Chemoselective carbon-carbon cross-coupling via palladium-catalyzed copper-mediated C-S cleavage of disulfides

Article abstract of DOI:10.1002/adsc.201300776

An efficient method for carbon-carbon bond formation is described. The process employs the palladium-catalyzed copper-mediated cross-coupling of diheteroaryl disulfides with arylboronic acids or alkynes to deliver C-C coupling products through unreactive C-S bond cleavage. The scope of the coupling reactions, including both the disulfides and arylboronic acids or alkynes, are documented.

Full text of DOI:10.1002/adsc.201300776

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DOI: 10.1002/adsc.201300776
Chemoselective Carbon-Carbon Cross-Coupling via Palladium-
À
Catalyzed Copper-Mediated C S Cleavage of Disulfides
Zheng-Jun Quan,a,* Ying Lv,a Fu-Qiang Jing,a Xiao-Dong Jia,a Cong-De Huo,a
and Xi-Cun Wanga,*
a
Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, China; Gansu Key Laboratory of
Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu
730070, Peopleꢀs Republic of China
Fax : (+86)-931-7972626; e-mail: quanzhengjun@hotmail.com or wangxicun@nwnu.edu.cn
Received: August 27, 2013; Revised: November 23, 2013; Published online: January 28, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300776.
Abstract: An efficient method for carbon-carbon
bond formation is described. The process employs
the palladium-catalyzed copper-mediated cross-cou-
pling of diheteroaryl disulfides with arylboronic
tions of boronic acid with different sulfur compounds,
which is well known as the Liebeskind–Srogl cross-
coupling reaction, have attracted extensive interest in
the organic chemistry community.[7] The cross-cou-
À
acids or alkynes to deliver C C coupling products
plings of thioACTHNGUTERNNUaG mide with boronic acids or alkynes as
À
through unreactive C S bond cleavage. The scope
a variant of the non-basic Liebeskind–Srogl reaction
have been studied by others,[8] most notably Kappe
and co-workers.[9] The Liebeskind–Srogl cross-cou-
pling implies a Cu ion pair with the thiolate in a ther-
of the coupling reactions, including both the disul-
fides and arylboronic acids or alkynes, are docu-
mented.
À
modynamically strong Cu SMe bond and the forma-
À
Keywords: alkynes; arylboronic acids; C S bond
tion of an intermediate from the oxidative addition of
2
3
À
À
cleavage; diheteroaryl disulfides; Liebeskind–Srogl
cross coupling
the CACHTNGUTRENNU(G sp ) S bond, rather than of the CACHTUNGRTEN(NUNG sp ) S bond,
to palladium (Scheme 1). We hypothesized that an sp2
hybridized disulfide-boronic acid cross-coupling car-
ried out under Liebeskind–Srogl reaction conditions
in the presence of a second sacrificial equivalent of
À
the Cu(I) would achieve the desired two C C cou-
Transition metal-catalyzed cross-couplings are some pling products. Furthermore, the successful develop-
of the most dependable and effectual methods for ment of such a reaction would demonstrate for the
[1]
forming C C bonds. The Suzuki–Miyaura[2] or the first time that disulfide activation is subject to selec-
À
Sonogashira[3] couplings have become one of the most tive C C bond formation. Here, we reveal the unique
À
2
2
À
useful tools to construct Csp Csp (Csp) bonds. Al- attributes of the Liebeskind–Srogl coupling system
kenyl/aryl halides are frequently used as the electro- applied to the cross-coupling of disulfides with aryl-
philes due to their relatively high reactivity and spec- boronic acids and terminal alkynes (Scheme 2).
tacular achievements have been made in recent de-
cades. However, some disadvantages have to be ac-
cepted.[4] For example, aryl halides are not always
easily available. Thus, the search for alternative elec-
trophiles as novel substrates to organic halides for the
cross-coupling reactions has been the focus of much
attenACHTUNGTRENNUNG
tion.[4a] Among these, O- and S-based electro-
philes as alternatives for the halides are particularly
attractive due to the ubiquitous presence of the O-
and S-based starting materials in both the natural
world and synthetic systems.[5] Transition metal-cata-
À
lyzed selective cleavage of C S bonds is a particularly
attractive route to C C bond formation. Cu(I) car-
[6]
À
Scheme 1. Proposed mechanism for the Liebeskind–Srogl re-
boxylate-mediated, Pd-catalyzed cross-coupling reac- action.
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Scheme 2. Strategy to construct heterobiaryl compounds and heteroalkynes via cleavage of C S bonds.
In 2007, Liebeskind reported the first catalytic CuI- without the desired product 3aa (entry 5). Continuing
3-methylsalicylate (CuMeSal)-catalyzed coupling of with CuTC, we investigated the influence of different
thiol esters with an excess of the boronic acids under Pd sources, ligands and solvents, PdCl2, and PdCl2
aerobic conditions without using a Pd catalyst.[10]
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
arylboronic acids, and organometallic reagents were product. Generally, 5 mol% of PdACHTUNTRGNEUNG(PPh3)4 and 3 equiv.
developed under aerobic conditions.[11–14] The Rh(I)- of CuTC with 3 equiv. of K3PO4 were sufficient to
catalyzed cross-coupling of boronic acid derivatives or achieve a good yield in 1,4-dioxane within 12 h at
À
terminal alkynes with aryl methyl sulfides by C SMe 1108C (entry 7). In THF, the reaction gave a lower
cleavage to construct C C bonds has been developed yield (entry 10). In the absence of Cu additive, no re-
À
by Willisꢀs[15] and Zhangꢀs[16] groups. At the same action was detected (entry 14). Without Pd the reac-
time, O. Kwon et al reported the Pd(0)-catalyzed and tion gave a mixture and 3aa in 25% yield (entry 15),
copper(I)-thiophene-2-carboxylate-(CuTC)-mediated
desulfitative couplings of nitrothioethers with boronic tries 16 and 17).
acids.[17]
Next, the optimized conditions developed for the
Diaryl disulfides are structurally symmetrical, air coupling of 1a and 2a were applied to a wide range of
but no 3aa was detected under an O2 atmosphere (en-
stable, and easy to handle. They are useful sulfenylat- arylboronic acid substrates (Table 2). The process
ing reagents and were widely used as sulfenyl and sul- proved to be broad in scope, tolerating a variety of
À
finyl reagents through S S cleavage with various re- steric and electronic changes to both reaction part-
agents.[18–23] However, there is a notable absence of ners. Both electron-rich methyl- and 2-methoxyphe-
examples of couplings of disulfides for the formation nylboronic acid and electron-poor 4-fluoro- and 4-
À
of C C bonds between arylboronic acids and disul- chlorophenylboronic acid underwent cross-couplings
fides (Scheme 2).[24,25]
to deliver the products 3ab–3ag in good yields. In ad-
Based on the wide ranging biological activity of 3,4- dition, the electron-deficient boronic acids, i.e., thio-
dihydropyrimidinones[26] and their utilization as im- pheneboronic acid and 1-naphthaleneboronic acid
portant precursors in the synthesis of pyrimidine were also successful substrates delivering the products
bases,[27] combined with our previous experience on (3ah, 3ai, 3ch and 3ci), although in these cases long
the synthesis of 3,4-dihydropyrimidinone deriva- reaction times (24 h) were required to ensure full con-
tives,[28] we selected the coupling of 1,2-di(pyrimidin- version. An ortho-substituted phenylboronic acid un-
2-yl) disulfide 1a (for the preparation, see the Sup- derwent cross-coupling with relatively moderate effi-
porting Information) and phenylboronic acid (2a) as ciency to form the product 3ad.
the model reaction. Gratifyingly, the reaction generat-
ed the C C coupling product 3aa in 55% yield in the were also suitable partners for the coupling reaction
Various pyrimidine functionalized-disulfides (1b–g)
À
presence of CuTC and K3PO4 using Pd
N
catalyst (Table 1, entry 1). In an attempt to find yields. Notably, couplings of 4-fluoro-, 4-chloro-, and
a more favored Cu source, we evaluated a number of 4-bromophenyl-substituted disulfides proceeded with
Cu additives including CuI, CuBr, copper(I) acetate phenylboronic acid with equally high efficiency to
À
[CuACHTUNGTRENNUNG(OAc)] and copper(II) acetate [CuACHTUNTGNER(NUGN OAc)2]. The yield the C C coupling products (3ca, 3da, 3ea, 3ch,
use of CuI or CuBr resulted in trace of the target 3ci). These results are particularly striking because
product, but with formation of the homo-coupling these aryl halides are typical substrates for Suzuki–
product biphenyl (entries 2 and 3). Although Miyaura cross-couplings, demonstrating the orthogo-
Cu
yield (50%) of 3aa was obtained (entry 4). When we
investigated Cu(OAc)2 as copper source, undesired coupling partners, we explored the couplings of the
products were detected by TLC, LC-MS and H NMR pyrimidine -functionalized disulfides 1 with terminal
ACHTUNGTRENNUNG
(OAc) gave almost complete conversion, a low nal reactivity of disulfides with arylboronic acids.[29]
To further expand the scope of the nucleophilic
ACHTUNGTRENNUNG
1
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[a]
À
Table 1. Optimization of the C C cross-coupling reaction of disulfide 1a with phenylboronic acid 2a.
Entry
Catalyst
Ligand/
[mol%]
Cu
Base
Yield[b] [%]
1
2
3
4
5
6
7
8
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
N
PPh3/20
PPh3/20
PPh3/20
PPh3/20
PPh3/20
DPE-Phos/6
–
–
CuTC
CuI
CuBr
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
K3PO4
Cs2CO3
K2CO3
K3PO4
K3PO4
K3PO4
–
55
trace[c]
trace
50
Cu
Cu
ACHTUNGTRENNUNG
A
trace
60
88
CuTC
CuTC
CuTC
CuTC
CuTC
CuTC
CuTC
CuTC
–
56
9
–
–
75
10
11
12
13
14
15
16
17
81[d]
65
PdCl2
PdCl2A(PPh3)2
(PPh3)4
(PPh3)4
DPE-Phos/6
DPE-Phos/6
–
–
–
–
G
70
63
Pd
Pd
–
K3PO4
K3PO4
K3PO4
–
CuTC
CuTC
CuTC
25[e]
0[f]
PdACHTNURTGENUNG(PPh3)4
0[g]
[a]
Conditions: 1 (0.25 mmol), 2 (0.75 mmol), PdACTHNUTRGNE(UNG PPh3)4 (5 mol%), Cu (3.0 equiv.), base (3.0 equiv.), 1,4-dioxane (4 mL),
argon atmosphere, 12 h unless otherwise noted.
Isolated yield (based on both pyrimidine groups from one molecule).
Determined by LC-MS and TLC.
THF was used as solvent at 808C for 12 h.
Undesired products were detected.
[b]
[c]
[d]
[e]
[f]
Under an O2 atmosphere.
20% mol of CuTC was used under an O2 atmosphere.
[g]
alkynes 4. These desulfitative coupling reactions ucts 3aa and 3ha. Subsequently, we subjected the
À
smoothly proceeded under the optimal reaction con- compound 1l to the C C cross-coupling with 1-oct
ditions using Et3N replace the K3PO4 as the base, 4b successfully giving both the desired products 5ab
G
with complete conversion observed. The cross-cou- and 5hb. In each case, the cleavage reaction occurred
À
plings of disulfides 1a–d and 1f with both aryl- and al- at the two C S bonds (Scheme 4).
À
kylalkynes selectively proceeded to deliver the C C
Compared with the tested nitrogen-containing di-
cross-coupling products 5aa–5fa in good yields sulfides, aryl disulfides showed much lower efficiency.
(Table 3).
For example, 1,2-bis(4-nitrophenyl) disulfide 1k react-
À
To fully delineate the inherent power of C C cross ed with 2a and 4a to deliver the products 3ka
coupling protocols, 1,2-di(pyridin-2-yl) disulfide and (Table 2) and 5ka (Table 3), respectively, albeit in
aryl disulfides were exposed to the C C cross-cou- lower yields. In additional, 1,2-diphenyldisulfane 1i
pling reaction. The reactivity of 1,2-di(pyridin-2-yl)di- and 1,2-di-p-tolyl disulfide 1j failed to produce the de-
sulfane 1h also induced the C C cross-coupling with sired product under the same conditions. Alternative-
aylboronic acids 2b, 2e and alkyne 4b to form desired ly, the homo-coupling of boronic acid or alkyne was
products 3hb, 3he (Table 2) and 5hb (Table 3), respec- significantly increased.
À
À
tively. In fact, the cross-coupling reaction of mercap-
On the basis of these observations, we propose that
À
topyridine 6 with 2a also gave the desired C C cou- the reaction mechanism is similar to that for the
pling product 3ha under the optimal conditions. With modified Liebeskind–Srogl cross-coupling reaction as
(pyridin-2-yl-sulfanylidene)copper (PySCu) 7 and 2a, shown in Scheme 5.[9] Nitrogen-containing disulfides
the desired product 3ha was also obtained are more efficient than aryl disulfides in the reaction,
(Scheme 3). Then, compound 1l was tested as sub- which may be due to the coordination of a soft basic
strate. It reacted with 2a smoothly generating prod- atom (such as N atom) to the copper salt promoting
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[a]
À
Table 2. Scope of disulfides (1) and boronic acids in the C C cross-coupling reaction.
[a]
Conditions: 1 (0.25 mmol), 2 (0.75 mmol), PdACTHNUTRGNEUNG(PPh3)4 (5 mol%), CuTC (3.0 equiv.), K3PO4 (3.0 equiv.), 1,4-dioxane
(4 mL), argon atmosphere, 12 h. Isolated yields.
À
À
C S activation to give the C C cross-coupling prod- mixture for 3aa gave a set of prominent peaks with
À
uct. A formal oxidative addition of copper into the S
a mass that is consistent with the molecular formula-
S bond affords Cu(II) dithiolato intermediate A.[30] tion of compound [Cu(II)(1a)] (A or B) (ESI-MS:
Subsequent reductive cleavage of the S S bond leads m/z=609). Then, oxidative addition of the Pd(0) to
À
to the formation of the corresponding copper(II) spe- the Cu(II) thiolato intermediate B results in forma-
cies B. In fact, the ESI-MS analysis of the reaction tion of complex C.[22] Transmetalation[1a] from boron
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Table 3. Coupling of disulfides with terminal alkynes.[a]
[a]
Conditions: 1 (0.25 mmol), 4 (0.75 mmol), PdACHTNUGTRNEG(UN PPh3)4 (5 mol%), CuTC (3.0 equiv.), Et3N (1.0 mL), argon atmosphere,
24 h. Isolated yields.
to palladium next occurs, and then reductive elimina-
À
tion, giving the C C cross-coupling products 3aa.
À
In conclusion, we reported a C C bond forming re-
action via a Liebeskind–Srogl-type cross-coupling in-
volving the cleavage of the C S bond of di-
(hetero)aryl disulfides by arylboronic acids or 1-alk-
À
Scheme 4. Couplings of 2-(pyridin-2-yldisulfanyl)pyrimidine.
A
ACHTUNGTRENNUNGynes. The use of a thiophilic additive such as
CuACHTUNGTRENNUNG
À
tion of the C C bond in these reactions. The reaction products in good to excellent yields.
using nitrogen-containing disulfides as substrates typi-
cally proceeds with high efficiency and chemoselectiv-
ity. This protocol exhibits broad substrate scope with
Experimental Section
General Procedure for the Synthesis of C-2-Aryl-
pyrimidines (3aa–3he)
A sealed tube (15 mL) initially fitted with a septum contain-
ing PdACHTNUTGRENUNG(PPh3)4 (19.3 mg, 0.05 equiv.) was evacuated and
purged with argon gas three times. Pyrimidin-2-yl disulfide
(1, 0.25 mmol), arylboronic acid (2, 0.75 mmol, 3.0 equiv.),
K3PO4 (0.75 mmol, 3.0 equiv.) and 1.4-dioxane (3 mL) were
added to the system and the reaction mixture was stirred at
1108C for 12 h until complete consumption of 1 (based on
TLC monitoring). After completion of reaction, the mixture
Scheme 3. Coupling of pyridine-2-thiol with 2a.
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A sealed tube (15 mL) initially fitted with a septum contain-
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purged with argon gas three times. Pyrimidin-2-yl disulfide
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(1 mL) and 1.4-dioxane (3 mL) were added to the system
and the reaction mixture was stirred at 1108C for 24 h until
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room temperature and quenched with saturated aqueous
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Acknowledgements
We are thankful for the financial support from the NSFC
(Nos. 21362032, 21362031 and 21062017), the NSF of Gansu
Province (No. 1208RJYA083), and the Scientific and Techno-
logical Innovation Engineering program of NWNU (Nos.
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