Palladium-catalysed intramolecular direct arylation of 2- bromobenzenesulfonic acid derivatives

Article abstract of DOI:10.1002/adsc.201200793

A palladium-catalysed intramolecular direct arylation of 2-bromobenzenesulfonic acid derivatives was found to proceed using 1 mol% of palladium acetate as the catalyst. The influence of the substituents on the phenol moiety of 2-bromobenzenesulfonic acid phenyl esters reveals that electron-donating substituents favour the reaction while electron-withdrawing ones are unfavourable. The reactivity of sulfonamides was also studied and, in all cases, a selective activation at sp² C-H vs. sp³ C-H was observed. A sulfonamide bearing both phenyl and benzyl substituents on nitrogen gave selectively the six-membered ring product.

Full text of DOI:10.1002/adsc.201200793

FULL PAPERS
DOI: 10.1002/adsc.201200793
Palladium-Catalysed Intramolecular Direct Arylation of
2-Bromobenzenesulfonic Acid Derivatives
Charles Beromeo Bheeter,a Jitendra K. Bera,b and Henri Douceta,*
a
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS – Universitꢀ de Rennes “Catalyse et Organometalliques”,
Campus de Beaulieu, 35042 Rennes, France
Fax: (33)-(0)2-2323-6939; phone: (+33)-(0)2-2323-6384; e-mail: henri.doucet@univ-rennes1.fr
Department of Chemistry, Indian Institute of Technology Kanpur, 208016 Kanpur, India
b
Received: September 3, 2012; Published online: December 4, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200793.
Abstract:
A
palladium-catalysed intramolecular ity of sulfonamides was also studied and, in all cases,
2 3
À
À
direct arylation of 2-bromobenzenesulfonic acid de- a selective activation at sp C H vs. sp C H was ob-
rivatives was found to proceed using 1 mol% of pal- served. A sulfonamide bearing both phenyl and
ladium acetate as the catalyst. The influence of the benzyl substituents on nitrogen gave selectively the
substituents on the phenol moiety of 2-bromobenz- six-membered ring product.
ACHTUNGTRENNUNGenesulfonic acid phenyl esters reveals that electron-
donating substituents favour the reaction while elec- Keywords: aryl bromides; atom economy; C H func-
tron-withdrawing ones are unfavourable. The reactiv- tionalization; cyclisation; palladium
À
Introduction
few examples of cyclisation of sulfonamides bearing
2-bromobenzyl substituents on the nitrogen atom
The palladium-catalysed direct arylation of several ar- have also been reported.[7] Finally, in the course of
À
omatics via a C H bond activation using aryl halides their study of intramolecular palladium-catalysed
has led to successes in recent years.[1,2] For such direct
coupling reactions, no preparation of an organometal-
lic derivative is required, and this is a tremendous ad-
vantage as compared to the more classical cross-cou-
pling procedures arising from more costly Suzuki–
Miyaura, Stille, or Negishi reactions. Moreover, the
direct arylation reaction provides only an acid (HX)
associated to a required base as by-product and there-
fore presents advantages both in terms of atom-econ-
omy and relatively inert wastes.
An intramolecular version of this reaction has al-
lowed the synthesis of several biaryls via the forma-
tion of 5- to 7-membered rings.[3–5] However, there are
still some limitations for such a cyclisation in terms of
substrate scope.
For example, although several benzenesulfonic acid
derivatives display important biological properties
(Figure 1), relatively few biaryls bearing SO2R sub-
stituents have been prepared by intramolecular palla-
[6–8]
À
dium-catalysed direct C H bond functionalization.
The reaction of 2-bromophenols with benzenesul-
fonyl chlorides provides benzenesulfonic acid 2-bro-
mophenyl esters which were cyclised by Majumdar
and co-workers to give the sultone derivatives using
Figure 1. Examples of bioactive compounds bearing SO2R
10 mol% Pd
G
A
substituents.
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Charles Beromeo Bheeter et al.
FULL PAPERS
Scheme 1.
3
À
direct alkane arylation via CACTHNUGTRNEUNG(sp ) H cleavage, Fagnou
and co-workers described the cyclisation of 2-bromo-
N-methyl-N-phenylbenzenesulfonamide via a selective
2
[8]
À
for CACHTUNGTRENNUNG(sp ) H arylation.
On the other hand, to the best of our knowledge,
cyclisation, via palladium-catalysed C H functionali-
À
zation of 2-bromobenzenesulfonic acid phenyl ester,
which can be easily obtained from 2-bromobenzene-
sulfonyl chloride and phenols has not been reported
(Scheme 1).[9–12] As a very wide variety of phenols are
commercially available, such a cyclisation would pro-
vide a very simple access to functionalized sultones.[13]
Here, we wish to report on the reactivity and regiose-
lectivity of 2-bromobenzenesulfonic acid phenyl
esters in the presence of a phosphine-free palladium
catalyst. reactivity
The
of
some
2-
bromobenzenesulfonACHTUNGTENRaNUNG mides under phosphine-free
conditions was also studied.
Results and Discussion
From commercially available 2-bromobenzenesulfonyl
chloride and phenols, products 1–16 were obtained in
almost quantitative yields (Scheme 2).
For the intramolecular direct arylations, we em-
ployed PdACHTUNGTRENNUNG(OAc)2 as the catalyst associated to KOAc
as the base in DMAc, as we previously observed that
these conditions are suitable for similar reactions.[2c]
Under these phosphine-free conditions, from 2-bro-
mobenzenesulfonic acid phenyl ester 1, the target
product 17 was selectively obtained in 95% yield
(Scheme 3).
Several mechanisms have been suggested for the
À
palladium-catalysed C H bond activation/functionali-
sation of arenes.[1,14] Under our reaction conditions,
we believe that the reaction proceeds via a classical
oxidative addition of the aryl bromide to a palladi-
Scheme 3. Direct intramolecular arylation of substrates 1–
16.
Scheme 2.
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Palladium-Catalysed Intramolecular Direct Arylation of 2-Bromobenzenesulfonic Acid Derivatives
the other hand, the cyclization 2-bromobenzenesul-
fonic acid benzo[1,3]dioxol-5-yl ester 15 was also re-
AHCTUNGTRENNUNG
gioselective, but the arylation occurs at the most hin-
dered position to produce 31 in high yield. Finally, the
reactivity of a phenol moiety bearing a benzyl at C-2
was examined. The CH2 of benzyl is known to be
quite reactive in the presence of aryl halides and pal-
ladium catalysts.[14a] However, only the arylation via
2
À
C
G
80% yield (Scheme 3).
As only 1 mol% of the phosphine-free catalytic
system PdACTHNURGTNEUNG(OAc)2 promotes very efficiently the cycli-
Scheme 4.
sation of 2-bromobenzenesulfonic acid phenyl esters,
we decided to extend the reaction to 2-bromo-N-phe-
nylbenzenesulfonamides 33–37 which were easily ob-
um(0) complex to give intermediate A, followed by tained from 2-bromobenzenesulfonyl chloride and
a concerted metallation/deprotonation to give inter- aniline derivatives (Scheme 5).
mediate B (Scheme 4). The good performance of po-
tassium acetate as the base for these reactions is con- cyclisation of 2-bromo-N-methyl-N-phenylbenzenesul-
sistent with such a pathway.[14] Then, a reductive elim- fonamide using 5 mol% Pd
(OAc)2 associated to
ination provides the cyclised product and regenerates 10 mol% PCy3.[8b] We observed that, using again
the Pd(0). 1 mol% Pd(OAc)2 as the catalyst, both 2-bromo-N-
We then evaluated the influence of the substituents butyl-N-phenylbenzenesulfonamide 33 and 2-bromo-
on the phenol moiety on the reactivity and selectivity. N-ethyl-N-phenylbenzenesulfonamide 34 react
Fagnou and co-workers have recently reported the
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
Methyl substituents at C-2 and C-4 led to 18 in 94% smoothly to give products 38 and 39 in very high
2
À
yield. It should be noted that no arylation at methyl yields with complete selectivity for C
(sp ) H aryla-
3
[15]
2
À
À
via a C
(sp ) H activation was detected.
A more tion (Scheme 6). A selective C
(sp ) H arylation on 1-
congested phenol bearing a 2-isopropyl and a 5-
methyl substituents gave 19 in a slightly lower yield.
Then, we compared the reactivity of phenol deriva-
tives substituted by methoxy, methyl or trifluorometh-
yl groups at both C-3 and C-5 positions. Both elec-
tron-donating substituents were found to support the
reactions to give 20 and 21 in 94 and 93% yields, re-
spectively. On the contrary, an unfavourable influence
of trifluoromethyl substituents was observed, and the Scheme 5. Synthesis of benzenesulfonamides.
starting material 6 was recovered unreacted.
A similar reactivity was observed with para-substi-
tuted phenol derivatives. Electron-donating substitu-
ents at C-4 such as methoxy or tert-butyl led to almost
quantitative yields in cyclised products 23 and 24.
Chloro- or fluoro-substituted phenol derivatives were
also cyclised to form 25 and 26 in 62 and 95% yields,
respectively. In the course of the cyclisation of 9, no
À
cleavage of the C Cl bond was observed, allowing
further transformations. On the other hand, in the
presence of nitro or ester substituents, the starting
materials 11 or 12 were recovered unreacted.
We also examined the regioselectivity of the reac-
À
tion when two reactive C H bonds on the phenol
À
moiety are available for C H bond functionalization.
From 2-bromobenzenesulfonic acid naphthalen-2-yl
ester 13, only the arylation at C-3 on the naphthol
moiety was observed to give 29 in 69% yield. Cyclisa-
tion of 2-bromobenzenesulfonic acid 3-N,N-dimethyl-
ACHTUNGTRENNUNG
Scheme 6. Direct intramolecular arylation of substrates 33–
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Charles Beromeo Bheeter et al.
FULL PAPERS
Conclusions
In summary, 1 mol% of phosphine-free PdACTHNURGTNEUNG(OAc)2 as
the catalyst associated to KOAc promotes the intra-
2
À
molecular direct arylation via an sp C H bond func-
tionalization of several 2-bromobenzenesulfonic acid
derivatives. For the cyclisation of 2-bromobenzenesul-
fonic acid phenyl esters, the nature of the substituents
on the phenol moiety was found to have a huge influ-
ence on the reaction. Electron-donating substituents
favoured the reaction, whereas electron-withdrawing
substituents are unfavourable. A high regioselectivity
was observed in all cases allowing the use of a wide
variety of phenols. To the best of our knowledge,
these are the first examples of palladium-catalysed in-
tramolecular direct arylations of 2-bromobenzenesul-
fonic acid phenyl ester. This phosphine-free proce-
dure also promotes the cyclisation of 2-bromosulfon-
Scheme 7. Formation of seven-membered rings via sp2 aryla-
tion.
2
3
À
À
AHCTUNGTRENNGaUN mides. Selective activation at sp C H vs. sp C H
was observed. A 2-bromosulfonamide bearing both
phenyl and benzyl substituents on nitrogen gave se-
lectively the six-membered ring product.
Scheme 8. Intramolecular direct arylation of 47.
Experimental Section
(2-bromobenzenesulfonyl)-2,3-dihydroindole 35 was General Procedure for the Synthesis of Compounds
also observed to give 40 in 91% yield. On the other 1–16
hand, from 2-bromo-N-phenylbenzenesulfonamide 36
no trace of the desired product 41 was detected. Fi-
As a typical experiment, the reaction of 2-bromobenzenesul-
fonyl chloride (0.510 g, 2 mmol), phenol derivative
nally, the sulfonamide 37 bearing both a phenyl and
a benzyl group on the nitrogen atom was employed.
Exclusive selectivity was observed for arylation at the
phenyl over the benzyl to form the six-membered ring
product 42 in 90% yield.
(2.2 mmol) and triethylamine (1.4 mL, 10 mmol) at room
temperature during 8–12 h in dry dichloromethane (10 mL)
affords the coupling product after addition of water
(20 mL), extraction with dichloromethane (20 mL), drying
on MgSO4, evaporation and purification on silica gel.
2-Bromobenzenesulfonic acid phenyl ester (1):[16] From 2-
bromobenzenesulfonyl chloride (0.510 g, 2 mmol) and
phenol (0.207 g, 2.2 mmol) 1 was obtained; yield; 0.563 g
(90%). 1H NMR (400 MHz, DMSO-d6): d=8.03 (d, J=
7.9 Hz, 1H), 7.93 (d, J=7.9 Hz, 1H), 7.70 (t, J=7.9 Hz,
1H), 7.58 (t, J=7.9 Hz, 1H), 7.39 (t, J=8.0 Hz, 2H), 7.31 (t,
J=8.0 Hz, 1H), 7.10 (d, J=8.0 Hz, 2H); 13C NMR (75 MHz,
DMSO-d6): d=148.8, 136.3, 136.0, 134.0, 132.5, 130.2, 128.5,
127.6, 121.7, 120.4.
Then, we performed a competition reaction to
probe the preference of this catalyst system for reac-
2
À
tivity at an sp C H bond to form a seven-membered
3
À
ring vs. an sp C H bond to form a five-membered
ring. Hanson and co-workers have recently reported
that the reaction of 43 in the presence of 10 mol%
PdACHTUNGTRENNUNG(OAc)2 associated to 20 mol% PPh3 and Cs2CO3
gave 45 in 83% yield.[8a] From N-benzyl-2-bromo-N-
methylbenzenesulfonamides 43 as the reactant, using
again 1 mol% PdACHTUNGTRENNUN(G OAc)2 as the catalyst, we observed
General Procedure for the Synthesis of Compounds
17–32, 38–42, 45 and 46
an exclusive formation of the seven-membered ring
product 45 (Scheme 7). From 44 the seven-membered
product 46 was also selectively obtained in high yield.
On the other hand, the use of 1-bromo-2-[(phenyl-
methyl)sulfonyl]benzene 47 in the presence of
1 mol% PdClACHTUNGTRENNUNG(C3H5)ACHUTNGTRENN(UGN dppb) as the catalyst led to
a poor yield of the target product 48 due to a partial
As a typical experiment, the reaction of the 2-bromobenz-
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
(2.24 mg, 0.01 mmol) under argon affords the coupling prod-
uct after addition of water (20 mL), extraction with di-
chloromethane (20 mL), drying on MgSO4, evaporation and
purification on silica gel.
conversion and also debromination of 47 (Scheme 8).
With this substrate, the use of 1 mol% PdACTHNURGTNEUNG(OAc)2 gave
À
no product 48. This result confirms a more easy C H
bond activation on electron-rich arenes such as
phenol or aniline derivatives.
2,4-DimethyldibenzoACTHNUTRGNE[NUG 1,2]oxathiine 6,6-dioxide (18): From
2 (0.341 g, 1 mmol) 18 was obtained as a white solid; yield:
1
0.245 g (94%); mp 127–1288C. H NMR (400 MHz, DMSO-
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Adv. Synth. Catal. 2012, 354, 3533 – 3538

Palladium-Catalysed Intramolecular Direct Arylation of 2-Bromobenzenesulfonic Acid Derivatives
1-Bromo-2-[(phenylmethyl)sulfonyl]benzene (47)[17]
d6): d=8.19 (d, J=7.9 Hz, 1H), 8.04 (d, J=7.9 Hz, 1H),
7.88 (t, J=7.9 Hz, 1H), 7.82 (s, 1H), 7.69 (t, J=7.9 Hz, 1H),
7.21 (s, 1H), 2.33 (s, 3H), 2.28 (s, 3H); 13C NMR (75 MHz,
DMSO-d6): d=145.5, 135.8, 134.4, 133.2, 131.1, 131.0, 129.6,
128.1, 125.7, 123.7, 123.6, 120.4, 20.4, 14.9; elemental analy-
sis: calcd. (%) for C14H12O3S (260.31): C 64.60, H 4.65;
found: C 64.51, H 4.79.
The reaction of 2-bromobenzenesulfonyl chloride (0.510 g,
2 mmol), sodium sulfite (0.510 g, 4 mmol) and NaHCO3
(0.340 g, 4 mmol) dissolved in water (30 mL) under an argon
atmosphere was carried out under heating at 1008C for
three hours. After cooling at room temperature, benzyl bro-
mide (0.427 g, 2.5 mmol) and the phase-transfer catalyst (n-
Bu)4NBr (0.110 g, 0.3 mmol) were added under the argon
flow. The reaction mixture was stirred overnight at 708C.
After cooling to room temperature, addition of water
(20 mL), extraction with dichloromethane (20 mL), drying
on MgSO4, evaporation and purification on silica gel, prod-
uct 47 was obtained; yield: 0.373 g (60%).
General Procedure for the Synthesis of Compounds
33–37
As a typical experiment, the reaction of 2-bromobenzenesul-
fonyl chloride (0.510 g, 2 mmol), aniline derivative
(2.4 mmol) and triethylamine (1.4 mL, 10 mmol) at room
temperature during 8–12 h in dry dichloromethane (20 mL)
affords the coupling product after addition of water
(40 mL), extraction with dichloromethane (40 mL), drying
on MgSO4, evaporation and purification on silica gel.
9-Thiaphenanthrene 9,9-Dioxide (48)[18]
The reaction of 1-bromo-2-[(phenylmethyl)sulfonyl]benzene
47 (0.311, 1 mmol), Cs2CO3 (0.652, 2 mmol), KOAc (0.276 g,
2 mmol) at 1508C during 16 h in DMAc (4 mL) in the pres-
2-Bromo-N-butyl-N-phenylbenzenesulfonamide
(33):
ence of PdClACTHNUTGRENN(UG C3H5)ACHTUTGNREN(NUNG dppb) (12.5 mg, 0.02 mmol) under
From 2-bromobenzenesulfonyl chloride (0.510 g, 2 mmol)
argon affords the coupling product 48 after addition of
water (20 mL), extraction with dichloromethane (20 mL),
drying on MgSO4, evaporation and purification on silica gel;
yield: 0.046 g (20%).
and n-butylphenylamine (0.358 g, 2.4 mmol) 33 was obtained
as
a white solid; yield: 0.670 g (91%); mp 81–828C.
1H NMR (400 MHz, DMSO-d6): d=7.86 (d, J=7.9 Hz, 1H),
7.79 (d, J=7.9 Hz, 1H), 7.51 (t, J=7.9 Hz, 1H), 7.46 (t, J=
7.9 Hz, 1H), 7.40–7.15 (m, 5H), 3.82 (t, J=7.6 Hz, 2H),
1.40–1.20 (m, 4H), 0.81 (t, J=7.6 Hz, 3H); 13C NMR
(75 MHz, DMSO)-d6: d=137.9, 137.6, 135.6, 134.4, 132.3,
129.2, 128.4, 128.0, 127.8, 119.6, 51.1, 30.2, 18.9, 13.4; ele-
mental analysis: calcd. (%) for C16H18BrNO2S (368.29): C
52.18, H 4.93; found: C 52.02, H 4.81.
Acknowledgements
This research was supported by a CEFIPRA fellowship. We
thank the CNRS and “Rennes Metropole” for providing fi-
nancial support.
N-Benzyl-2-bromo-N-methylbenzenesulfonamide
(43)[8a]
The reaction of 2-bromobenzenesulfonyl chloride (0.255 g,
1 mmol), N-methylbenzylamine (0.145 g, 1.2 mmol) and tri-
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(44)
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1 mmol), N-isopropylbenzylamine (0.179 g, 1.2 mmol) and
triethylamine (0.7 mL, 5 mmol) at room temperature during
12 h in dry dichloromethane (10 mL) affords the coupling
product 44 after addition of water (20 mL), extraction with
dichloromethane (20 mL), drying on MgSO4, evaporation
and purification on silica gel as a white solid; yield: 0.334 g
1
(91%); mp 134–1358C. H NMR (400 MHz, DMSO-d6): d=
8.05–8.00 (m, 1H), 7.90–7.85 (m, 1H), 7.55–7.50 (m, 2H),
7.38 (d, J=7.6 Hz, 2H), 7.29 (t, J=7.5 Hz, 2H), 7.21 (t, J=
7.5 Hz, 1H), 4.62 (s, 2H), 3.96 (sept., J=7.6 Hz, 1H), 0.94
(d, J=7.6 Hz, 6H); 13C NMR (75 MHz, DMSO-d6): d=
139.3, 139.2, 135.5, 134.1, 132.1, 128.1, 127.3, 127.0, 119.3,
49.5, 46.8, 20.6; elemental analysis: calcd. (%) for
C16H18BrNO2S (368.29): C 52.18, H 4.93; found: C 52.40, H
4.78.
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Charles Beromeo Bheeter et al.
FULL PAPERS
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3538
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Adv. Synth. Catal. 2012, 354, 3533 – 3538