Ruthenium(II)-Catalyzed Oxidant-Free C–H Olefination of Aromatic Carboxamides with Allyl Acetate

Article abstract of DOI:10.1002/adsc.201600569

An inexpensive ruthenium-catalyzed direct C–H olefination of aromatic carboxamides with allyl acetate was developed. This external oxidant-free protocol provided an efficient route for the synthesis of useful trans-styrene derivatives in high to excellent yields. The olefination reaction exhibited excellent regioselectivities and allowed the presence of a wide range of functional groups, such as OMe, F, Cl, Br, I, CF₃, NMe₂, as well as NO₂. (Figure presented.).

Full text of DOI:10.1002/adsc.201600569

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DOI: 10.1002/adsc.201600569
Ruthenium(II)-Catalyzed Oxidant-Free C–H Olefination of
Aromatic Carboxamides with Allyl Acetate
Feifei Li,+a Cong Shen,+a Jian Zhang,a,* Ling Wu,a Xupeng Zhuo,a Liyuan Ding,a
and Guofu Zhonga,*
a
College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, No. 16 Xuelin Street,
Hangzhou 310036, Peopleꢀs Republic of China
E-mail: zhangjian@hznu.edu.cn or zgf@hznu.edu.cn
+
F. L. and C. S. contributed equally to this work.
Received: May 31, 2016; Revised: September 11, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600569.
Abstract: An inexpensive ruthenium-catalyzed
direct C–H olefination of aromatic carboxamides
with allyl acetate was developed. This external oxi-
dant-free protocol provided an efficient route for
the synthesis of useful trans-styrene derivatives in
high to excellent yields. The olefination reaction ex-
hibited excellent regioselectivities and allowed the
presence of a wide range of functional groups, such
as OMe, F, Cl, Br, I, CF3, NMe2, as well as NO2.
the development of even more efficient reactions with
new patterns of coupling partners in the absence of
external oxidant is still highly desirable.
Allyl derivatives such as allyl acetate, allylic car-
bonate, allyl alcohol, and allyl phosphate have proved
to be efficient allylation reagents.[6] To date, some re-
search groups, such as those of Glorius,[6a,b] Loh,[6c]
Miura,[6d] Kim,[6e] Jeganmohan,[6f] Inoue,[6g] Kanai,[6h]
You,[6i] Sawamura,[6j] and Zhang,[6k,l] have already re-
ported direct allylations of aromatic and vinylic C–H
bonds with allyl derivatives using Rh, Ru or Co com-
plexes. There are also reports on transition metal-cat-
alyzed allyation reactions with allenes and vinylcyclo-
propanes.[7] Recently, Wang and co-workers reported
a unique alkylation of azobenzenes with allyl acetates
by Rh-catalyzed C–H activation.[8] However, double
Keywords: allyl acetate; cross-coupling; olefination;
ruthenium; styrenes
The styrene moiety represents an exceptionally useful bond migration was usually inevitable and was difficult
functional group, offering numerous applications in to control. Furthermore, the reactions often suffered
synthetic and polymer chemistry.[1,2] In this context, from poor regioselectivities and/or limited substrate
numerous aromatic C–H olefination reactions cata- scopes. These reported results promoted us to explore
lyzed by different transition metals have been report- novel external oxidant-free olefination reactions.
ed as they minimize waste formation and obviate pre-
More recently, inexpensive ruthenium catalysts
functionalization steps.[3] The introduction of ortho-di- such as [RuCl2(p-cymene)]2[9] have been demonstrated
recting groups (DGs) to aromatic rings has efficiently to be efficient for C–H bond functionalizations, espe-
improved the regioselectivities of the olefination reac- cially alkenylations.[10] During our studies on C–H ole-
tions. Alkenylation reactions assisted by remote di- fination chemistry,[11] we developed a ruthenium-cata-
recting groups such as ester, acid, and amine also lyzed olefination of aromatic amides with allyl acetate
have been reported, providing the corresponding sty- without an external oxidant.
rene derivatives in high efficiency.[4] Despite these sig-
At the outset, the reaction of N,N-dimethyl-4-ethyl-
nificant recent advances, the reactions are largely lim- benzamide 1g and allyl acetate 2a was chosen to
ited to alkenes and metal oxidants are commonly re- screen the catalytic conditions, using [RuCl2(p-
quired to regenerate the active catalytic intermediates cymene)]2 as the catalyst (Table 1). Commercially
which produce stoichiometric amounts of toxic heavy available AgSbF6 salt was used as an additive as it
metal waste. Recently, molecular oxygen is emerging may abstract chloride to generate a cationic rutheni-
as an ideal oxidant and the Ackermann group has re- um complex which can mediate electrophilic C–H ac-
ported a novel ruthenium(II)-catalyzed oxidative al- tivation.[10]
kenylation reaction using ambient oxygen as the sole
Firstly, we screened a series of representative sol-
oxidant under mild reaction conditions.[5] However, vents. The olefination reaction afforded no desired
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Table 1. Optimization of the catalytic conditions.[a]
tries 8–11). Moreover, the reaction led to no product
in the absence of AgSbF6 regardless of whether
HOAc was added or not (Table 1, entries 12 and 13).
Also, the reaction remained sluggish in the absence of
the [RuCl2(p-cymene)]2 complex (Table 1, entry 14).
A simple ruthenium salts such as RuCl3 was tested,
but it exhibited no catalytic activity (Table 1,
entry 15). Interestingly, styrene could also be obtained
in good yield if the reaction was performed under an
air atmosphere (Table 1, entry 16).
With the optimized catalytic conditions in hand, we
turned to explore the scope of the Ru-catalyzed olefi-
nation by employing differently substituted benza-
mides 1 (Table 2). Benzamides bearing different alkyl
groups on the nitrogen atom were screened and all of
them reacted smoothly, and the styrene derivatives
were formed in good to excellent yields (3a–e).[12a] To
our delight, this simple protocol also exhibited
a broad spectrum of functional group compatibility
regardless of their electron-donating or electron-with-
drawing properties, forming the desired styrene prod-
ucts 3 in good to excellent yields. It is worthy of note
that valuable functional groups such as nitro (3i), me-
thoxy (3j and 3k), dimethylamino (3l), trifluoromethyl
(3m), iodo (3n), bromo (3o), chloro (3p), and fluoro
(3q and 3r) were well tolerated. It should be men-
tioned that when meta-substituted benzamides were
used, excellent site selectivities were observed, deliv-
ering solely the C-6 olefination products, likely due to
steric interactions (3i and 3m). In contrast, in the case
of meta-fluoro-substituted benzamide, the reaction
mainly delivered the C-2 olefination product 3r,[10k–l]
and the regioisomeric ratio decreased to 85:15.[12b]
To gain a better understanding of the protocol,
other allyl sources such as allyl carbonates (2b and
2c) were also tested, but they showed poor reactivities
(Scheme 1a). If allyl methacrylate (2f) with two ter-
minal alkene moieties was applied, the alkenylation
still proceeded via allyl carboxylate, and the desired
product 3g was obtained in 78% yield (Scheme 1b).
Next, we screened some representative substituted
acetate derivatives. Due to the steric hinderance of
Entry Catalyst
Additive Solvent Yield [%]
1
2
[RuCl2(p-cymene)]2 AgSbF6 CH3CN
[RuCl2(p-cymene)]2 AgSbF6 DMF
0
0
3
[RuCl2(p-cymene)]2 AgSbF6 toluene 18 (91:9)
4
5
6
7
[RuCl2(p-cymene)]2 AgSbF6 EtOH
[RuCl2(p-cymene)]2 AgSbF6 THF
[RuCl2(p-cymene)]2 AgSbF6 DME
[RuCl2(p-cymene)]2 AgSbF6 DCE
[RuCl2(p-cymene)]2 AgSbF6 DCE
[RuCl2(p-cymene)]2 AgSbF6 DCE
[RuCl2(p-cymene)]2 AgSbF6 DCE
[RuCl2(p-cymene)]2 AgSbF6 DCE
9 (85:15)
45 (93:7)
57 (86:14)
82 (–)
71 (78:22)
87 (69:31)
70 (91:9)
0
8[b]
9[c]
10[d]
11[e]
12
13
14
15
16[f]
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2 HOAc
–
–
DCE
DCE
0
0
AgSbF6 DCE
AgSbF6 DCE
0
0
RuCl3
[RuCl2(p-cymene)]2 AgSbF6 DCE
69 (–)
[a]
Reaction conditions unless otherwise specified: 1a
(0.2 mmol, 1.0 equiv.), 2a (0.3 mmol, 1.5 equiv.), [Ru]
(5.0 mol%), and an additive (20 mol%) in a specific sol-
vent (1 mL), at 1108C, under argon, 18 h. The yields indi-
cated in the Table are isolated yields of 3g and 4g. Re-
gioisomeric ratios of 3g/4g described in brackets were de-
termined by H NMR if 4g was observed.
Cu(OAc)2 (50 mol%) was added.
HOAc (1.0 equiv.) was added.
H2O (1.0 equiv.) was added.
1
[b]
[c]
[d]
[e]
[f]
K2CO3 (1.0 equiv.) was added.
The reaction was performed under air. DCE=1,2-di-
chloroethane; DME=1,2-dimethoxyethane; DMF=N,N-
dimethylformamide.
product using DMF or CH3CN as the solvent the phenyl or methyl group, neither cinnamyl acetate
(Table 1, entries 1 and 2). Application of ethanol or (2g) nor 2-methylallyl acetate (2h) showed reactivity
toluene as the solvent led to very low yields (Table 1, toward benzamide even at elevated temperatures
entries 3 and 4). However, DME and THF were dem- (Scheme 1c and d). In contrast, allyl acetate 2i with-
onstrated to be more efficient for the olefination, de- out any substituent on the alkene moiety showed
livering allylation product 4g in low yields (Table 1, good reactivity, forming a mixture of alkenylation and
entries 5 and 6). It is worth noting that the desired allylation products (3s/4s=10:7) in 71% total yield
styrene was obtained in 82% yield when the reaction (Scheme 1e).
was performed in 1,2-dichloroethane (DCE) at 1108C
Intermolecular competition experiments between
under an argon atmosphere, and no allylation product differently decorated benzamides 1q and 1g exhibited
4g was observed (Table 1, entry 7).[6] Next, reactions the electron-rich substrate to preferentially react,
with different additives were investigated. While addi- which revealed an electrophilic C–H activation mani-
tion of Cu(OAc)2 or AcOH favoured the allylation fold (Scheme 2).[10,13]
process more than water, addition of a base such as
To obtain some mechanistic insights, we performed
K2CO3 totally retarded the reaction (Table 1, en- isotopic labelling experiments (Scheme 3). When
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Table 2. Olefination of benzamides with allyl acetate by
ruthenium catalysis.[a]
Scheme 1. Scope of allyl acetate derivatives.
[a]
The reactions were carried out as follows: amide
1 (0.2 mmol), allyl acetate 2a (0.3 mmol), [RuCl2(p-
cymene)]2 (2.5 mol%), AgSbF6 (20 mol%), in DCE
(1 mL) at 1108C, 16–18 h.
[b]
The yields indicated in the Table are isolated yields. Re-
gioisomeric ratios between internal and terminal olefins
1
in brackets were determined by H NMR analysis.
Scheme 2. Intermolecular competition experiment with
benzACTHUNRTGNEUNGamides 1q and 1g.
amide 1g was treated under the standard conditions
in the presence of D2O (10.0 equiv,), no deuterium in-
corporation to 1g was observed. Interestingly, treat- competition reactions of 1a and deuterio-1a-d5 with
ment of 1g under the standard conditions in the pres- allyl acetate were performed under the standard reac-
ence of AcOH (5.0 equiv.) and D2O (10.0 equiv.) for tion conditions for 10 min., which led to a kinetic iso-
6 h provided the ortho-selective deuterium product tope effect (kH/kD) of 2.0, thus suggesting that the aro-
1g-d in 98% yield (Scheme 3a). This clearly indicated matic C–H bond cleavage is probably involved in the
a carboxylate-assisted and reversible C–H bond met- rate-limiting step (Scheme 3c). Moreover, this reac-
allation step on the aromatic ring by the help of the tion provided mainly allylation products (3a/4a=
cationic ruthenium(II) complex.[10,13] The reaction of 1:10), indicating that styrene was generated from the
1g and 2a conducted in mixed DCE/D2O revealed allylation product by double bond migratory isomeri-
a significant H/D scrambling of protons in the prod- zation.
uct, indicating amide-directed sp2 C–H metallation
and isomerization steps (Scheme 3b). Furthermore, 4e was obtained according to a reported method[6e]
To further confirm our hypothesis, allylated product
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Scheme 4. Formation of 3e from 4e by double bond migrato-
ry isomerization.
On the basis of these mechanistic studies and previ-
ous reports,[6,10,13] we propose the possible mechanism
(Scheme 5). Firstly, an active cationic ruthenium com-
plexe I was generated from [RuCl2(p-cymene)]2 and
the silver salt. Then, an acetic acid-assisted reversible
C–H bond activation occurred by an electrophilic-
type cycloruthenation, forming complex II.[10,13] Subse-
quent coordination and migratory insertion of alkene
2 delivered a seven-membered Ru(II) species IV. As
coordination of the amide group may prevent syn b-
hydride elimination of the benzylic hydrogen atom by
conformational restriction,[6a–b,14] the following b-
oxygen elimination[15] should be facile to produce the
allylation product 4 and regenerate the active Ru(II)
complex I. The final styrene 3 of the thermodynami-
cally more stable product was formed via migratory
isomerization of the double bond with the help of the
active [Ru] species.
Scheme 3. Isotopic labelling experiment.
and was subjected to the standard conditions. After
In summary, we have disclosed an inexpensive Ru-
16 hours, styrene 3e was obtained in good yield as catalyzed protocol for the direct olefination of benza-
a regioisomeric mixture (3e/4e=89:11), clearly indi- mides with allyl acetate, delivering useful trans-sty-
cating a double bond migration event under the cata- rene derivatives in high to excellent yields without
lytic conditions (Scheme 4).
any oxidant. This external oxidant-free and acetic
Scheme 5. Proposed catalytic cycle for the olefination.
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[4] a) Y. Deng, J.-Q. Yu, Angew. Chem. 2015, 127, 902;
Angew. Chem. Int. Ed. 2015, 54, 888; b) R. Tang, G. Li,
J.-Q. Yu, Nature 2014, 507, 215; c) G.-J. Cheng, Y.-F.
Yang, P. Liu, P. Chen, T.-Y. Sun, G. Li, X. Zhang, K. N.
Houk, J.-Q. Yu, Y.-D. Wu, J. Am. Chem. Soc. 2014, 136,
894; d) L. Wan, N. Dastbaravardeh, G. Li, J.-Q. Yu, J.
Am. Chem. Soc. 2013, 135, 18056.
[5] A. Bechtoldt, C. Tirler, K. Raghuvanshi, S. Warratz, C.
Kornhaaß, L. Ackermann, Angew. Chem. 2016, 128,
272; Angew. Chem. Int. Ed. 2016, 55, 264.
acid-assisted transformation also shows excellent re-
gioselectivity and broad functional group compatibili-
ty, thus, it should have broad potential applications in
organic synthesis.
Experimental Section
General Procedure for Ru-Catalyzed C–H
Olefination of Aromatic Carboxamides
[6] a) H. Wang, N. SchrÅder, F. Glorius, Angew. Chem.
2013, 125, 5495; Angew. Chem. Int. Ed. 2013, 52, 5386;
b) T. Gensch, S. Vꢃsquez-Cꢄspedes, D.-G. Yu, F. Glo-
rius, Org. Lett. 2015, 17, 3714; c) C. Feng, D. Feng, T.-P.
Loh, Chem. Commun. 2015, 51, 342; d) T. Yao, K.
Hirano, T. Satoh, M. Miura, Angew. Chem. 2011, 123,
3046; Angew. Chem. Int. Ed. 2011, 50, 2990; e) M. Kim,
S. Sharma, N. K. Mishra, S. Han, J. Park, M. Kim, Y.
Shin, J. H. Kwak, S. H. Han, I. S. Kim, Chem.
Commun. 2014, 50, 11303; f) R. Manikandan, P. Madas-
amy, M. Jeganmohan, Chem. Eur. J. 2015, 21, 1; g) S.
Oi, Y. Tanaka, Y. Inoue, Organometallics 2006, 25,
4773; h) Y. Suzuki, B. Sun, K. Sakata, T. Yoshino, S.
Matsunaga, M. Kanai, Angew. Chem. 2015, 127, 10082;
Angew. Chem. Int. Ed. 2015, 54, 9944; i) C.-X. Zhuo, Y.
Zhou, S.-L. You, J. Am. Chem. Soc. 2014, 136, 6590;
j) Y. Makida, H. Ohmiya, M. Sawamura, Angew. Chem.
2012, 124, 4198; Angew. Chem. Int. Ed. 2012, 51, 4122;
k) S. Fan, F. Chen, X. Zhang, Angew. Chem. 2011, 123,
6040; Angew. Chem. Int. Ed. 2011, 50, 5918; l) Y. B. Yu,
S. Fan, X. Zhang, Chem. Eur. J. 2012, 18, 14643; m) Y.
Zhang, Z. Li, Z.-Q. Liu, Org. Lett. 2012, 14, 226;
n) G. S. Kumar, M. Kapur, Org. Lett. 2016, 18, 1112;
o) Y. Bunno, N. Murakami, Y. Suzuki, M. Kanai, T.
Yoshino, S. Matsunaga, Org. Lett. 2016, 18, 2216; p) W.
Liu, S. C. Richter, Y. Zhang, L. Ackermann, Angew.
Chem. 2016, 128, 7878; Angew. Chem. Int. Ed. 2016, 55,
7747; q) H. Dai, C. Yu, C. Lu, H. Yan, Eur. J. Org.
Chem. 2016, 1255; r) M. Moselage, N. Sauermann, J.
Koeller, W. Liu, D. Gelman, L. Ackermann, Synlett
2015, 1596.
[7] a) J.-Q. Wu, Z.-P. Qiu, S.-S. Zhang, J.-G. Liu, Y.-X. Lao,
L.-Q. Gu, Z.-S. Huang, J. Li, H. Wang, Chem.
Commun. 2015, 51, 77; b) S. Nakanowatari, L. Acker-
mann, Chem. Eur. J. 2015, 21, 16246.
[8] H. Deng, H. Li, L. Wang, Org. Lett. 2015, 17, 2450.
[9] [Cp*RhCl2]2: 7476 CNY/g versus [RuCl2(p-cymene)]2:
758 CNY/g (Sigma–Aldrich, 2015).
[10] For recent reviews on ruthenium-catalyzed C–H bond
functionalizations, see: a) S. I. Kozhushkov, L. Acker-
mann, Chem. Sci. 2013, 4, 886; b) B. Li, P. H. Dixneuf,
Chem. Soc. Rev. 2013, 42, 5744; c) P. B. Arockiam, C.
Bruneau, P. H. Dixneuf, Chem. Rev. 2012, 112, 5879;
d) L. Ackermann, R. Vicente, Top. Curr. Chem. 2010,
292, 211; e) S. J. Blanksby, G. B. Ellison, Acc. Chem.
Res. 2003, 36, 255; f) L. Ackermann, Chem. Rev. 2011,
111, 1315; g) C. Liu, J. Yuan, M. Gao, S. Tang, W. Li,
R. Shi, A. Lei, Chem. Rev. 2015, 115, 12138; h) V. P.
Boyarskiy, D. S. Ryabukhin, N. A. Bokach, A. V. Vasi-
lyev, Chem. Rev. 2016, 116, 5894; i) X. Xue, J. Xu, L.
Zhang, C. Xu, Y. Pan, L. Xu, H. Li, W. Zhang, Adv.
Synth. Catal. 2016, 358, 573; j) Y. Ogiwara, M. Tamura,
An oven-dried, screw-cap vial was charged with [RuCl2(p-
cymene)]2 (0.005 mmol, 2.5 mol%), AgSbF6 (0.04 mmol,
20 mol%) and DCE (1 mL). Then, benzamide (1.0 equiv.,
0.20 mmol) and allyl acetate (1.5 equiv., 0.30 mmol) were
added into the solution in sequence. The vial was sealed
under argon and heated to 1108C with stirring for 18 hours.
After cooling down, the mixture was diluted with DCM, fil-
tered and washed with water and brine. The organic layer
was dried, filtered and concentrated to give the crude prod-
uct which was directly applied to a flash column chromatog-
raphy (EtOAc/hexanes mixtures).
Acknowledgements
We gratefully acknowledge Hangzhou Normal University, the
National Natural Science Foundation of China (NSFC) (Nos.
21502037 and 21373073), the Natural Science Foundation of
Zhejiang Province (ZJNSF) (No. LY15B020008), and the
PCSIRT (No. IRT 1231) for financial support. G. Z. ac-
knowledges a Qianjiang Scholar award from Zhejiang Prov-
ince, China.
References
[1] a) B. S. Lane, K. Burgess, Chem. Rev. 2003, 103, 2457;
b) Q. H. Xia, H. Q. Ge, C. P. Ye, Z. M. Liu, K. X. Su,
Chem. Rev. 2005, 105, 1603; c) A. B. Dounay, L. E.
Overman, Chem. Rev. 2003, 103, 2945; d) M. Shibasaki,
E. M. Vogl, T. Ohshima, Adv. Synth. Catal. 2004, 346,
1533.
[2] a) F. Agbossou, J.-F. Carpentier, A. Mortreux, Chem.
Rev. 1995, 95, 2485; b) A. Hirao, S. Loykulnant, T. Ishi-
zone, Prog. Polym. Sci. 2002, 27, 1399; c) J. Schellen-
berg, N. Tomotsu, Prog. Polym. Sci. 2002, 27, 1925;
d) J. Scheirs, D. B. Priddy, Modern Styrenic Polymers:
Polystyrenes and Styrenic Copolymers, John Wiley &
Sons, Chichester, U.K., 2003.
[3] a) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew.
Chem. 2009, 121, 5196; Angew. Chem. Int. Ed. 2009, 48,
5094; b) T. Satoh, M. Miura, Chem. Eur. J. 2010, 16,
11212; c) F. W. Patureau, J. Wencel-Delord, F. Glorius,
Aldrichimica Acta 2012, 45, 31; d) G. Song, F. Wang, X.
Li, Chem. Soc. Rev. 2012, 41, 3651; e) L. R. Odell, J.
Sꢂvmarker, J. Lindh, P. Nilsson, M. Larhed, in: Com-
prehensive Organic Synthesis, 2nd edn., (Eds.: G. A. Mo-
lander, P. Knochel), Elsevier, Oxford, 2014, Vol. 7,
p 492.
Adv. Synth. Catal. 0000, 000, 0 – 0
5
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
T. Kochi, Y. Matsuura, N. Chatani, F. Kakiuchi, Orga-
nometallics 2014, 33, 402; k) L. Ackermann, L. Wang,
R. Wolfram, A. V. Lygin, Org. Lett. 2012, 14, 728; l) K.
Graczyk, W. Ma, L. Ackermann, Org. Lett. 2012, 14,
4110.
[13] a) V. S. Thirunavukkarasu, K. Raghuvanshi, L. Acker-
mann, Org. Lett. 2013, 15, 3286; b) F. Yang, L. Acker-
mann, Org. Lett. 2013, 15, 718; c) J. Li, M. John, L. Ac-
kermann, Chem. Eur. J. 2014, 20, 5403; d) L. Acker-
mann, L. Wang, R. Wolfram, A. V. Lygin, Org. Lett.
2012, 14, 728; e) S. I. Kozhushkov, L. Ackermann,
Chem. Sci. 2013, 4, 886.
[11] The Loh group reported a Rh(III)-catalyzed direct C–
H olefination of arenes with allyl acetates: C. Feng, D.
Feng, T.-P. Loh, Org. Lett. 2013, 15, 3670.
[14] D.-H. Wang, K.-M. Engle, B.-F. Shi, J.-Q. Yu, Science
[12] a) Some other amides such as primary amides and
Weinreb amide were also tested, but no desired prod-
uct was detected. b) In most of the cases described in
Table 2, nearly no allylated product was observed.
However, cis-styrenes were usually observed in trace
2010, 327, 315.
[15] a) Q. Zhang, X. Lu, X. Han, J. Org. Chem. 2001, 66,
7676; b) H. Ohmiya, Y. Makida, D. Li, M. Tanabe, M.
Sawamura, J. Am. Chem. Soc. 2008, 130, 17276; c) N.
Sakiyama, K. Noguchi, K. Tanaka, Angew. Chem. 2012,
124, 6078; Angew. Chem. Int. Ed. 2012, 51, 5976.
1
amounts by H NMR.
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Ruthenium(II)-Catalyzed Oxidant-Free C–H Olefination of
Aromatic Carboxamides with Allyl Acetate
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Feifei Li, Cong Shen, Jian Zhang,* Ling Wu, Xupeng Zhuo,
Liyuan Ding, Guofu Zhong*
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