocol uses readily available
sodium arenesulfinates, dialkyl but-2-ynedioates, and
Experimental Section
General Procedure for Synthesis of Compounds 3a–k,
3z, 3a’
A 25-mL Schlenk tube was charged with a magnetic stirrer
and 1,2-dichloroethane (2.5 mL); sodium arenesulfinate (1)
(0.25 mmol), dialkyl but-2-ynedioate (0.75 mmol), AgOAc
(0.5 mmol, 83 mg), [RhCp*Cl2]2 (0.0125 mmol, 7.7 mg) and
AcOH (0. 3 mmol, 18 mg) were added to the tube. The tube
was evacuated and refilled with a nitrogen atmosphere for
diarylalkACHTUNGTRENNUNGynes as the starting materials, and the proce-
dures involve sequential rhodium(III)-catalyzed de-
sulfination, intermolecular addition of aryl-Rh(III)
complexes to dialkyl but-2-ynedioates and diarylal-
À
kynes, and intramolecular oxidative annulation via C
H activation. The present method is the first example three times, and the mixture was stirred at 708C for 30 or
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Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates
Scheme 4. Possible mechanism for the rhodium(III)-catalyzed desulfination and oxidative annulation.
36 h under a nitrogen atmosphere. The resulting mixture
was cooled to room temperature, the solvent was removed
on a rotary evaporator, and the residue was purified by
column chromatography on silica gel using hexane/ethyl
acetate as the eluent to give the desired target product (3a–
k, 3z, 3a’).
(65%); white solid; mp 112–1138C; 1H NMR (CDCl3,
400 MHz): d=8.26 (s, 1H), 7.95 (d, 1H, J=9.2 Hz), 7.76 (d,
1H, J=8.7 Hz), 4.01 (s, 3H), 4.00 (s, 3H), 3.94 (s, 6H);
13C NMR (CDCl3, 100 MHz): d=166.8, 166.7, 166.5, 166.4,
136.5, 134.1, 133.3, 132.7, 131.2, 129.2, 128.6, 128.5, 127.9,
124.9, 53.4, 53.3; HR-MS (ESI+): m/z=456.0295, calcd. for
C18H19BrNO8, [M+NH4]+: 456.0289.
Dimethyl
3,4-diphenyl-6-(trifluoromethyl)naphthalene-
General Procedure for Synthesis of Compounds 3l–y
1,2-dicarboxylate (3o): Eluent: hexane/ethyl acetate (10:1);
yield: 64 mg (55%); white solid; mp 183–1848C; H NMR
1
A 25-mL Schlenk tube was charged with a magnetic stirrer
and 1,2-dichloroethane (2.5 mL); sodium arylsulfinate (1)
(0.25 mmol), dialkyl but-2-ynedioate (0.3 mmol), 1,2-diphe-
(CDCl3, 400 MHz): d=8.43 (d, 1H, J=9.2 Hz), 7.89 (s, 1H),
7.76 (d, 1H, J=9.2 Hz), 7.31–7.24 (m, 3H), 7.18–7.12 (m,
3H), 7.11–7.01 (m, 4H), 4.03 (s, 3H), 3.50 (s, 3H); 13C NMR
(CDCl3, 100 MHz): d=168.5, 167.6, 143.6, 138.2, 137.2,
136.8, 134.9, 132.4, 130.7, 130.5, 130.0, 129.5 (q, J=32.4 Hz),
128.7, 128.2, 127.8, 127.6, 127.3, 127.2, 125.1 (q, J=3.8 Hz),
124.0 (q, J=270.8 Hz), 123.3 (q, J=2.9 Hz), 53.2, 52.5; HR-
MS (ESI+): m/z=482.1577, calcd. for C27H23F3NO4, [M+
NH4]+: 482.1574.
nylethyne
(0.5 mmol),
AgOAc
(0.5 mmol,
83 mg),
[RhCp*Cl2]2 (0.0125 mmol, 7.7 mg) and AcOH (0.30 mmol,
18 mg) were added to the tube. The tube was evacuated and
refilled with a nitrogen atmosphere for three times, and the
mixture was stirred at 708C for 36 h under a nitrogen atmos-
phere. The resulting mixture was cooled to room tempera-
ture, the solvent was removed on a rotary evaporator, and
the residue was purified by column chromatography on
silica gel using hexane/ethyl acetate as the eluent to give the
desired target product (3l–y).
Dimethyl
6-bromo-3,4-bis[4-(trifluoromethyl)phenyl]-
naphthalene-1,2-dicarboxylate (3x): Eluent: hexane/ethyl
acetate (10:1); yield: 101 mg (66%); white solid; mp 214–
2158C; 1H NMR (CDCl3, 600 MHz): d=8.18 (d, 1H, J=
8.9 Hz), 7.73 (dd, 1H, J=8.9 Hz, J=2.1 Hz), 7.60 (d, 1H,
J=1.4 Hz), 7.56 (d, 2H, J=8.3 Hz), 7.44 (d, 2H, J=7.6 Hz),
7.19 (d, 2H, J=7.6 Hz), 7.16 (d, 2H, J=7.6 Hz), 4.03 (s,
3H), 3.51 (s, 3H); 13C NMR (CDCl3, 150 MHz): d=168.0,
167.4, 141.8, 140.6, 140.0, 135.7, 134.0, 132.2, 131.9, 131.1,
130.4, 130.3, 130.2 (q, J=32.7 Hz), 129.7 (q, J=33.0 Hz),
129.1, 128.0, 127.9, 125.4 (q, J=2.9 Hz), 124.7 (q, J=2.9 Hz),
124.0 (q, J=271.5 Hz), 123.9 (q, J=271.5 Hz), 123.9 (q, J=
271.4 Hz), 53.3, 52.6; HR-MS (ESI+): m/z=628.0548, calcd.
for C28H21BrF6NO4, [M+NH4]+: 628.0553.
Four representative examples are shown below.
Tetramethyl 6-methylnaphthalene-1,2,3,4-tetracarboxylate
(3c): Eluent: hexane/ethyl acetate (5:1); yield: 67 mg
(72%); white solid; mp 154–1558C; 1H NMR (CDCl3,
400 MHz): d=7.95 (d, 1H, J=8.7 Hz), 7.80 (s, 1H), 7.51
(dd, 1H, J=8.7 Hz, J=1.4 Hz), 4.01 (s, 3H), 4.00 (s, 3H),
3.90 (s, 6H), 2.53 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=
167.5, 166.9, 166.8, 140.4, 133.9, 133.3, 132.1, 130.4, 128.4,
127.7, 126.6, 126.1, 125.2, 53.2, 22.1; HR-MS (ESI+): m/z=
392.1344, calcd. for C19H22NO8, [M+NH4]+: 392.1340.
Tetramethyl 6-bromonaphthalene-1,2,3,4-tetracarboxylate
(3h): Eluent: hexane/ethyl acetate (5:1); yield: 71 mg
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Acknowledgements
The authors wish to thank the National Natural Science
Foundation of China (Grant Nos. 21172128, 21372139 and
21221062), and the Ministry of Science and Technology of
China (Grant No. 2012CB722605) for financial support.
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FULL PAPERS
Rhodium-Catalyzed Desulfination of Sodium Arenesulfinates
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Adv. Synth. Catal. 0000, 000, 0 – 0
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These are not the final page numbers!

FULL PAPERS
12 Rhodium-Catalyzed Desulfination of Sodium
Arenesulfinates and Oxidative Annulation with Alkynes
Adv. Synth. Catal. 2015, 357, 1 – 12
Hui Wang, Yuyuan Wang, Haijun Yang, Chunyan Tan,
Yuyang Jiang, Yufen Zhao, Hua Fu*
12
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ꢁ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!