Controllable mono-/dialkenylation of benzyl thioethers through rh-catalyzed aryl C-H activation

Article abstract of DOI:10.1002/chem.201300829

Under solvent control: Benzyl thioethers were alkenylated in excellent yields with broad substrate scope and the selectivity (mono- vs. disubstituted product) was controlled by the solvent and ratio of reactants (see scheme). Sequential alkenylation with two different alkenes was also carried out in a one-pot process. In addition, the thioether directing group was removed in a one-pot process with simultaneous hydrogenation of the double bond to give the toluene derivatives. Copyright

Full text of DOI:10.1002/chem.201300829

DOI: 10.1002/chem.201300829
Controllable Mono-/Dialkenylation of Benzyl Thioethers through Rh-
À
Catalyzed Aryl C H Activation
Xi-Sha Zhang,[a] Qi-Lei Zhu,[a] Yun-Fei Zhang,[a] Yan-Bang Li,[a] and Zhang-Jie Shi*[a, b]
À
C H bond functionalization is a direct, economical, and
efficient way to construct complex molecules that has drawn
considerable attention in the past few decades.[1] One power-
ful and widely used strategy to improve the efficiency and
sulfur-tethered directing groups.[24] The use of a thioether as
a directing group poses an extra challenge because of their
ability to poison many transition-metal catalysts. However,
their use as a directing group also has several advantages:
1) sulfur is contained in many natural and useful mole-
cules,[25] functional materials, organocatalysts and water-re-
duction catalysts;[26] 2) a thioether directing group can be
easily removed under reductive conditions either stoichio-
metrically or catalytically;[27] and 3) the thioether can under-
go many other transformations.[28,29] To the best of our
knowledge, there is no report introducing the thioether as a
directing group in rhodium catalysis, although elegant exam-
ples of Pd-catalyzed transformations have been reported.[19]
Herein, we report a successful example of controllable alke-
À
control the selectivity of C H activation is to introduce a di-
recting group on the substrates.[2] In general, a relatively
stable metallocycle intermediate can be formed with direct-
À
ing groups, promoting both the C H activation and the sub-
sequent functionalization. The most widely used directing
groups usually contain sp2-hybridized heteroatoms, including
carbonyl-containing groups[3–9] and N-/O-containing hetero-
cycles,[10] among others.[11] Several removable and/or trans-
formable mono-/bidentate directing groups[12,13] have recent-
ly been developed. Other directing groups have also been
explored recently by forming anions under basic conditions,
including carboxylic acids, electron-deficient amides,[14] hy-
droxyl groups,[15] and carbon anions.[16] In comparison, neu-
tral sp3-hybridized heteroatoms have been less thoroughly
investigated as directing groups (amines, ethers, and thioeth-
À
nylation through thioether-directed C H activation under
Rh catalysis. Most importantly, the selectivity between
mono- and difunctionalization was well controlled by use of
different solvents (Scheme 1a and b). Unactivated styrenes
also react smoothly under the conditions provided (Sche-
me 1c). Sequential functionalization with two different al-
ers).[17–19] Herein, we report an sp3-hybridized-thioether-di-
rected C H alkenylation through Rh catalysis.
Recently, great progress has been made in the field of C
[19]
À
kenes was further achieved in
a
one-pot process
À
(Scheme 1d). Furthermore, functionalized toluene deriva-
tives can be obtained in one pot by direct treatment of the
reaction mixture with Raney Ni (Scheme 1e).
H functionalization through Rh catalysis.[20] Rhodium cataly-
sis complements Pd catalysis because it has good functional-
group tolerance and high catalytic efficiency, and many ele-
gant examples have been reported recently.[21–23] Because
the directing-group strategy is also one of the most powerful
Initially, we selected benzylACTHNUTRGENUGN(methyl)sulfane (1a) and ethyl
acrylate (2a) as model substrates to screen the reaction con-
ditions (Table 1). Catalyst screening showed that RhIII cata-
lysts promoted the desired transformation and gave a mix-
ture of the mono- and dialkenylation products (3a and 4a,
À
ways to increase selectivity in C H functionalization, the de-
velopment of new and useful directing groups in Rh cataly-
sis is necessary to expand the applications of Rh-catalyzed
respectively) in the presence of Cu
methanol (Table 1, entries 1 and 2). Clearly, cationic catalyst
[Cp*Rh(CH3CN)3][SbF6]2 gave better yield than
ACHTUNGRTEN(NGNU OAc)2 and AgOAc in
À
C H transformations.
In fact, sulfur-containing groups are rarely used as direct-
A
R
a
ing groups,[11b,c,13c,19] despite the development of several
[{RhCp*Cl2}2], with monoalkenylated 3a as the major prod-
uct (Table 1, entry 2). To our surprise, some other alcoholic
solvents, for example, tBuOH and tert-AmylOH, inversed
the selectivity and dialkenylated 4a became the major prod-
uct (Table 1, entries 8 and 9). This observation suggested the
potential to control the selectivity of this alkenylation by
changing the solvent.
First of all, we conducted the reaction of several represen-
tative substrates in different solvents to investigate the sol-
vent effect (Table 2). Apart from styrene, the reaction of
other substrates gave moderate to good yield and good se-
lectivity; MeOH favors monoalkenylation whereas tBuOH
favors dialkenylation. For styrene, the reactivity was low
and a low yield was obtained (Table 2, entries 5 and 6). In-
[a] X.-S. Zhang, Q.-L. Zhu, Y.-F. Zhang, Y.-B. Li, Prof. Dr. Z.-J. Shi
Beijing National Laboratory of Molecular Sciences (BNLMS) and
Key Laboratory of Bioorganic Chemistry and
Molecular Engineering of Ministry of Education
College of Chemistry and Molecular Engineering and
Green Chemistry Center
Peking University, Beijing 100871 (P.R. China)
E-mail: zshi@pku.edu.cn
[b] Prof. Dr. Z.-J. Shi
State Key Laboratory of Organometallic Chemistry
Chinese Academy of Sciences, Shanghai 200032 (P.R. China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201300829.
11898
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 11898 – 11903

COMMUNICATION
Supporting Information). After
the screening of conditions, a
93% yield of 4a was obtained
by increasing the amount of
CuACHTNURTGNE(UNG OAc)2 (3.0 equiv) and 2a
(3.0 equiv), as well as slightly
increasing the temperature
(Table S2, entry 4 in the Sup-
porting Information).
With the best conditions in
hand, we explored the general-
ity for the monoalkenylation
(Table 3).
With
benzyl-
AHCTUNGTERG(NNUN methyl)sulfane (1a) as the
model substrate, both methyl
acrylate and butyl acrylate
gave the corresponding prod-
ucts in high yields (3b and 3c).
As well as acrylates, acryla-
mides also underwent the alke-
nylation, albeit in lower yields
(3e and 3 f). For methyl(naph-
Scheme 1. Summary of this work (EWG=electron-withdrawing group; Cp*=pentamethylcyclopentadienyl).
Table 1. Catalyst screening and the solvent effect on the selectivity of mono- and dia-
thalen-2-ylmethyl)sulfane, the alkenylation occur-
red selectively in high yield at the b-position (3d)
as a result of steric hindrance. Of other thioethers
used in the reaction, the ethyl group showed excel-
lent reactivity (3g). However, phenyl and tolyl
groups gave low to moderate yields, respectively
(3h and 3i). The sensitivity of the reaction to the
protecting group on sulfur probably resulted from
slight changes in their electronic effects, which
strongly affected the ability of sulfur to coordinate
with the catalytic metal center. Other groups, mer-
capto, sulfinyl, sulphonyl, hydroxyl, and ether, all
failed to result in reaction (3j, 3k, 3l, 3m, 3n).
Due to the facile preparation, benzyl(para-tolyl)-
sulfane derivatives were synthesized and used to
investigate the functional group tolerance. Methyl
substitution at ortho-, meta-, and para-positions all
gave good to excellent results (3n, 3o, and 3p).
Chloride, cyano, methoxyl, and ester groups were
tolerated, giving acceptable yields (3q–3u). Com-
parably, electron-deficient substituents (3r and 3s)
lkenylation.[a]
Entry
x
y
Catalyst (5 mol%)
Solvent
MeOH
T
t
Yield
(mono/di)
[%][b]
[8C] [h]
ACHTUNGTRENNUNG
1
2
3
4
5
6
7
8
9
0.10 0.25
0.10 0.25
0.10 0.25 [{RhCAHTUNGTRENNNUG
A
90
90
90
90
90
90
90
90
24 53.2:14.0
24 79.7:28.3
24 trace
24 trace
24 trace
24 51.2:14.3
24 51.4:11.1
24 15.1:58.8
24 17.8:79.5
A
U
ACHTUNGTRENNUNG
N
MeOH
MeOH
R
0.10 0.25
0.10 0.25
0.10 0.25
0.10 0.25
A
U
A
A
U
ACHTUNGTRENNUNG
A
U
ACHTUNGTRENNUNG
A
U
ACHTUNGTREN[NUNG SbF6]2 tert-AmylOH 90
[a] cod=1,5-cxclooctadienyl; acac=acetylacetonate; tert-AmylOH=2-methylbutan-2-
ol [b] NMR spectroscopic yield with CH2Br2 the as internal standard.
creasing the reaction temperature and amount of styrene
(2d) gave a better yield and selectivity (Table 1, entries 7
and 8). Although the ability of the solvent to control the se-
lectivity was demonstrated by these substrates, the chemical
yields were not good enough, so we conducted further opti-
mization of the reaction conditions based on the results pro-
vided in Table 1 and Table 2.
After systematic screening (Table S1 in the Supporting In-
formation), we found that the best conditions (82%,
Table S1, entry 13 in the Supporting Information) for form-
ing monoalkenylated product 3a were in the presence of
are better than electron-rich groups (3q and 3t), indicating
À
that the C H activation might occur through a concerted
metalated dehydrogenation (CMD) rather than a direct
electrophilic substitution pathway. Again, acrylamide
showed slightly better reactivity than N,N-dimethylacryla-
mide (3v vs. 3w). It is important to note that an internal
alkene can also be used in the reaction, albeit in a lower
yield (3x).
We further extended the scope of the reaction with re-
spect to the alkene to include styrene derivatives (Table 4).
To provide high efficiency, the amount of both catalyst and
oxidant needed to be increased. (2-Methylbenzyl)(para-tol-
yl)sulfane (1b) was also used as the partner in this transfor-
mation and 2.5 equivalents of the styrene derivatives were
CuACHTUNGTRENNUNG(OAc)2 and AgOAc in MeOH when an excess of 1a was
present.[30] The key to selective dialkenylation was to change
the solvent from methanol to tert-butanol (Table S2 in the
Chem. Eur. J. 2013, 19, 11898 – 11903
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11899

Z.-J. Shi et al.
Table 2. Investigation of the solvent effect on the selectivity for mono-
and disubstitution for several representative substrates.
Table 3. Monoalkenylation with various thioethers and electron-deficient
alkenes.[a]
Entry 1 (R1, R3) 2 (R2)
Solvent 3 [%][a]
4 [%][a]
3/4
1
1a
(Me, H)
2a
ACHTUNGTRENNUNG(CO2Et)
MeOH 79.7 (3a) 28.3 (4a) 2.8:1
U
2
3
1a
1a
2a
2c
tBuOH 15.1
MeOH 82.9 (3c) 13.5 (4c) 5.5:1
58.8
1:3.9
ACHTUNGTRENNUNG(CO2Bu)
4
5
1a
1a
2c
tBuOH 13.5
MeOH 36.8 (3y)
90.6
7.5 (4y) 4.9:1
1:6.7
2d
(Ph)
2d
2d
2d
2a
6
1a
1a
1a
1o
tBuOH 46.2
MeOH 48.7
tBuOH 32.9
MeOH 64.9 (3i)
23.6
13.4
29
2.0:1
3.6:1
1.1:1
7[b]
8[b]
9
9.8 (4 f) 4.7:1
ACHTUNGTRENNUNG(Tol, H)
10
11
1o
1d
ACHTUNGTRENNUNG(Tol, Me)
1d
1i
ACHTUNGTRENNUNG
2a
2a
tBuOH 23.1
MeOH 59.5 (3n) 10.5 (4h) 5.7:1
66.3 1:2.9
[a] Reaction conditions: Thioether (A, 0.2 mmol, 2 equiv), alkene (B,
0.1 mmol), catalyst [Cp*Rh
ACHTUNTGRENNG(U CH3CN)3]ACHTUNTGREN[NUGN SbF6]2 (5 mol%), oxidant Cu-
AHCTUNGTRENNUNG
12
13
2a
2a
tBuOH 38.5
MeOH 40.3 (3r)
70.1
1:1.9
1208C for 24 h under a N2 atmosphere. [b] NMR spectroscopic yield with
CH2Br2 as the internal standard. [c] 1 equivalent of A, 4 equivalents of B,
6.6 (4g) 6.1:1
10% of Rh, and 4 equivalents of Cu
3 equivalents of B, 10% of Rh, and 3 equivalents of Cu
[e] 1 equivalent of A, 6 equivalents of B, 10% of Rh and 3 equivalents of
Cu(OAc)2, and tBuOH (1 mL) was used as the solvent.
ACHTUNGTRENNUNG
14
2a
tBuOH 42.3
58.6
1:1.4
ACHTUNGTRENNUNG
[a] NMR spectroscopic yield of the crude reaction system with CH2Br2 as
the internal standard. [b] 3 equivalents of alkene were used at 1208C.
AHCTUNGTRENNUNG
used. We found that styrene, 4-methylstyrene, and 4-vinyl-
1,1’-biphenyl worked well and gave good to excellent yields
(3ba, 3bb, and 3bd). Steric hindrance did not affect the re-
action efficiency (3bc). Importantly, halogen atoms were tol-
erated, providing the possibility for orthogonal functionali-
zations[31] (3bf and 3bg). Electron-rich and -deficient styr-
ene derivatives both reacted smoothly to give the desired
products, whereas electron-deficient alkenes were more re-
active (3be and 3bf). Unfortunately, nitro and cyano groups
were not tolerated, probably as a result of the competitive
coordination of the nitro and cyano groups to the metal
Table 4. Substrate scope of styrene derivatives.[a]
À
center, thus inhibiting the C H activation (3bh, 3bi).
[a] Reaction conditions: Thioether (1b, 0.1 mmol, 1 equiv), alkene (2,
0.25 mmol, 2.5 equiv), catalyst [Cp*Rh
dant Cu(OAc)2 (2 equiv), and AgOAc (0.3 equiv) reacted in MeOH
(1 mL) at 1208C for 24 h under a N2 atmosphere.
ACHTUNTGRENGU(N CH3CN)3]AHCUTNGTREN[NUNG SbF6]2 (10 mol%), oxi-
Subsequently, we investigated the substrate scope for the
dialkenylation with the use of tert-butanol as the solvent
(Table 5). We found that: 1) activated alkenes worked well
and the desired products were obtained in excellent yields
(4a, 4b, 4c, and 4d); 2) different thioethers could be used
as the directing groups with moderate to excellent reactivity
(4e, 4 f, and 4i); and 3) chloride survived well and the di-
functionalized product was isolated in a moderate yield
(4g).
AHCTUNGTRENNUNG
and tBuOH as a solvent. To our delight, the sequential alke-
nylation of two different alkenes was achieved in 56% yield
and high purity [Scheme 2, Eq. (1)]. Notably, if the catalyst
was recharged, a quantitative yield was achieved in this se-
quential dialkenylation with different alkenes [Scheme 2,
Eq. (2)].
Since the mono- and dialkenylation have been carried out
in different solvents, we set out to think about the stepwise
alkenylation with different alkenes with the same catalytic
system by changing the solvents in one pot. We removed
methanol under vacuum from the product mixture of the
first alkenylation and added a second alkene, more oxidant,
In the deuterium-labeling experiments (Scheme 3), proton
scrambling was observed, indicating that an equilibrium
À
exists at the C H activation step, which is inconsistent with
previous reports about RhIII catalysis.[23] Thus, we proposed
the catalytic cycle shown in Scheme 4. With the assistance of
11900
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Chem. Eur. J. 2013, 19, 11898 – 11903

Mono-/Dialkenylation of Benzyl Thioethers
Table 5. Substrate scope of the dialkenylation.[a]
COMMUNICATION
OAcÀ, the sulfur-directed C H activation proceeded
À
through a CMD pathway to give 5-membered intermediate
I. Subsequent alkene insertion and b-hydride elimination
finished the catalytic cycle and released the final product.
Scheme 4. Proposed mechanism.
Further efforts have been
made to explore the applica-
tions of this method. As we
know, thioethers can easily be
reduced under different condi-
tions. For example, the alkeny-
lated product has been submit-
ted to the reduction conditions
with Raney Ni in ethanol and
the directing group can be
easily removed at room tem-
perature (Scheme 5). Notably,
the alkenes were reduced at
the same time, providing 3-
phenylpropanoic acid deriva-
tives (and toluene derivatives),
which are important skeletons
in organic synthesis [Eqs. (5)
and (6)].[32] To simplify the
procedure for these transfor-
mations, we constructed the al-
kylated toluene derivatives in
a one-pot process by directly
adding Raney Ni to the prod-
uct mixture from the first alke-
Scheme 2. Semi-one-pot dialkenylation reaction of thioether 1a with two different alkenes.
nylation
step
[Scheme 6,
Eqs. (7) and (8)]. This study
provides a convenient process
to make such useful chemicals.
In summary, we successfully
developed the thioether-direct-
ed rhodium
ACHTUNGTRENNUNG
À
Scheme 3. Deuterium-labeling experiments (Tol=tolyl).
Chem. Eur. J. 2013, 19, 11898 – 11903
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Z.-J. Shi et al.
À
Keywords: alkenylation
thioethers
· C H activation · rhodium ·
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Experimental Section
General procedure for monoalkenylation: Synthesis of 3 (Table 4): The
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Acknowledgements
Support of this work by the “973” Project from the MOST of China
(2009CB825300) and the NSFC (Nos. 20925207 and 21002001) is grateful-
ly acknowledged.
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Mono-/Dialkenylation of Benzyl Thioethers
COMMUNICATION
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Received: March 3, 2013
Revised: June 7, 2013
Published online: August 16, 2013
Chem. Eur. J. 2013, 19, 11898 – 11903
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
11903