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RhCl3.3H2O-Catalyzed Ligand-Enabled Highly Regioselective Thiolation of Acrylic Acids Can Liu, Yi Fang, Shun-Yi Wang, and Shun-Jun Ji ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b02982 • Publication Date (Web): 22 Aug 2019 Downloaded from pubs.acs.org on August 22, 2019
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ACS Catalysis
RhCl33H2O-Catalyzed Ligand-Enabled Highly Regioselective Thiolation of Acrylic Acids Can Liu,†,‡ Yi Fang,†,‡ Shun-Yi Wang,*,†,‡ and Shun-Jun Ji*,†,‡ † Key
Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China. ‡Collaborative
Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou, 215123, China.
Supporting Information Placeholder ABSTRACT: A simple inorganic rhodium salt RhCl33H2O was used as the
catalyst to achieve the thiolation of acrylic acids, with a series of (Z)-alkenyl sulfides obtained exclusively. It is noteworthy that [Cp*RhCl2]2 was not as efficient as RhCl33H2O in this strategy. Furthermore, the product could be transferred to biological and pharmacological thioflavone conveniently.
R1
COOH
R2
H
INTRODUCTION
RhCl3 3H2O
R1
COOH
R2
SR3
* Higher catalytic efficiency than [Cp*RhCl2]2 * Easier derivative carboxyl group as DG
KEYWORDS: RhCl33H2O, carboxylate-directed, alkenyl sulfide, C-H activation, regioselectivity
R3SSR3
(Scheme 1).3 Nevertheless, limited research has been conducted on non-aromatic C(sp2)-H activation, and aromatic reaction still predominates in current research. Therefore, developing carboxylate-directed non-aromatic C(sp2)-H activation has important practical significance.
C-H activation has attracted much attention in recent years due to its high atom economy and diversity of reaction, and has become one of the important strategies of organic synthesis. However, in order to ensure regioselectivity, directing group (DG) is usually indispensable. Strong directing groups such as pyridine, pyrimidine and 8-aminoquinoline were first used in C-H activation reactions.1 Soon after, weak guiding groups such as oxime ether, ketone and amide have also been reported.2 Since 2007, carboxyl group has been initially used as directing group of C-H activation reaction because of its non-toxicity, easy removal, widespread existence in nature and abundant derivative reactions. During the past decade, carboxyl group show extraordinary talents in this field. Palladium-, rhodium-, ruthenium- and iridiumcatalyzed systems have been developed successfully to achieve arylation, alkylation, alkenylation, thiolation and selenation
[Cp*RhCl2]2 (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) is the most used catalyst in existing rhodium-catalyzed C-H activation reactions. The Cp* ligand is believed to be helpful in stabilizing rhodium intermediates, as well as promoting eliminating processes due to the steric hindrance effect. Indeed, a large number of reported facts prove that the catalyst has high efficiency, regioselectivity and excellent functional group tolerance.4 [Cp*RhCl2]2 is generally prepared from the coordination reaction of RhCl33H2O with excess 1,2,3,4,5pentamethylcyclopentadiene in methanol under an inert atmosphere. However, as the precursor of [Cp*RhCl2]2, COOH
R Ar 2015, Gooßen, ref 3m COOH
COOH
R
COOH
R R
XR' X = S or Se
HOOC
[Ru(p-cymene)Cl2]2
COOH R
Ar
Ar 2007, Daugulis, ref 3a
2017, Baidya, ref 3i
2018, Baidya, ref 3h
R
R
[IrCp*Cl2]2
2011, Larrosa, ref 3b
Pd(OAc)2 O COOH
COOH
R
R
O O
N R'
n
O
[Rh(nbd)Cl2]2
[RhCp*Cl2]2
2017, Ackermann & Baidya ref 3j & ref 3k
2018, Gooßen, ref 3l
CH2OBn
Bu
2013, Yu, ref 3c
R'
O
R
R
2015, Yu, ref 3d
R Het 2015, Su, ref 3f O R
COOH R R HOOC 2015, Li, ref 3e
HOOC 2019, Gooßen, ref 3g
Scheme 1. Carboxylate-directed C-H activation of benzoic acids under Pd, Rh, Ru and Ir catalysis
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RhCl33H2O was used to be the catalyst of C-H activation rarely.5 In 1990, the RhCl(PPh3)3/Cu2+ redox couple was used in carboxylation of aromatic rings. Inspired by this work, Witulski and cooperators used RhCl33H2O and Cu(II) salts to achieve intramolecular C-H/C-H Coupling.6 Since then, there are only a few articles which have reported RhCl33H2O-catalyzed C-H activation and relevant research.7 Alkenyl sulfides are a class of important sulfur-containing compounds, which are widely used in organic synthesis, material science and biopharmaceuticals.8 With the development of related research, its synthesis is becoming more simple and efficient. Initial synthetic strategies required unfriendly sulfur sources, low atomic economy, poor selectivity and harsh reaction conditions (Scheme 2, A & B),9 but now these shortcomings have been overcome. In 2018, we reported an N-tosylamide-assisted synthesis of (Z)--alkenyl sulfides through [Cp*RhCl2]2-catalyzed thiolation of alkenes with high efficiency and good substrate tolerance (Scheme 2, C).10 However, we failed to remove the directing group, which hinders the subsequent application. Therefore, we hope to develop a system with directing group which is easier to remove or derive. Meanwhile, we also desire to apply RhCl33H2O to this system with the help of ligand. Herein, we demonstrated a RhCl3.3H2O-catalyzed ligand-enabled highly regioselective thiolation of acrylic acids to afford (Z)--alkenyl sulfides(Scheme 2, D). Scheme 2. Synthesis of alkenyl sulfides through different processes. A. Nucleophilic addition of thiols to alkynes R1SH
R2
R 1S
R2
1
R S
R2
smelly and toxic thiol poor regioselectivity
B. Cross-coupling of thiols and vinyl halides X R1SH
R2 or
X
R 1S
R2
[M]
R2
harsh conditions low atom economy
or R 1S
R2
C. Our previous work: regioselective synthesis of (Z)--alkenyl sulfides O R1 R
N H
2
Ts
H
R3XXR3
[Cp*RhCl2]2
X = S, Se
O R1 R
2
N H XR3
Ts
difficult-removed DG complicated catalyst
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the yield up to 75% further (Table 1, entry 16). By the following investigation, reaction time and temperature were determined to 6 h and 120 oC, respectively. Under this condition, the ligand was replaced by cheaper tris(2,6-dimethoxyphenyl)phosphane (L37), and the yield could still maintain at 79% (Table 1, entry 20). In addition, when [Cp*RhCl2]2 was employed in this reaction, the yield decreased to 69% (Table 1, entry 21). Table 1. Optimization of the Rh-catalyzed thiolation of 1a with 2aa H PhSSPh
Cu(OAc)2
ligand
T (oC)
Time(h)
solvent, T, 6 h
2a
4a
1
/
/
120
12
0
2
10
/
120
12
17
3
20
/
120
12
27
4
50
/
120
12
40
5
100
/
120
12
49
6
150
/
120
12
38
7
100
L2
120
12
25
8
100
L8
120
12
25
9
100
L19
120
12
52
10
100
L33
120
12
57
11
100
L34
120
12
59
12
100
L35
120
12
37
13
100
L36
120
12
71
14
100
L36
80
12
Trace
15
100
L36
100
12
73
16c
100
L36
120
12
75
17 c
100
L36
140
12
72
18 c
100
L36
120
6
80
19 c
100
L36
120
18
75
20 c
100
L37
120
6
79(77 d)
21 c,e
100
L37
120
6
69
PPh2 PPh2
NHAc
R2
COOH
N
H
COOH
N
R3XXR3 X = S, Se
RhCl3 3H2O
R1 R2
COOH
L2
XR3
RESULTS AND DISCUSSION
O
Initially, atropic acid 1a and diphenyl disulfide 2a were chose to investigate the reaction conditions (Table 1, see Supporting Information for more details). Rh catalyst could not be replaced by other transition metals such as Pd, Co, Ni, Ru. The reaction could not undergo in common solvents such as ether, benzene and alcohols other than amide solvents and MeCN. The amount and type of Cu salts are key factors of the reaction. The yield peaked when 1 equiv Cu(OAc)2 was added (Table 1, entry 5). Subsequently, different ligands were applied to the reaction. Phosphine ligands were found to be beneficial to the reaction. The desired product could be obtained in 68% yield when 30 mol % tris(2,4,6-trimethoxyphenyl)phosphane (L36) was added. And the yield would increase to 71% when the amount of ligand reduced to 15 mol % (Table 1, entry 13). The increment of 2a also brings
O
O P O
simple DG simple catalyst
O
LC-Yield(%)b
(mol %)
D. This work R1
COOH
COOH 1a
Entry
SPh
RhCl3 3H2O (5 mol %) Cu(OAc)2 Ligand
P
O
L8
L19
O
O
O
L34
O O
P
O O
O O
O O P
P O
L35
L33
OO O
OO
L36
O
L37
aReaction
conditions: 1a (0.1 mmol, 1.0 equiv), 2a (0.1 mmol, 1.0 equiv), RhCl33H2O (5 mol %), ligand (15 mol %), Cu(OAc)2(1 equiv), DMF (1 mL), 120 oC, 12 h. bLC yield using biphenyl as the internal standard. cPhSSPh 2 equiv. dIsolated yield. e[Cp*RhCl ] (2.5 mol %). DMF = N,N-dimethylformamide. 2 2 With the optimal conditions in hand, we explored the substrate scope of acrylic acids (Table 2). Ortho- and meta-substituted substrates could undergo the reaction but the yield went down (3a and 3b). Electron effect did not show obvious effect on this reaction, corresponding products were obtained in 72-78% yield,
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ACS Catalysis respectively (3c-3e). Benzyl acrylic acid could also react smoothly with 76% yield (3f). Unactivated alkyl acrylic acids could also adapt to this system to give desired products in moderate yield (3g and 3h). It is worth mentioning that this strategy could also be applied to the thiolation of nonterminal alkenes, although the yields were not so ideal (3i-3k). However, cinnamic acid could not afford products successfully (3l). We assume that it is due to the steric hindrance effect. Table 2. Substrate scope of acrylic
Table 3. Substrate scope of disulfidesa
COOH
RhCl3 3H2O (5 mol %) Cu(OAc)2 (1 equiv) L37 (15 mol %)
RSSR
1a (1 equiv)
4
2 (2 equiv)
OMe
acidsa
S R2
COOH
1 (1 equiv)
Ph
RhCl3 3H2O (5 mol %) Cu(OAc)2 (1 equiv) L37 (15 mol %)
H S
COOH
DMF, 120 oC
S
R1
SR
R
DMF, 120 oC
1
S
R2
S
COOH
Ph
Ph
4b: 77%
4a: 77%
COOH 3
2b (2 equiv)
COOH
S
Cl
Br
S
S
COOH 4c: 73%
F S
S
S
S
S
COOH
COOH
COOH
COOH
MeO 3a: 59%
3b: 56%
COOH
Ph
4d: 75%
3c: 76%
3d: 72%
S
S
S
S
COOH
COOH
COOH
COOH
F 3f: 76%
Ph
COOH
COOH 4f: 62%
4e: 73%
COOH
Ph
4g: 22%b
Cl
3h: 48%
3g: 52%
COOH
4h: 52%b
S
S
S Ph
3e: 78%
Ph
S
Ph
Ph
COOH
4i: 36%
COOH
Se Ph
COOH
4k: 22%b
4j: 31%c
b
aReaction conditions: 1 (0.3 mmol), 2b (0.6 mmol), RhCl 3H O 3 2 (5 mol %), Cu(OAc)2 (1 equiv), L37 (15 mol %), DMF (3 mL), 120 oC, 6 h. b140 oC, 12 h. cRhCl33H2O (10 mol %), L37 (30 mol %), 140 oC, 12 h.
Scheme 3. Scale-up synthesis. S COOH 3i: 39%
S COOH 3j: 35%b
S COOH 3k: 26%
Ph
S COOH
COOH
3l: trace
aReaction conditions: 1 (0.3 mmol), 2b (0.6 mmol), RhCl 3H O 3 2 (5 mol %), Cu(OAc)2 (1 equiv), L37 (15 mol %), DMF (3 mL), 120 oC, 6 h. b140 oC, 12 h.
Next, we investigate the tolerance of disulfides (Table 3). For electron-rich substrates such as methyl- (4b) and methoxy- (4c), weak electron-deficient substrates such as F-, Cl-, Br-substituted disulfides (4d-4f), the reaction underwent smoothly, and the corresponding target products could be obtained in 62-77% yields, respectively. But for strong electron-deficient nitro-substituted disulfides, the reaction could not occur. For alkyl disulfides, the reaction temperature should be increased to 140 oC, and the yield decreased in varying degrees (4g-4j). We also tried to apply diselenides to this system, but the result was not ideal. The target product (4k) was merely obtained in 22% yield. Meanwhile, we attempted to amplify the template reaction to gram level. With reaction time prolonged to 24 h, 4a could be obtained in 60% isolated yield (scheme 3), which implies the possibility of large-scale industrial production.
1a (6 mmol)
PhSSPh
RhCl3 3H2O (5 mol %) Cu(OAc)2 (1 equiv) L37 (15 mol %)
SPh COOH
DMF, 120 oC, 24 h
2a (12 mmol)
4a, 0.9260g isolated yield: 60%
Thioflavone is the core moiety of various natural products with biopharmaceutical activities. In addition, thioflavone and its oxide can be further derived to protect many light-unstable functional groups11. Based on the structure of aforementioned products, Friedel-Crafts acylation was considered to achieve the construction of thioflavone. When 4a was stirred in 0.5 mL trifluoromethanesulfonic acid for 3 hours under 120 oC heating, the derivative thioflavone could be obtained in 88% yield. Meanwhile, 4a was successfully reduced to corresponding alcohol in 50% yield (Scheme 4). Scheme 4. Derivative reaction. S
TfOH (0.5 ml)
LiAlH4 (3 equiv) S
120 oC, 3 h
Ph
S
THF, reflux, 1 h
O Ph der1, 88%
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COOH 4a
Ph
CH2OH
der2, 50%
ACS Catalysis Scheme 6. XPS & AES spectra of yellow precipitate. Cu2p Scan
LC1 Survey
3.00E+05
1.00E+06 9.00E+05 8.00E+05 7.00E+05
2.00E+05 Counts / s
6.00E+05 5.00E+05 4.00E+05
1.00E+05
3.00E+05 2.00E+05 1.00E+05
0.00E+00 0
0.00E+00 1200
1000
800
600
400
200
960
950
940
930
Binding Energy (eV)
Binding Energy (eV)
a. XPS survey spectrum of yellow precipitate
b. XPS sprectra of yellow precipitate
CuLM2 Scan 6.00E+04
5.00E+04
Counts / s
To explore the plausible mechanism, a series controlled experiments were conducted. Under standard condition, atropic acid 1a was replaced by ethyl 2-phenylacrylate to undergo the reaction (Scheme 5, A). However, corresponding product was not obtained, which reveals the direction of carboxyl group is indispensable. At the same time, the path of Michael additionelimination was ruled out. Next, we investigated Kinetic Isotope Effect (KIE) of the system (Scheme 5, B). Through a competitive experiment between 1a and 1a-d2, the KIE value was calculated as 3.0, which suggested a concerted metalation deprotonation (CMD) process. In addition, it was found that a large amount of precipitate was produced after the reaction. The yellow precipitate is poorly soluble in organic solvents, but it can dissolve in concentrated acids to generate diphenyl disulfide. Therefore, we speculate that the solid may be a low valent copper species bound to disulfide. By X-ray photoelectron spectroscopy (XPS) characterization, from the survey spectrum (Scheme 6, a), we could confirm the existence of copper. From the high resolution XPS spectrum (Scheme 6, b), characteristic satellite peaks of Cu(II) (standard spectra see Scheme 6, c) did not appear, which indicated the precipitate did not contain Cu(II). By Auger Electron Spectroscopy (AES) characterization (Scheme 6, d), two groups of peaks were found, which reveals the existence of Cu(0) and Cu(I). That is to say, the precipitate is the mixture of low valence copper species.
Counts / s
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 4 of 6
4.00E+04
3.00E+04
2.00E+04
1.00E+04 582 580 578 576 574 572 570 568 566 564 562 560 558 Binding Energy (eV)
Scheme 5. Controlled experiments. A. Replaced by ethyl 2-phenylacrylate
c. Standard XPS spectra of different kinds of Cu
RhCl3 3H2O (5 mol %) Cu(OAc)2 (1 equiv) L37 (15 mol %) Ph
COOEt
PhSSPh DMF, 120 oC, 6 h
SPh
Scheme 7. Plausible mechanism. Ph
COOEt
RhCl3 3H2O Ligand
B. Competitive experiment between 1a and 1a-d2
RhCl3 3H2O (5 mol %) Cu(OAc)2 (1 equiv) L37 (15 mol %)
COOH 1a S
D
D
S
DMF, 120 oC, 1.5 h kH/kD = 3.0
Ph
COOH 1a-d2
D/H Ph
A
S
Ph
HOAc
4c and 4c-d
[LRhIIISPh]OAc
2AcOH
C L SPh Ph
RhIII O
COOH 4a
In summary, a RhCl33H2O-Catalyzed thiolation of acrylic acids was reported. With higher efficiency than [Cp*RhCl2]2, this strategy provides a novel way to construct C-S bond through C-H activation. The reaction can be successfully enlarged to gram scale, and the product can be efficiently converted into thioflavone with potential biopharmaceutical activity, which shows practical application in industrial production.
COOH 1a
CuII
COOH
OMe
CONCLUSION
H
LRhIII(OAc)2
PhSCu0, I
Based on above experimental results and related literatures, we proposed a plausible mechanism (Scheme 7). Ligand and Cu(OAc)2 enabled RhCl33H2O to form the active RhIII species A. A reacts with substrate 1a to generate five-membered rhodacycle B through a CMD process. Then, product 4a and intermediate C are obtained by the nucleophilic substitution of B and disulfide. At last, the active species A is regenerated through oxidation of inactive intermediate C by Cu(OAc)2, and the low valence Cu species is formed simultaneously.
Cu(OAc)2
OMe
OMe Ph
d. AES sprectra of yellow precipitate
Ph PhSSPh HOAc
O B
ASSOCIATED CONTENT
Supporting Information
Detailed experimental procedures. This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
[email protected];
[email protected] Notes The authors declare no competing financial interests.
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ACS Catalysis
Rh(III)-Catalyzed Acceptorless Dehydrogenative Coupling of (Hetero)arenes with 2-Carboxyl Allylic Alcohols. Org. Lett. 2018, 20, 740-743.
ACKNOWLEDGMENT
We gratefully acknowledge the National Natural Science Foundation of China (21971174, 21772137, 21672157), the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 16KJA150002), the Ph.D. Programs Foundation of PAPD, the project of scientific and technologic infrastructure of Suzhou (SZS201708), and Soochow University for financial support. We thank Rong Zhang in this group for reproducing the result of 3f, 3i, 4b, 4f.
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