Nickel- or Cobalt-Catalyzed Cross-Coupling of Arylsulfonic Acid Salts with Grignard Reagents

Article abstract of DOI:10.1002/adsc.201500304

The use of arylsulfonic acid salts as electrophiles in a nickel- or cobalt-catalyzed cross-coupling with Grignard reagents is described. Bis(tricyclohexylphosphine)nickel dichloride [NiCl₂(PCy₃)₂] was found to be the optimal catalyst, and reactions with this catalyst proceeded in most cases at room temperature. The analogous cobalt catalyst [CoCl₂(PCy₃)₂] was also found to promote the cross-coupling reaction at higher temperature (60C).

Full text of DOI:10.1002/adsc.201500304

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DOI: 10.1002/adsc.201500304
Nickel- or Cobalt-Catalyzed Cross-Coupling of Arylsulfonic Acid
Salts with Grignard Reagents
a
b
c,
c
Christian A. Malapit, Michael D. Visco, Jonathan T. Reeves, * Carl A. Busacca,
a
c
Amy R. Howell, and Chris H. Senanayake
a
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, USA
Department of Chemistry and Biochemistry, Ohio State University, Columbus, Ohio 43210, USA
Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc., 900 Ridgebury Road/P.O. Box 368, Ridgefield,
Connecticut 06877-0368, USA
b
c
Fax: (+1)-203-791-6130; e-mail: jonathan.reeves@boehringer-ingelheim.com
Received: March 27, 2015; Published online: June 10, 2015
Dedicated to Prof. Stephen L. Buchwald on the occasion of his 60 birthday.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500304.
th
Abstract: The use of arylsulfonic acid salts as elec-
trophiles in a nickel- or cobalt-catalyzed cross-cou-
pling with Grignard reagents is described. Bis(tricy-
clohexylphosphine)nickel dichloride [NiCl (PCy ) ]
was found to be the optimal catalyst, and reactions
with this catalyst proceeded in most cases at room
temperature. The analogous cobalt catalyst
of vinyl sulfides, aryl thiols, aryl sulfides, aryl sulfox-
ides, aryl sulfones, and arylsulfinate salts with
[14]
Grignard reagents.
The use of aryl tert-butyl sul-
[15]
fones (Julia and co-workers),[ neopentyl arylsulfo-
2
3 2
16]
nates (Park and co-workers), and N,N-diethylaryl-
[17]
sulfonamides (Snieckus and co-workers) was subse-
quently reported for Ni-catalyzed cross-coupling with
Grignard reagents. Vogel and co-workers have devel-
oped several desulfinylative cross-coupling reactions
[
CoCl (PCy ) ] was also found to promote the
2 3 2
cross-coupling reaction at higher temperature
608C).
[18]
(
with arylsulfonyl chlorides as the electrophiles.
Aryl-sulfur electrophiles have shown compatibility
with an array of different transition metal-catalyzed
cross-coupling reactions.
Keywords: cobalt; cross-coupling; Grignard re-
agents; nickel; sulfonic acids
[19]
Aromatic sulfonylation is one of the fundamental
aromatic heterofunctionalization reactions along with
[20]
halogenation, oxidation and nitration (Figure 1).
This reaction was first demonstrated in 1825 when
The electrophiles employed in transition metal-cata- Faraday reported that the treatment of naphthalene
lyzed cross-coupling reactions have historically been with sulfuric acid gave 1- and 2-naphthalenesulfonic
[
1]
predominantly aryl halides. Alternative, non-halo- acids, which he converted to several different alkali
[21]
gen electrophiles have been developed, however, and salts. While aryl halides, phenol derivatives and ani-
are seeing increased applications in recent years. line derivatives have been examined as electrophiles
Phenol-derived electrophiles, including phenolic in cross-coupling reactions, nitroarenes and arylsul-
[
2]
[3]
[4]
[5]
[6]
salts, sulfonates, s[u8]lfates, phosphates, ethers,
fonic acids, products of two of the fundamental aro-
[
7]
[8b]
esters,
carbamates,
carbonates,
have been shown to be competent CÀO tially unexplored. Herein we report the cross-cou-
electrophiles in many types of cross-coupling reac- pling of arylsulfonic acid salts with Grignard reagents
tions. Arylamine derivatives such as diazonium under mild conditions using NiCl (PCy ) or
and sulfam- matic heterofunctionalization reactions, remain essen-
[
8a–b,9]
[22]
ates
2
3 2
[
10]
[11]
[12]
salts, trimethylammonium salts, triazenes, and CoCl (PCy ) as catalyst.
2
3 2
[
13]
even anilines have been developed as CÀN based
electrophiles. The use of aryl-sulfur derivatives as catalysts, the reaction of sodium benzenesulfonate
electrophiles was pioneered by Wenkert and co-work- with 4-methoxyphenylmagnesium bromide
To screen the feasibility of the reaction with various
1
[23]
ers in 1979, when they extended their work on the Ni- (3 equiv) in THF at ambient temperature was em-
catalyzed coupling of vinyl and aryl ethers with ployed (Table 1). In the absence of catalyst, no reac-
Grignard reagents to the analogous cross-coupling tion took place (entry 1). Using non-ligated NiCl2
[
6a]
Adv. Synth. Catal. 2015, 357, 2199 – 2204
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Christian A. Malapit et al.
COMMUNICATIONS
[
a]
Table 1. Catalyst screening results.
[b]
Entry
Catalyst
Yield [%]
1
2
3
4
5
6
7
8
9
none
NiCl2
0
53
52
98
45
46
0
63
38
93
NiCl (PPh )
2
3 2
NiCl (PCy )
3 2
2
[
c]
NiCl (dppe)
2
[
d]
NiCl (dppf)
2
PdCl (PPh )
CoCl2
CoCl (PPh )
CoCl (PCy )
2 3 2
2
3
2
[
e]
[
e]
2
3 2
[
e]
1
0
[
a]
Typical reaction conditions: 0.5 mmol 1, 1.5 mmol
ArMgBr, 1 mol% catalyst, THF, room temperature, 20 h.
HPLC assay yield of 2.
dppe=1,2-bis(diphenylphosphino)ethane.
dppf=1,2-bis(diphenylphosphino)ferrocene.
Reaction performed at 608C.
[
[
[
[
b]
c]
d]
e]
agents were employed (products 2–4, 8, 9), the reac-
tions proceeded to completion at room temperature
within 20 h and provided good yields of biaryl prod-
Figure 1. Fundamental methods of aromatic heterofunction- ucts. Notably, the reaction was also effective when the
alization and utility of products as electrophiles in cross-cou- free sulfonic acid PhSO H was used. An additional
3
pling reactions.
equivalent of Grignard reagent was employed to de-
protonate the sulfonic acid. In the case of the cou-
pling with sterically demanding 2-mesitylmagnesium
gave biaryl 2 in 53% yield. The use of NiCl (PPh ) as bromide (product 5), the reaction required heating to
2
3 2
catalyst gave no increase in yield (entry 3). Employing 608C to complete within 20 h. Nonetheless, biaryl 5
the more electron-rich complex NiCl (PCy ) provid- was obtained in excellent yield (83%). The use of
2
3 2
ed a dramatic improvement, furnishing 2 in 98% yield electron-poor aryl Grignard reagents also required
(
entry 4). The power of NiCl (PCy ) in cross-coupling raising the reaction temperature to 608C to achieve
2
3 2
reactions which necessitate challenging oxidative ad- a reasonable reaction rate (products 6 and 7). The use
[
4,6b,c,7,8,24]
ditions has been well documented.
Nickel of aryl Grignard reagents generated from aryl bro-
complexes with bidentate ligands (entries 5 and 6) mides and Mg/LiCl according to Knochelꢁs procedure
[25]
gave 2 in low yields. The use of a palladium complex was also effective (products 8 and 9).
entry 7) gave no product. Cobalt catalysis was also We next explored the reaction scope with various
investigated. Non-ligated CoCl gave a 63% yield of 2 arylsulfonic acid salts (Scheme 2). The coupling of
(
2
(
entry 8), while CoCl (PPh ) gave a reduced yield of sodium p-toluenesulfonate with PhMgBr required
2 3 2
38% (entry 9). Interestingly, employing the cobalt 48 h to reach completion at room temperature, giving
complex [CoCl (PCy ) ] structurally analogous to the 4 in 55% yield. Reaction of the more electron-rich 4-
2
3 2
most effective nickel catalyst gave a 93% yield when methoxyphenylmagnesium bromide with p-TsONa
the reaction temperature was raised to 608C proceeded to completion within 20 h at room temper-
(
entry 10).
ature to furnish 10 in 72% yield. The coupling of
The scope of the nickel-catalyzed cross-coupling re- bulky 2-mesitylmagnesium bromide with p-TsONa re-
action of sodium benzenesulfonate 1 was explored quired heating at 608C, and gave biaryl 11 in 67%
with respect to variation of the Grignard reagent yield. The reaction of more sterically hindered aryl-
(
Scheme 1). When electron-rich aryl Grignard re- sulfonic acid salts, such as sodium 2,4-dimethylben-
2
200
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COMMUNICATIONS Nickel- or Cobalt-Catalyzed Cross-Coupling of Arylsulfonic Acid Salts
Scheme 1. Scope of Ni-catalyzed coupling of 1 with different
aryl Grignard reagents. Reaction conditions: 2.0 mmol 1,
6
.0 mmol ArMgBr, 1 mol% NiCl (PCy ) , THF, room tem-
2 3 2
perature or 608C, 20 h. Isolated yields unless noted other-
wise.
zenesulfonate and sodium 2-mesitylenesulfonate, also
required heating at 608C to give products 12 and 13 Scheme 2. Scope of Ni-catalyzed coupling with different ar-
ylsulfonic acids. Reaction conditions: 2.0 mmol ArSO Na,
in moderate yields. To the best of our knowledge, the
use of either a sterically hindered 2-mesityl Grignard
as nucleophile or of a 2-mesityl electrophile is unpre-
3
6
.0 mmol ArMgBr, 1 mol% NiCl (PCy ) , THF, room tem-
2
3 2
perature or 608C, 20 h. Isolated yields unless noted other-
wise.
cedented with
a
sulfur-derived electrophile in
a Kumada coupling. The highly lipophilic sodium 4-n-
octylbenzensulfonate coupled well with both 4-me-
thoxyphenyl- and 2-mesitylmagnesium bromide to
give 14 and 15 in good yields. Sodium 2-naphthalene-
sulfonate and sodium 1-naphthalenesulfonate reacted
smoothly to yield products 16–19 in good yields.
Sodium benzene-1,3-disulfonate reacted with 6 equiv.
of 2-mesitylmagnesium bromide to give the sterically
hindered terphenyl 20 in 54% yield. The cross-cou-
pling also worked with the heterocyclic sodium 3-pyri-
dinesulfonate to yield biaryl 21 in good yield.
The Ni-catalyzed cross-coupling reaction could also
be extended to alkyl Grignard reagents (Scheme 3).
Sodium 2-naphthalenesulfonate coupled smoothly
with MeMgCl, Me SiCH MgCl, allylMgCl, and
3
2
BnMgCl at room temperature, providing the corre-
sponding products 22, 24, 25 and 27 in good yields. In
the case of the allylMgCl coupling, the product 25
was partially isomerized under the reaction conditions
to the conjugated isomeric compound (E)-2-(prop-1-
Scheme 3. Scope of Ni-catalyzed coupling with different
alkyl Grignard reagents. Reaction conditions: 2.0 mmol
ArSO Na, 6.0 mmol RMgX, 1 mol% NiCl (PCy ) , THF,
en-1-yl)naphthalene. PhSO Na also coupled with
3
Me SiCH MgCl and BnMgCl to give products 23 and
3
2
3
2
3 2
26 in good yields. Interestingly, the reaction with cy- room temperature, 20 h. Isolated yields unless noted other-
clopropyl-magnesium bromide failed to give any con- wise.
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Christian A. Malapit et al.
COMMUNICATIONS
[a]
Table 2. Competition experiments with other electrophiles.
Entry PhX
Yield of 4
Unreacted
1 [%]
Unreacted PhX
[b]
[
b]
[b]
[%]
[%]
1
2
3
4
5
PhCl
PhBr
PhI
PhOTf 98
PhSMe 65
97
67
62
5
0
38
51
<2
17
25
20
0
37
[
a]
Reaction conditions: 0.5 mmol 1, 0.5 mmol PhX,
.0 mmol 4-MeC H MgBr, 1 mol% NiCl (PCy ) , THF,
Scheme 4. Scope of Co-catalyzed coupling. Reaction condi-
2
6
4
2
3 2
tions: 2.0 mmol ArSO Na, 6.0 mmol RMgBr, 1 mol%
3
room temperature, 20 h.
HPLC assay yields.
CoCl (PCy ) , THF, 608C, 24 h. Isolated yields unless noted
[b]
2
3 2
otherwise.
version of the arylsulfonate to product 28, even when
the reaction temperature was raised to 608C. The use
of i-PrMgCl resulted in reduction to give 29 in 76%
yield, thus providing a convenient method for reduc-
[
17]
tive removal of the sulfonic acid moiety.
The scope of the cross-coupling reaction was next
explored using the cobalt catalyst CoCl (PCy )
3 2
2
(
Scheme 4). Employing 1 mol% catalyst, the reaction Scheme 5. Test for oxidative addition versus radical mecha-
proceeded at 608C to give biaryl products in good nism.
yields after 24 h (products 2–4 and 17). The reaction
was also amenable to the use of MeMgCl (product
2
2) and reduction with i-PrMgCl (product 29). The of Ni(0) to the ArÀS bond or by a radical/single elec-
[26]
complex CoCl (PCy ) was first prepared in 1965
tron transfer mechanism, we conducted the reaction
2
3 2
and has been used as a catalyst for butadiene poly- of 2-naphthalenesulfonic acid sodium salt with i-
[
27]
merization.
the first use of this complex as an efficient catalyst for was quenched upon complete conversion with D O.
To the best of our knowledge, this is PrMgCl in 1:1 THF/THF-d (Scheme 5). The reaction
8
2
1
a cross-coupling reaction.
H NMR and GC-MS analysis of the product showed
Competition experiments were conducted to exam- <1% incorporation of deuterium. This suggests that
ine the relative reactivity of different electrophiles the reaction proceeds by a traditional oxidative addi-
compared to a sulfonic acid salt using NiCl (PCy ) as tion of Ni(0) into the ArÀS bond, followed by trans-
2
3 2
catalyst (Table 2). A 1:1 mixture of either PhCl, PhBr, metallation of the isopropyl group, b-hydride elimina-
PhI, PhOTf or PhSMe and PhSO Na and 1 mol% tion, and reductive elimination to give 29 and Ni(0).
3
NiCl (PCy ) in THF was treated at room tempera- For a reaction proceeding through the intermediacy
2
3 2
ture with 4-MeC H MgBr (4 equiv.). The reaction of radicals, H or D abstraction from the solvent
6
4
mixtures were allowed to stir at room temperature for would be expected to lead to significant D incorpora-
0 h, were quenched, and the crude product mixtures tion. These results are in concurrence with the find-
were analyzed by HPLC for assay yields of product 4 ings of Snieckus and Milburn for the mechanism of
2
[17,28]
as well as of unreacted 1 and PhX. Based on the data, the Kumada cross-coupling of arylsulfonamides.
it can be concluded that the relative reactivity order In conclusion, arylsulfonic acid salts have been
of electrophiles under these reaction conditions is demonstrated to be competent electrophiles in the
PhOTfꢀPhCl>PhBrꢀPhI>PhSO Na>PhSMe.
nickel- or cobalt-catalyzed cross-coupling with
To probe whether the mechanism of the cross-cou- Grignard reagents. Importantly, arylsulfonic acids are
pling reaction proceeds through an oxidative addition products of one of the oldest and most fundamental
3
2
202
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COMMUNICATIONS Nickel- or Cobalt-Catalyzed Cross-Coupling of Arylsulfonic Acid Salts
methods of direct aromatic heterofunctionalization.
Their utility as electrophiles in other cross-coupling
reactions merits further exploration. While the nickel
catalyst NiCl (PCy ) was shown to be optimal for the
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2
3 2
present reaction, the analogous cobalt catalyst
CoCl (PCy ) was also shown to be effective at
2
3 2
a higher temperature of 608C. The efficacy of
CoCl (PCy ) as a catalyst for other cross-coupling re-
131, 9590–9599.
2
3
2
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Experimental Section
Typical Experimental Procedure (Compound 2)
120, 4944–4947; Angew. Chem. Int. Ed. 2008, 47, 4866–
An argon-purged flask equipped with a magnetic stir bar
was charged with sodium arylsulfonate 1 (0.36 g, 2.0 mmol,
4869.
[
7] a) K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem.
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.0 equiv.) and NiCl (PCy ) (13 mg, 1 mol%). The flask was
2 3 2
sealed with a rubber septum, evacuated and filled with
argon. THF (1.3 mL) was charged via a syringe. To this
slurry, 4-methoxyphenylmagnesium bromide (12.0 mL, 0.5M
in THF, 3.0 equiv.) was added dropwise under argon. After
the addition was complete, the reaction mixture was stirred
at room temperature. After 20 h, HPLC analysis indicated
complete consumption of sodium arylsulfonate 1. The reac-
tion mixture was cooled in an ice bath and quenched with
1
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saturated aqueous NH Cl (10 mL) and extracted with
4
MTBE (10 mL”3). The combined organic layers were dried
over Na SO , filtered, and concentrated under vacuum. The
2
4
crude product was purified by chromatography on SiO2
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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2
204
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