Oxidative cycloaddition and cross-coupling processes on unactivated benzene derivatives

Article abstract of DOI:10.1039/c2sc22318j

Treatment of phenols or anilines containing a sulfonyl group in the presence of a hypervalent iodine reagent promotes a formal dearomatizing [2 + 3] cycloaddition reaction on unactivated benzene and naphthalene derivatives. This process occurs via an intramolecular nucleophilic addition to the Wheland species generated during the oxidative activation. Subsequent treatment under acidic conditions readily transforms the tricyclic system into a biaryl via a formal cross-coupling process.

Full text of DOI:10.1039/c2sc22318j

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Oxidative cycloaddition and cross-coupling processes on
unactivated benzene derivatives†
Cite this: Chem. Sci., 2013, 4, 1287
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Guillaume Jacquemot, Marc-Andre Menard, Chloe L'Homme and Sylvain Canesi
Treatment of phenols or anilines containing a sulfonyl group in the presence of a hypervalent iodine
reagent promotes a formal dearomatizing [2 + 3] cycloaddition reaction on unactivated benzene and
naphthalene derivatives. This process occurs via an intramolecular nucleophilic addition to the Wheland
species generated during the oxidative activation. Subsequent treatment under acidic conditions readily
transforms the tricyclic system into a biaryl via a formal cross-coupling process.
Received 29th September 2012
Accepted 2nd January 2013
DOI: 10.1039/c2sc22318j
www.rsc.org/chemicalscience
and have not been successfully extended to include “dipolar-
ophiles” similar to the aryl system 2, Fig. 1.
Introduction
Cycloaddition1 and cross-coupling2 transformations are exten-
sively used in organic synthesis. Cycloadditions are generally
performed on alkenes and alkynes; however, a similar trans-
formation involving dearomatization of the normally inert p-
bonds of an aromatic core would provide a means of preparing
key polyfunctional intermediates. Only a few examples of such
cycloaddition methods have been reported in the literature.3
Although the reported reactions have been exclusively intra-
molecular, a bimolecular approach would provide a greater
variety of potential synthetic avenues. In particular, the
remaining double bonds could be readily involved in further
transformations to rapidly generate elaborate products from
inexpensive aromatic derivatives. From a chemical standpoint,
such a transformation has been regarded as difficult to achieve.
However, biaryl syntheses involving cross-coupling of two
unactivated aromatic systems have received attention due to the
large number of natural targets incorporating these cores4 and
the potential for using axially chiral bi-aromatics as ligands in
asymmetric reactions.5 Previous methods of achieving this type
of transformation have generally involved heavy metals, but a
recent report in the literature suggested that similar cross-
coupling methodologies may be accomplished under metal-free
conditions using hypervalent iodine reagents6 and thio-
phenes,6a polymethylbenzenes,6b or anisole derivatives6f as
coupling partners. Other noteworthy cross-coupling processes
involving hypervalent iodine reagents in combination with
copper triate have been efficiently developed by Gaunt and co-
workers. In these reactions the copper salt remains crucial.7 The
few reported metal-free cycloaddition reactions involving
phenols have been limited to electron-rich alkenes8 and furan9
In this paper, we present a versatile methodology facilitating
[2 + 3] cycloaddition processes between benzene derivatives and
phenols or anilines. Slightly modied conditions may be used
to produce the cross-coupling adduct from these two unac-
tivated aromatic subunits. The processes are reminiscent of
Friedel–Cras chemistry in their approach to the connection of
two aromatic units under metal-free conditions.
Results and discussion
For the reactions to proceed, one of the systems must be
converted into an electrophilic species for trapping by the
remaining aryl acting as a nucleophile. This reversal of reac-
tivity may be thought of as involving “aromatic ring umpo-
lung”.10 An indication of how such selective aromatic
activations may be accomplished is provided in the work of
Kita,11 who demonstrated the reactivity of electron-rich
systems such as phenols in the presence of hypervalent iodine
reagents,12 for example (diacetoxyiodo)benzene (DIB) or phe-
nyliodine bis(triuoroacetate) (PIFA).13 The activation is best
performed in solvents such as triuoroethanol (TFE) or hexa-
uoroisopropanol (HFIP)10f and involves electron transfer to
produce a phenoxonium ion 3. This ion is readily trapped by
an aryl partner 2, leading to a Wheland species 4. At this stage
one of two pathways may occur, a classical elimination
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Laboratoire de Methodologie et Synthese de Produits Naturels, Universite du Quebec a
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Montreal, C.P. 8888, Succ. Centre-Ville, Montreal, H3C 3P8, Quebec, Canada. E-mail:
canesi.sylvain@uqam.ca
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c2sc22318j
Fig. 1 Cross-coupling and aromatic cycloaddition.
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(pathway a) affording the biaryl core 5 or an intramolecular
nucleophilic attack on arenium ion 4 (pathway b) leading to
the polycycle 6, Fig. 2.
A key aspect of this transformation is the relative stability of
the electrophilic species generated. Indeed, the phenoxonium 3
and arenium 4 ions produced during the umpolung activation
must be sufficiently stable to react with their respective nucle-
ophile partners in order to avoid competitive elimination
pathways such as benzylic hydrogen elimination from 3, which
generates an unstable polymerizable quinone methide (Fig. 3).
Because of its polar and non-nucleophilic properties, HFIP is
a valuable solvent that provides sufficient stabilization of elec-
trophilic species 3 and 4 in the presence of fairly reactive and
electron-rich partners such as enol ethers or furans.8c However,
the reaction is inefficient with simple benzene derivatives such
as iodo-aryls, naphthalene or benzene. To promote reactions
with these important compounds other issues must be resolved.
For instance, we have observed that a sulfonyl moiety on the
lateral chain behaves similarly to HFIP, enabling nucleophilic
attack even with poor electron systems such as iodobenzene.
We assume that in an intramolecular pathway the poor nucle-
ophilicity of the lone pairs on the sulfonyl oxygen atoms stabi-
lize the transition state 10 by overlapping phenoxonium ion
3 (n–p* interaction) without producing a carbon–oxygen
bond, Fig. 4.
Direct formation of compound 5 would be an interesting
example of cross-coupling; however, the nascent relatively
electron-rich system 5 would be reoxidized more quickly by the
unreacted hypervalent iodine reagent than the remaining
starting material 1. It appears that formation of the cycloadduct
6 is essential during the process. In a sense, compound 6 serves
as a protecting group for the phenol or aniline functionality and
minimizes undesirable overoxidation of the latter. Moreover,
further treatment of 6 in a second step under acidic conditions
and in the absence of hypervalent iodine regenerates the are-
nium species 4 and displaces the equilibrium in favor of the
irreversible pathway a, leading to biaryl 5. For this reason, it is
important to control the acidity of the medium during the
reaction to avoid reopening the cycloadduct 6, leading to
compound 5 that could be subsequently overoxidized due to the
presence of NH or OH bonds. Several conditions and hyper-
valent iodine reagents were investigated. Iodobenzene was the
rst “dipolarophile” tried because it is released during the
process following reduction of the hypervalent iodine reagent.
Bis(pivalate)iodobenzene (PIB, entry d) was the oxidizing agent
Fig. 3 Competitive transformations of phenoxonium species 3.
of choice, and the reaction was optimized at ꢀ4 ꢁC in a mixture
of HFIP–DCM (2 : 1). Pivalic acid, a weak carboxylic acid, was
released during the reaction. Similar results were observed
using DIB combined with Na2CO3 to neutralize the acetic acid
released, as the pH of the solution seems to be an important
aspect of this transformation. As expected, compound 11 was
not produced under harsher conditions employing PIFA. Since
this process occurred in an intermolecular manner and due to
the instability of species 3 (Fig. 3), ten equivalents of inexpen-
sive iodobenzene were used to favor formation of compound 11
over the polymeric by-products. If desired, the excess aromatic
partner could be chromatographically separated and reused. In
no case was it necessary to add more than ten equivalents of
iodobenzene (see Table 1, entries d, f and g). The nature of the
sulfonyl group does not really inuence the transformation,
although a slight diminution of yield was observed in the
presence of a withdrawing group (entry j). The reaction occurred
in the presence of a Julia–Kocienski auxiliary14 that could be
useful for further elaboration of the lateral chain, Table 1.
With the optimized conditions in hand, we investigated the
use of other aromatic systems as dipolarophiles. Iodo-aryl
compounds were competent substrates for this transformation.
The regioselectivity observed with para-substituted iodo-aryl
compounds appears to be controlled by steric factors, and a
protecting group was tolerated (entry e). In addition, the crucial
sulfone moiety may be successfully incorporated in a six-
membered-ring transition state with a lower overall yield as
expected (entry f). We were pleased to observe that the new
process even occurred using benzene and was efficient when
naphthalene was used (72%), most probably due to the fact
that one aromatic core remains intact during the formation of
12h, Table 2.
In some cases when iodobenzene was not used as a dipo-
larophile, a small amount of compound 11 (ꢂ5%) was observed,
originating from a competition with iodobenzene released
during the umpolung activation. The successful extension of
Fig. 2 Oxidative cross-coupling vs. cycloaddition.
1288 | Chem. Sci., 2013, 4, 1287–1292
Fig. 4 Oxidative dearomatizing “2 + 3” cycloaddition.
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Table 1 Cycloaddition optimization conditions
Compound 9i reacted in the presence of furan to afford 14 in
95% yield. It should be stressed that in the presence of PIB and
with a sulfone on the lateral chain, the overall yield observed
was double that of the same transformation employing ethyl-
phenol9c and furan, a fairly reactive and electron-rich partner
(ꢂ45% yield), demonstrating the importance of the sulfonyl
moiety as a stabilizing and anchimeric assisting group for the
phenoxonium species generated in the reaction, Scheme 1.
Although the sulfone moiety present on the lateral chain
could be further transformed using Julia–Kocienski chemistry
(compound 11k), it would be more convenient to introduce a
removable auxiliary to enable the cycloaddition by stabilizing
the electrophilic species 16. In addition, the valence of the
oxygen atom makes development of an asymmetric pathway
difficult. Toward this goal a similar reaction involving a
sulfonamide group has been envisaged; in this case the
required stabilizing sulfonyl group is directly connected to the
aniline and may stabilize the ortho positions of the electro-
philic species 16 in a manner similar to 10. This option could
lead to a further asymmetric pathway through the introduction
of a chiral sulfonamide. This alternative tolerated a variety of
spectator functionalities and several sulfonamides. However,
lower yields were observed with substituted sulfonamides
(Table 3, entries 17c and 17d). Naphthalene underwent effi-
cient reaction with sulfonamides 15, most probably because
the second aromatic ring stabilized the resulting areniun ion 4
(Table 3).
Entry
R
Iodine(III)
PhI equiv.
Yield (%)
a
b
c
d
e
f
g
h
i
Ph
Ph
Ph
Ph
Ph
Ph
Ph
PIFA
DIB
DIB + Na2CO3
PIB
10
10
10
10
10
20
5
10
10
10
10
—
34
47
51
50
53
37
55
48
41
45
PIB + Na2CO3
PIB
PIB
PIB
PIB
PIB
PIB
n-Propyl
p-PhOMe
p-PhNO2
Benzothiazol
j
k
Table 2 Cycloadditions with benzene derivatives
Entry
n
2 (equiv.)
R1
R2
R3
Yield (%)
Only ve equivalents of naphthalene were required when a
sulfonamide was used as the polarophile. This process repre-
sents an expeditious route to indoline cores, an important
functionality present in a large number of bioactive products.
The synthesis of scaffolds such as 12 or 17 has not been docu-
mented in the literature, and only a few examples of isomers
having modied connectivity have been prepared from benzo-
furan, oxabicycle and styrene derivatives.16 Most of these
methods have involved transition metals. Reactions have been
attempted using other aromatic partners in combination with
sulfonamide 15, including a substituted naphthalene, to
generate tetracycle 18. Highly electron-rich methoxynaph-
thalene derivatives were unsatisfactory substrates for the
cycloaddition pathway and led to several cross-coupling
adducts. However, when using a moderate electron-donor
group such as a mesylate, cycloadduct 18 was obtained as well
as the C–N cross-coupling compound 19 resulting from direct
attack of the naphthalene derivative on the nascent electro-
philic nitrogen generated during the umpolung activation. A
a
b
c
d
e
f
1
1
1
1
1
2
1
1
10
10
10
10
8
10
20
10
H
H
H
H
H
H
H
H
Me
Et
iPr
CH2OTBS
I
I
I
I
I
I
51
54
47
40
35
31
40
72
H
H
g
h
H
H
CH]CHCH]CH
this process to systems other than iodobenzene provides
support for the mechanism proposed in Fig. 2 and rules out an
intramolecular process involving the hypervalent iodine
reagent. This method could be employed in total syntheses of
natural products containing hydrodibenzofuran cores such as
linderol A,15a a potent inhibitor of melanin biosynthesis in
cultured B-16 melanoma cells, or rubiyunnanin A15b (Fig. 5).
Other systems have been tested including anthracene, in
which a formal “4 + 3” cycloaddition occurred to produce 13.
Fig. 5 Natural products containing hydrodibenzofuran cores.
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Scheme 1 Anthracene and furan cycloadditions.
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Table 3 Cycloaddition with sulfonamides
Table 4 Formal cross-coupling process
Entry
R1
R
Yield (%)
Entry
X
R
R1 R2
R3 Yield (%)
a
b
c
d
e
f
g
h
i
Me
Et
Me
Me
Me
Me
Me
Cl
iPr
nPr
61
59
32
38
45
51
52
51
54
53
62
52
43
a
b
c
d
e
f
g
h
i
O
O
O
O
O
O
O
CH2CH2SO2Ph
CH2CH2SO2Ph
CH2CH2SO2Ph
CH2CH2SO2Ph
CH2CH2SO2Ph
CH2CH2SO2C6H4OMe
CH2CH2SO2Ph
Me
H
H
H
H
H
H
H
I
I
I
I
H
I
H
H
H
H
H
H
H
97
91
98
90
97
87
98
97
83
97
76
79b
94
Me
Et
iPr
H
Tol
iPr
Bn
Me
Me
Me
Me
Me
Me
Me
Me
H
–C4H4–a
–C4H4–
–C4H4–
–C4H4–
–C4H4–
–C4H4–
–C4H4–
NSO2Et
NSO2Me nPr
NSO2Me iPr
NSO2Me CH2CH2OH
NSO2Me CH2CH2OTBS
NSO2Me CH2CH2SO2Ph
CH2CH2SO2Ph
CH2OH
CH2CH2OH
CH2CH2OTBS
TMS
j
k
l
j
k
l
m
m
a
b
–C4H4– ¼ –CH]CHCH]CH–. The triuoro ester derivative is
isolated.
similar transformation was observed in the presence of
anthracene, and we assumed that the quite stable dibenzylic
arenium ion 4 generated from the anthracene attack was trap-
ped by pivalic acid released in the medium, leading to
compound 20 in 46% yield, Scheme 2.
Interestingly, in a second step under acidic conditions
mediated by triuoroacetic acid, the conversion of cycloadduct
21 to biaryl 5 was quantitatively observed, probably via regen-
eration of species 4 and displacement of the equilibrium in
favor of pathway a as discussed in Fig. 2. This suggests that
further acid treatment of compounds 12 or 17 leads to a formal
cross-coupling process involving unactivated aromatic subunits
as a route to C–H activation, Table 4.
A direct cross-coupling process may also be undertaken
from the sulfamide derivative 22. In this case biaryl systems
were directly obtained and only a small amount of cycloadduct
product was occasionally detected. This compound was rapidly
transformed into the biaryl 23 in the presence of slightly
acidied CDCl3. This result may be rationalized if we consider
that the new cycloadduct derivative is rapidly transformed into
23 due to the presence of the additional basic pyrrolidine
moiety. The sulfamide segment appears to be a direct C–H
inductor, enabling cross-coupling with naphthalene deriva-
tives, Table 5.
Guziec and Wang have described reductive removal of the
sulfonamido group17 in the presence of NH2Cl and NaH to
produce biaryls 25 from compound 24 through an overall
sequence that neatly complements established methods, Fig. 6.
An interesting aspect of this transformation is its ability to
dearomatize a benzene derivative into a functionalized system
ready for further transformations. As an illustration of some
possibilities provided by this method, several conventional
reactions enabling quick transformation of the key cycloaddi-
tion product into further functionalized cores are presented in
Scheme 3. For example, Diels–Alder reaction of 12a led to
compound 26 in 59% yield. Hydrogenation of 17a provided the
tetracyclic indoline 27 in 66% yield, and treatment of 17a with
OsO4 and NMO produced diol 28 in 60% yield.
Table 5 Direct cross-coupling process
Entry
R
Yield (%)
a
b
c
d
e
f
Me
Et
iPr
Cl
CH2CO2Me
TMS
55
64
54
81
36
52
Scheme 2 O-Mesylnaphthol and anthracene.
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Scheme 3 Functionalization of cycloadducts 12 and 17.
Conclusions
In summary, a new oxidative dearomatizing cycloaddition
process between phenols or anilines and aromatic derivatives
has been developed. This process is made possible by the
introduction of a key sulfonyl group to stabilize the electrophilic
species generated during the hypervalent iodine-mediated
umpolung activation. Slightly modied conditions may be used
to obtain a cross-coupling adduct from these two unactivated
aromatic subunits as an alternative C–H activation trans-
formation. Ongoing investigations of these processes, including
an asymmetric version with a chiral sulfonamide moiety, and
potential applications will be disclosed in due course.
Acknowledgements
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Research Council of Canada (NSERC), the Canada Foundation
for Innovation (CFI), the provincial government of Quebec
(FQRNT and CCVC)and Boehringer Ingelheim (Canada) Ltd for
their precious nancial support in this research.
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1292 | Chem. Sci., 2013, 4, 1287–1292
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