Rhodium-catalyzed decarbonylative direct olefination of arenes with vinyl carboxylic acids

Article abstract of DOI:10.1002/adsc.201401020

A rhodium(I)-catalyzed direct C-H bond olefination of pyridyl-substituted arenes with readily available vinyl carboxylic acids has been realized. This reaction occurred efficiently without the need for any external oxidant, affording the ortho-olefinated products in high yields and excellent regioselectivities. Diversely substituted vinyl carboxylic acids behaved as efficient olefination reagents under the reaction conditions, and a range of functional groups in both coupling partners was well tolerated. Mechanistic studies indicated that a decarbonylation step is involved in this catalytic process, and pivalic anhydride [(t-BuCO)₂O] acts as the activator of the carboxylic acids for the in situ generation of highly active anhydrides.

Full text of DOI:10.1002/adsc.201401020

FULL PAPERS
DOI: 10.1002/adsc.201401020
Rhodium-Catalyzed Decarbonylative Direct Olefination of
Arenes with Vinyl Carboxylic Acids
Ruiying Qiu,a Lingjuan Zhang,a Conghui Xu,a Yixiao Pan,a Hongze Pang,a
Lijin Xu,a,* and Huanrong Lia,*
a
Department of Chemistry, Renmin University of China, Beijing 100872, Peopleꢀs Republic of China
Fax : (+86)-10-6251-6444; phone: (+86)-10-6251-1528; e-mail: xulj@chem.ruc.edu.cn or hrli@chem.ruc.edu.cn
Received: October 27, 2014; Revised: January 15, 2015; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201401020.
À
Abstract: A rhodium(I)-catalyzed direct C H bond groups in both coupling partners was well tolerated.
olefination of pyridyl-substituted arenes with readily Mechanistic studies indicated that a decarbonylation
available vinyl carboxylic acids has been realized. step is involved in this catalytic process, and pivalic
This reaction occurred efficiently without the need anhydride [(t-BuCO)2O] acts as the activator of the
for any external oxidant, affording the ortho-olefi- carboxylic acids for the in situ generation of highly
nated products in high yields and excellent regiose- active anhydrides.
lectivities. Diversely substituted vinyl carboxylic
acids behaved as efficient olefination reagents under Keywords: anhydrides; decarbonylation; olefination;
the reaction conditions, and a range of functional rhodium; vinyl carboxylic acids
Introduction
simple arenes could serve as useful coupling partners
to react directly with olefins under palladium cataly-
Within the last decade the transition metal-catalyzed sis.[2] Following this significant lead, extensive efforts
dehydrogenative coupling reaction of simple arenes have been made in the development of more active
with olefins has been highlighted as a powerful alter- and selective transition metal catalytic systems. Con-
native to the traditional Pd-catalyzed Mirozoki–Heck sequently, recent studies have shown that the pres-
reaction.[1] This process obviates the requirement of ence of a suitable directing group could greatly facili-
À
a tedious and costly halogenation step, allowing the tate the regioselective direct C H ortho-olefination of
normally unreactive arene C H bonds to undergo arenes, and the catalysts derived from palladium,[3]
À
direct coupling with olefins to produce the arylated ruthenium[4] and rhodium complexes[5] proved to be
olefins. Fujiwara and Moritani first revealed that highly effective. Despite these spectacular advances,
Scheme 1.
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Table 1. Screening conditions for direct olefination of 2-
(meta-tolyl)pyridine (1a) with cinnamic acid (2a).[a]
there is still much room for improvement, particularly
in terms of substrate scope and catalytic efficiency.
Owing to their easy availability, structural diversity
and safety, carboxylic acids and their derivatives have
been recently recognized as reliable coupling partners
in transition metal-catalyzed decarboxylative or de-
carbonylative cross-coupling reactions.[6] In this con-
text, using vinyl carboxylic acids and their derivatives
as the olefin sources has drawn increasing attention,
and a number of useful protocols are known in the lit-
erature.[7,8] In the hope of further improving the atom
economy and catalytic efficiency, chemists became in-
terested in the combination of decarbonylation or de-
carboxylation of vinyl carboxylates with direct func-
Entry [Rh]
Solvent Time [h] Yield [%][b]
1
2
3
4
5
6
7
8
[Rh(COD)2]OTf
toluene 24
toluene 24
toluene 24
toluene 24
toluene 24
95
30
54
0
89
46
8
[Rh(COD)Cl]2
[Rh(COD)2]BF4
[Rh(NBD)Cl]2
[Rh(NBD)2]BF4
[Rh(1,5-HD)Cl]2 toluene 24
[Rh(C2H4)2Cl]2 toluene 24
[Rh(acac)(C2H4)2] toluene 24
À
tionalization of C H bonds, and exciting progress has
been accomplished.[9] Notably, Yu and co-workers
demonstrated that, in the presence of a Rh(I) catalyst
0
À
and a suitable base, the direct olefination of arene C
9
[Rh(PPh3)3Cl]
[Rh(acac)(CO)2]
[RhCp*Cl2]2
[Rh(CO)2Cl]2
[Rh(COD)2]OTf toluene 12
toluene 24
toluene 24
toluene 24
toluene 24
0
60
0
H bonds via decarbonylation of cinnamoyl chlorides
and cinnamic anhydrides could be readily realized to
give the olefinated products in high yields with good
functional group tolerance (Scheme 1, a).[9a–c] Impor-
tantly, unlike the decarboxylation process, no external
oxidant is required in these reactions. However, this
chemistry is plagued by the necessity of prior prepara-
tion of cinnamoyl chlorides and cinnamic anhydrides
from the parent vinyl carboxylic acids via tedious op-
erations. Very recently we reported that vinyl carbox-
ylic acids could serve as effective olefination reagents
in Rh(I)-catalyzed decarbonylative direct olefination
of indoles.[10] Following this success, herein we report
that, in the presence of a Rh(I) catalyst and an appro-
priate activator, arylpyridines could undergo highly
efficient and selective decarbonylative olefination
with various vinyl carboxylic acids in the absence of
any external oxidants under relatively mild conditions
(Scheme 1, b).
10
11
12
13
14
15
16
17
18
19
20
21[c]
22[d]
23[e]
24[f]
25[g]
26[h]
27[i]
28[j]
29
30[k]
91
95
65
71
77
72
89
67
21
67
7
29
0
0
70
35
87
0
[Rh(NBD)2]BF4
[Rh(CO)2Cl]2
toluene 12
toluene 12
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
[Rh(COD)2]OTf
none
PhCl
12
p-xylene 12
anisole
DMF
12
12
DMSO 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
toluene 12
[Rh(COD)2]OTf
0
[a]
Reaction conditions: 1a (0.5 mmol), 2a (0.75 mmol), [Rh]
(5.0 mol%), (t-BuCO)2O (0.75 mmol), solvent (3.0 mL),
1408C. COD=cyclooctadiene; NBD=norbornadiene;
acac=acetylacetonate; HD=hexadiene; Cp*=pentame-
thylcyclopentadiene.
Results and Discussion
We initiated our investigations by choosing the cou-
pling reaction of 2-(meta-tolyl)pyridine (1a) with cin-
namic acid (2a) as our model system for the optimiza-
tion studies. Using (t-BuCO)2O as the additive and
toluene as the reaction medium, we first examined
the catalytic performance of different rhodium com-
plexes. It was found that [Rh(COD)2]OTf displayed
the highest catalytic activity, affording the desired
product (E)-2-(5-methyl-2-styrylphenyl)pyridine (3aa)
in 95% yield (Table 1, entry 1). Comparable catalytic
efficiency was observed with [Rh(NBD)2]BF4 and
[Rh(CO)2Cl]2 (Table 1, entries 5 and 12), but switch-
ing to other rhodium complexes led to either dimin-
[b]
[c]
Isolated yields reported.
Boc2O was used to replace (t-BuCO)2O. Boc =tert-butyl-
AHCTUNGTREGUNoNN xycarbonyl.
[d]
[e]
[f]
Ac2O was used to replace (t-BuCO)2O.
t-BuCOCl was used to replace (t-BuCO)2O.
(CF3CO)2O was used to replace (t-BuCO)2O.
(MeOCO)2O was used to replace (t-BuCO)2O.
Reaction temperature 1208C.
[Rh(COD)2]OTf (2.5 mol%) was used.
(t-BuCO)2O (0.5 mmol) was used.
No (t-BuCO)2O was added.
[g]
[h]
[i]
[j]
[k]
ished yields or no reactivity (Table 1, entries 2–4 and mained
efficient
(Table 1,
entry 13),
but
6–11). Further studies indicated that, when the reac- [Rh(NBD)2]BF4 and [Rh(CO)2Cl]2 turned out
tion time was shortened to 12 h, [Rh(COD)2]OTf re- to be ineffective (Table 1, entries 14 and 15). With
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Rhodium-Catalyzed Decarbonylative Direct Olefination of Arenes
Table 2. Rh-catalyzed direct olefination of 1a with b-substi-
Table 3. Rh-catalyzed direct olefination of 1a with a-substi-
tuted acrylic acids.[a,b]
tuted acrylic acids.[a,b]
[a]
Reaction conditions: 1a (0.5 mmol),
4 (0.75 mmol),
[Rh(COD)2]OTf (5.0 mol%), (t-BuCO)2O (0.75 mmol) in
3.0 mL toluene, 1408C, 24 h.
Isolated yields reported.
[b]
verted to the expected products (3ab–3as) in good to
excellent yields with exclusive E stereochemistry, and
various functional groups could well survive under
the reaction conditions regardless of their electronic
properties and substitution positions. Notably, the
sensitive halogen (3ai–3am) and pinacolboryl (3an)
substitutuents were tolerated, providing useful han-
dles for further elaboration. Furthermore, the hetero-
[a]
Reaction conditions: 1a (0.5 mmol.),
[Rh(COD)2]OTf (5.0 mol%), (t-BuCO)2O (0.75 mmol),
toluene (3.0 mL), 1408C, 12 h.
Isolated yields reported.
2 (0.75 mmol),
[b]
[Rh(COD)2]OTf as the catalyst, subsequent optimiza- aryl-substituted acrylic acids could furnish the desired
tion revealed that toluene was the optimal choice, E-configurated products (3at and 3au) in excellent
and reduced yields were obtained in other solvents, yields. More than 90% yields and excellent E stereo-
such as PhCl, para-xylene, anisole, DMF and DMSO selectivity (3av and 3aw) were also observed in the re-
(Table 1, entries 16–20). The performance of other ad- actions of (E)-but-2-enoic acid (2v) and (E)-hex-2-
ditives was also evaluated, but they were all inferior enoic acid (2w). The b,b-disubstituted acrylic acids ex-
to (t-BuCO)2O (Table 1, entries 21–25). Lowering the hibited excellent reactivity, delivering the products
reaction temperature retarded the reaction as the 3ax and 3ay in 94% and 95% yields, respectively.
yield of 3aa dropped to 70% at 1208C (Table 1,
The reaction is not limited to b-substituted acrylic
entry 26). When the catalyst loading or the amount of acids only, and a-substituted acrylic acids also partici-
additive was reduced, the yield decreased as well pated well although a longer reaction time was re-
(Table 1, entries 27 and 28). The control experiments quired. As shown in Table 3, the a-substituted acrylic
showed that no reaction occurred in the absence of acids 4a–d successfully engaged in the coupling reac-
either [Rh(COD)2]OTf or (t-BuCO)2O (Table 1, en- tion, affording the corresponding E-configurated
tries 29 and 30). Thus the optimal reaction conditions products 5aa–5ad in good yields. The a,b-trisubstitut-
were finally determined as follows: [Rh(COD)2]OTf ed acrylic acids 4e–g reacted smoothly to give the de-
(5 mol%) and (t-BuCO)2O (1.5 equiv.) in toluene at sired products (5ae–5ag) in 85–92% yields with excel-
1408C for 12 h.
lent E stereoselectivity. Noteworthy is that the chal-
Having the optimized conditions in hand, we then lenging tetra-substituted acrylic acid 4h underwent
explored the vinylation of 1a with a range of electron- clean conversion to furnish 5ah in 92% yield.
ically and sterically diverse vinyl carboxylic acids. As
This cross-coupling reaction was further extended
shown in Table 2, cinnamic acids with a wide range of to other 2-arylpyridine derivatives as shown in
substituents on the benzene ring were effectively con- Table 4. Similar to arene 1a, 2-arylpyridines (1b–h)
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Table 4. Rh-catalyzed direct olefination of arenes with cin-
namic acid (2a).[a,b,c]
Scheme 2. Olefination of 2-(1H-pyrrol-1-yl)pyrimidine (1v)
with 2a and removal of the directing group.
the target products (6la–6na) in 88–93% yields. How-
ever, when 2-phenylpyridine (1o) was employed, a 2:1
mixture of mono- and diolefinated products was ob-
served. Using 2-arylpyridines bearing para-substitu-
ents on the aryl ring (1p–s), 1-phenyl-1H-pyrazole
(1t) and 2-(thiophen-3-yl)pyridine (1u) led to similar
results. To our delight, increasing the amount of 2a
and (t-BuCO)2O to 3.0 equivalents led to the exclu-
sive formation of diolefinated products (6oa–6ua) in
excellent yields. It is noteworthy that 2-(1H-pyrrol-1-
yl)pyrimidine (1v) was also effective in this reaction,
and the pyrimidyl group could be readily removed
(Scheme 2).[10] It should be noted that only the E-con-
figurated products were obtained in all cases studied.
Unexpectedly, in the case of using [Rh(1,5-HD)Cl]2
as the catalyst, the coupling reaction of 2-phenylpyri-
dine (1o) with 2a primarily provided the mono-olefi-
Table 5. Rh-catalyzed direct mono-olefination of arenes with
2a.[a,b]
[a]
Reaction conditions:
1 (0.5 mmol), 2a (0.75 mmol),
[Rh(COD)2]OTf (5.0 mol%), (t-BuCO)2O (0.75 mmol) in
3.0 mL toluene, 1408C, 12 h.
Isolated yields reported.
For arenes 1o–u, 3.0 equiv. of 2a and (t-BuCO)2O were
employed.
[b]
[c]
bearing meta- or ortho-substituents on the aryl ring
could efficiently couple with 2a to form the desired
ortho-alkenylated products (6ba–6ha). 2-(meta-Tolyl)-
quinoline (1i), benzo[h]quinoline (1j) and 1-(meta-
tolyl)-1H-pyrazole (1k) could also be smoothly olefi-
nated, and high isolated yields (6ia–6ka) were
achieved. Likewise, this protocol worked well for the
direct olefination of 1-arylisoquinolines (1l–n), giving
[a]
Reaction conditions:
[Rh(1,5-HD)Cl]2 (5.0 mol%), (t-BuCO)2O (0.6 mmol) in
3.0 mL toluene, 1408C, 24 h.
Isolated yields reported.
1
(0.5 mmol), 2a (0.6 mmol),
[b]
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Rhodium-Catalyzed Decarbonylative Direct Olefination of Arenes
3aa in high yields in 12 h (Scheme 4, a and b), but (t-
BuCO)2O was totally unreactive under otherwise
identical conditions (Scheme 4, c). These results clear-
ly indicated that the in situ generated anhydrides did
contribute to the formation of the olefinated product
3aa. This is consistent with the previous reports by
Yamamoto,[11] Goossen,[12] Ryu,[13] and Shi.[14] Analyz-
ing the gas phase of the reaction mixture with GC-
TCD confirmed the generation of CO during the re-
action, clearly suggesting that a decarbonylation step
is involved in the current transformation.
To explore the stereochemistry of this transforma-
tion, we next investigated the coupling reaction of 1a
with cis-cinnamic acid (2a’) and cis-crontonic acid
(2v’). To our surprise, only the E-configurated prod-
ucts were obtained (Scheme 5). It is likely that a cis-
Scheme 3. Reaction of (E)-2-(2-styrylphenyl)pyridine (8oa)
with (E)-3-(4-bromophenyl)acrylic acid (2i).
nation product 8oa, and the diolefinated product 6oa trans isomerization of the olefin took place in the
was only isolated in 11% yield. Encouraged by this course of the reaction. In an effort to elucidate this
finding, we then examined the mono-olefination of process, we carried out experiments with 2a’ moni-
other arenes (1p–u), and satisfactory results (8pa–
8ua) were achieved (Table 5). As exemplified in
Scheme 3, the mono-olefinated arylpyridine 8oa could
be further olefinated with 2i to afford the diolefinated
product 9.
In order to obtain mechanistic insights, a mixture of
equimolar amounts of 2a and (t-BuCO)2O in toluene
was stirred at 1408C for 1 h, and subsequent analysis
by 1H NMR revealed the existence of three anhy-
drides, trans-cinnamic pivalic anhydride 10, trans-cin-
namic anhydride 11 and (t-BuCO)2O, in a ratio of
1:0.36:0.83. After overnight stirring, the ratio became
1:0.45:0.41 with the mixed anhydride 10 present in the
largest amount. We then examined the coupling reac-
tion of these anhydrides with 1a under the catalysis of
[Rh(COD)2]OTf. Both anhydrides 10 and 11 were
smoothly coupled to exclusively provide the product (2a’)and cis-crotonic acid (2v’).
Scheme 5. Direct olefination of 1a with cis-cinnamic acid
Scheme 4. The coupling reaction of anhydrides with 1a.
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for 3 h afforded a 6:1 mixture of trans-product 3aa
and cis-product 3aa’, which could be totally converted
to the trans isomer in 2 h in the presence of the
[Rh(COD)2]OTf catalyst (Scheme 6, d). Based on
these results, it is clear that this olefination is stereo-
specific, and the Rh(I)-catalyzed cis-trans isomeriza-
tion of olefins should be responsible for the stereo-
chemistry observed.
On the basis of the above studies, a plausible mech-
anism is suggested (Scheme 7). First, the arylpyridine
1 reacted with the rhodium(I) species to give the cy-
clorhodium intermediate A via the pyridyl nitrogen-
À
assisted C H activation. The anhydrides B and C de-
rived from the reaction of vinyl carboxylic acid and
(t-BuCO)2O underwent reaction with A to selectively
deliver the intermediates D and E, which produced
the intermediates F and G through the loss of CO.
With treatment of HOTf, intermediates H and I were
generated with the release of carboxylic acids. The
following reductive elimination of H and I liberated
the desired product 3. Finally, the rhodium(I) was re-
formed to finish the catalytic cycle. In the case of cis
Scheme 6. Rh(I)-catalyzed cis-trans isomerization of olefins.
tored by NMR, and three important pieces of infor- vinyl carboxylic acid, the Rh(I)-catalyzed cis-trans iso-
mation were obtained: (a) 2a’ was in situ activated by merization was involved to convert the in situ gener-
(t-BuCO)2O to generate cis-cinnamic pivalic ated cis anhydrides and the cis olefination product to
anhydride 12 and cis-cinnamic anhydride 13, and their trans isomers.
[Rh(COD)2]OTf could efficiently catalyze the isomer-
ization of 12 and 13 to their trans analogues 10 and 11
in 3 h (Scheme 6, a, b), but no isomerization could be Conclusions
detected in the absence of [Rh(COD)2]OTf catalyst;
(b) 2a’ could not be isomerized under the catalysis of In summary, a protocol for the direct olefination of
[Rh(COD)2]OTf even after overnight stirring arylpyridines employing vinyl carboxylic acids as the
(Scheme 6, c); (c) because the catalytic isomerization vinyl sources has been developed, providing a general
of cis-anhydrides was not very rapid, it is possible that and convenient way to access various olefinated
the cis-anhydride might react with 1a to give the cis- arenes. A range of functional groups survived this
product; indeed, the coupling reaction of 2a’ with 1a new transformation, and differently substituted vinyl
Scheme 7. Proposed mechanism for the decarbonylative direct olefination of arylpyridines.
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Rhodium-Catalyzed Decarbonylative Direct Olefination of Arenes
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À
ing direct C H olefination of arenes known in the lit-
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Ackermann, L. Wang, R. Wolfram, A. V. Lygin, Org.
Lett. 2012, 14, 728; f) B. Li, J. Ma, N. Wang, H. Feng, S.
Xu, b. Wang, Org. Lett. 2012, 14, 736; g) K. Padala, M.
Jeganmohan, Org. Lett. 2012, 14, 1134; h) K. Graczyk,
W. Ma, L. Ackermann, Org. Lett. 2012, 14, 4006; i) V.
Lanke, K. R. Prabhu, Org. Lett. 2013, 15, 2818; j) V.
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General Methods
Unless otherwise noted, all experiments were carried out
under a nitrogen atmosphere. H NMR and 13C NMR spec-
1
tra were recorded on a Bruker Model Avance DMX 400
Spectrometer (1H 400 MHz and 13C 106 MHz, respectively).
Chemical shifts (d) are given in ppm and are referenced to
residual solvent peaks, and coupling constants (J) are re-
ported in Hertz. The commercially available chemicals were
used as received without further purification.
General Procedure for Decarbonylative Direct
Olefination of Arenes with Vinyl Carboxylic Acids
To an oven-dried pressure tube were sequentially ad
ACHTUNGTRNEdNUNG ed the
arene (0.5 mmol), acrylic acid (0.75 mmol),
1
2
[Rh(COD)2]OTf (11.7 mg, 5 mol%), (t-BuCO)2O (139.5 mg,
0.75 mmol) and toluene (3.0 mL). After being degassed
three times, the tube was heated and stirred vigorously at
1408C for 12 h in an oil bath under a nitrogen atmosphere.
Then the tube was removed from the oil bath and cooled to
room temperature. The solvent was removed by vacuum
evaporation, and the residue was purified by column chro-
matography on silica gel using a mixture of ethyl acetate
and hexane to give the pure product.
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (21372258, 21072225, 21172258 and 91127039)
is greatly acknowledged.
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asc.wiley-vch.de
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Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

FULL PAPERS
Rhodium-Catalyzed Decarbonylative Direct Olefination of
Arenes with Vinyl Carboxylic Acids
9
Adv. Synth. Catal. 2015, 357, 1 – 9
Ruiying Qiu, Lingjuan Zhang, Conghui Xu, Yixiao Pan,
Hongze Pang, Lijin Xu,* Huanrong Li*
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
ÞÞ
These are not the final page numbers!