Rhodium-catalyzed ortho-C-H olefination of aromatic aldehydes employing transient directing strategy

Article abstract of DOI:10.1002/aoc.4039

A Rhodium(III)-catalyzed ortho-C-H olefination of aromatic aldehydes in the presence of catalytic amount of TsNH₂ has been developed. The in situ generated imine intermediate from aldehyde and TsNH₂ worked as a transient directing gr

Full text of DOI:10.1002/aoc.4039

Received: 10 June 2017
DOI: 10.1002/aoc.4039
Revised: 19 July 2017
Accepted: 21 July 2017
F U L L P A P E R
Rhodium‐catalyzed ortho‐C‐H olefination of aromatic
aldehydes employing transient directing strategy
Xi Liu | Zhonghao Wang | Qun Chen | Ming‐yang He | Liang Wang
School of Petrochemical Engineering and
A Rhodium(III)‐catalyzed ortho‐C‐H olefination of aromatic aldehydes in the
Jiangsu Key Laboratory of Advanced
Catalytic Materials & Technology,
presence of catalytic amount of TsNH2 has been developed. The in situ gener-
Changzhou University, Changzhou
ated imine intermediate from aldehyde and TsNH2 worked as a transient
213164, P. R. China
directing group. Both electron‐rich and electron‐deficient aromatic aldehydes
Correspondence
Ming‐yang He and Liang Wang, School of
Petrochemical Engineering and Jiangsu
were tolerated, affording the corresponding products in moderate to good
yields. Importantly, the present protocol provides a straightforward access to
Key Laboratory of Advanced Catalytic
Materials & Technology, Changzhou
University, Changzhou, 213164, P. R.
China.
olefinated aromatic aldehydes with aldehydes as the simple starting materials.
KEYWORDS
aryl aldehydes, C‐H activation, olefination, transient directing groups
Email: hemingyangjpu@yahoo.com;
liangwang@cczu.edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21302014;
Jiangsu Key Laboratory of Advanced Cat-
alytic Materials and Technology, Grant/
Award Number: BM2012110; the Priority
Academic Program Development (PAPD)
of Jiangsu Higher Education Institutions
1 | INTRODUCTION
amount of DG would be necessary since it would dissociate
from the product after reaction. Moreover, the synthetic
Over the past decades, transition metal‐catalyzed C‐H
activation has emerged as a powerful and atom‐economic
strategy to convert inert C‐H bonds into diverse C‐C and
C‐heteroatom bonds.[1] Particularly, the reactivity of C‐H
bonds as well as the regioselectivity can be significantly
promoted with the assistance of well‐defined directing
groups (DGs).[2] Despite the great progress in this field,
this approach still has some limitations. Generally, addi-
tional steps are required for installation and removal of
the DGs. Sometimes, these reaction conditions are harsh,
thereby diminishing the efficiency and compatibility of
the reactions.
value would be further increased if the DG is readily avail-
able and cost‐effective. Since the pioneering work reported
by Jun and co‐workers on Rh‐catalyzed functionalization
of aldehydes using 2‐aminopyridine as the transient
DG,[3] significant advance has been achieved in transient
directing groups (TDG)‐assisted C‐H activations in recent
years. For example, amino acids,[4–7] acetohydrazide,[8]
and 3,5‐bis(trifluoromethyl)aniline[9] were successfully
employed as TDGs for direct C‐H functionalization of
aromatic or aliphatic aldehydes. Glyoxylic acid,[10] 8‐
formylquinoline,[11] 2‐hydroxynicotinaldehyde,[12] and
3,5‐ditert‐butylsalicylaldehyde[13] were also found to be
effective in β‐C(sp3) − H arylation of aliphatic amines.
Encouraged by the aforementioned success in this field,
An ideal solution is introduction of a transient DG that
binds reversibly to the substrate. In this case, only catalytic
Appl Organometal Chem. 2017;e4039.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4039

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LIU ET AL.
we recently focused on the direct C‐H olefination, namely
the Fujiwara − Moritani reaction.[14] Although this kind of
reaction has been widely reported with the assistance of
diverse DGs,[15] the direct C‐H olefination of aryl alde-
hydes still remains a big challenge, which was mainly
attributed to the low ligating ability of the aldehyde oxygen
as well as the instability of the aldehyde group. To the best
of our knowledge, reports on direct C‐H olefination of aryl
aldehydes are still rare. In 2012, Jeganmohan and co‐
workers[16] reported a ruthenium(II)‐catalyzed direct C‐H
olefination of aryl aldehydes. However, the reaction scope
was limited and the yields were unsatisfactory. Later, Li
and co‐workers[17] reported a rhodium(III)‐catalyzed the
synthesis of ortho‐olefinated benzaldehydes using N‐sulfo-
nyl imines as the starting materials. Inspired these contri-
butions, we envisioned that if aldimine intermediates
could be reversibly generated from the corresponding alde-
hydes and an elaborated TDG, then the in situ formed
aldimine group might serve as the efficient DG for C − H
bond activation. Herein, we report a Rhodium(III)‐cata-
lyzed ortho‐C‐H olefination of aromatic aldehydes in the
presence of catalytic amount of p‐toluenesulfonamide
(TsNH2) (Scheme 1).
0.4 equiv), [RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%),
Cu(OAc)2•H2O (0.4 mmol, 2 equiv) and 1,2‐dichloroeth-
ane (DCE) (2 ml). The mixture was kept stirring under
air at 100 °C for 16 h. After completion of the reaction,
the mixture was cooled to room temperature, concen-
trated in vacuum, and the residue was purified by flash
column chromatography on silica gel with petroleum
ether and ethyl acetate as eluent to give the pure desired
product.
2.3 | Characterization data for new
compounds
2.3.1 | Methyl (E)‐3‐(5‐chloro‐2‐
formylphenyl)acrylate (3e)
1H NMR (300 MHz, CDCl3) δ 10.22 (s, 1H), 8.43 (d,
J = 15.9 Hz, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.58 (d,
J = 1.9 Hz, 1H), 7.51 (dd, J = 8.3, 2.0 Hz, 1H), 6.37
(d,
J =
15.9 Hz, 1H), 3.82 (s, 3H). 13C NMR
(75 MHz, CDCl3) δ 190.4, 166.2, 140.4, 139.7, 138.0,
133.5, 132.0, 129.9, 127.9, 123.8, 52.0. HRMS (ESI):
Calcd for C11H9ClNaO3 [M + Na]+ 247.0132; Found:
247.0140.
2 | EXPERIMENTAL
2.1 | General remarks
2.3.2 | Methyl (E)‐3‐(5‐bromo‐2‐
formylphenyl)acrylate (3f)
All reagents were obtained from local commercial sup-
pliers and used without further purification. The progress
of the reaction was monitored by TLC using analytical‐
1H NMR (300 MHz, CDCl3) δ 10.21 (s, 1H), 8.42 (d,
J
= 15.9 Hz, 1H), 7.77–7.65 (m, 3H), 6.36 (d,
1
J = 15.9 Hz, 1H), 3.82 (s, 3H). 13C NMR (75 MHz, CDCl3)
δ 190.6, 166.2, 139.6, 138.1, 133.5, 132.9, 132.4, 130.9,
129.1, 123.8, 52.0. HRMS (ESI): Calcd for C11H9BrNaO3
[M + Na]+ 290.9627; Found: 290.9633.
grade silica gel plates (GF254) under UV light. H and
13C NMR were recorded at ambient temperature on a
Bruker 300 MHz NMR spectrometer using CDCl3 as sol-
vent and TMS as an internal reference. Chemical shifts
are given in parts per million (δ, ppm) and the coupling
constants J are given in Hz. Mass spectrometry was per-
formed on an LCMS‐2010 EV (Shimadzu) instrument
with an ESI source. High‐resolution mass spectrometry
(HRMS) was performed on a TOF MS instrument with
an ESI source.
2.3.3 | Methyl (E)‐3‐(2‐formyl‐5‐nitrophe-
nyl)acrylate (3 h)
1H NMR (300 MHz, CDCl3) δ 10.4 (s, 1H), 8.46 (dd,
J = 9.0, 6.9 Hz, 2H), 8.36 (dd, J = 8.4, 2.2 Hz, 1H), 8.08
(d, J = 8.5 Hz, 1H), 6.53 (d, J = 15.9 Hz, 1H), 3.85 (s,
3H). 13C NMR (75 MHz, CDCl3) δ189.9, 165.9, 150.5,
138.5, 138.1, 137.2, 132.9, 125.3, 124.1, 123.0, 52.2. HRMS
(ESI): Calcd for C11H9NNaO5 [M + Na]+ 258.0373;
Found: 258.0377.
2.2 | General procedure for mono‐
olefination of aryl aldehydes
A sealed tube was charged with aldehyde (0.2 mmol, 1
equiv), olefin (0.3 mmol, 1.5 equiv), TsNH2 (0.08 mmol,
SCHEME 1 Rhodium(III)‐catalyzed
ortho‐C‐H olefination of aromatic
aldehydes

LIU ET AL.
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J = 15.9 Hz, 1H), 3.81 (s, 3H). 13C NMR (75 MHz, CDCl3)
δ 191.4, 166.5, 142.7, 138.9, 138.2, 134.0, 131.5, 130.7,
127.1, 122.5, 51.9. HRMS (ESI): Calcd for C11H9ClNaO3
(M + Na)+ 247.0132, found 247.0140.
2.3.4 | Methyl (E)‐3‐(2‐formyl‐3‐
methylphenyl)acrylate (3 l)
1H NMR (300 MHz, CDCl3) δ 10.60 (s, 1H), 8.29 (d,
J = 15.8 Hz, 1H), 7.50–7.37 (m, 2H), 7.30–7.27 (m, 1H),
6.27 (d, J = 15.8 Hz, 1H), 3.82 (s, 3H), 2.65 (s, 3H). 13C
NMR (75 MHz, CDCl3) δ 192.6, 166.7, 143.3, 141.2,
137.4, 133.2, 133.0, 132.5, 126.5, 122.2 51.9, 20.0. HRMS
(ESI): Calcd for C12H12NaO3 (M + Na)+ 227.0679, found
227.0684.
2.3.6 | Methyl (E)‐3‐(2‐formyl‐4‐
methylphenyl)acrylate (3 l)
1H NMR (300 MHz, CDCl3) δ 10.26 (s, 1H), 8.50 (d,
J = 15.9 Hz, 1H), 7.67 (d, J = 1.1 Hz, 1H), 7.54 (d,
J = 7.9 Hz, 1H), 7.43–7.39 (m, 1H), 6.35 (d, J = 15.9 Hz,
1H), 3.81 (s, 3H), 2.44 (s, 3H). 13C NMR (75 MHz, CDCl3)
δ 192.0, 166.8, 141.0, 140.4, 134.7 (2C), 133.7, 132.8, 127.8,
121.8, 51.8, 21.1. HRMS (ESI): Calcd for C12H12NaO3
[M + Na]+ 227.0679; Found: 227.0686.
2.3.5 | Methyl (E)‐3‐(3‐chloro‐2‐
formylphenyl)acrylate (3j)
1H NMR (300 MHz, CDCl3) δ 10.63 (s, 1H), 8.26 (d,
J
= 15.9 Hz, 1H), 7.51–7.45 (m, 3H), 6.28 (d,
TABLE 1 Initial screening of reaction conditionsa
Entry
Catalyst
Additive
Oxidant
Solvent
Yield(%)b
1
‐
‐
Cu(OAc)2
DCE
n.r.
2
[RhCp*Cl2]2
Rh(OOCCF3)2
RhCl3
‐
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
‐
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DMF
DMSO
THF
7
3
‐
n.r.
4
‐
n.r.
5
[RuCl2(p‐Cymene)]2
Pd(OAc)2
‐
n.r.
6
‐
n.r.
7
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
AgSbF6
AgBF4
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
20
8
11
9
trace
trace
trace
trace
trace
trace
trace
37
10
11
12
13
14
15
16
17
18
19
20
21
22
dioxane
toluene
AcOH
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
Cu(OAc)2•H2O
Cu(OTf)2
AgOAc
29
trace
trace
trace
trace
36c, 24d, 21e
Ag2CO3
BQ
O2
Cu(OAc)2•H2O
aReaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), glycine (0.4 equiv), catalyst (5 mol%), additive (20 mol%), oxidant (0.4 mmol, 2 equiv), solvent (2 ml), 16 h.
bNMR yields using 1,1,2,2‐tetrachloroethane as internal standard.
cCatalyst (10 mol%) was used.
dCatalyst (2 mol%) was used.
eUnder N2.

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LIU ET AL.
2.3.7 | Methyl (E)‐3‐(4‐bromo‐2‐
formylphenyl)acrylate (3n)
3 | RESULTS AND DISCUSSION
Initially, benzaldehyde 1a and methyl acrylate 2a were
selected as the substrates to screen the reaction
conditions in the presence of catalytic amount of glycine
that was widely used as an efficient TDG in previous
reports.[4–7] Results are summarized in Table 1. The
reaction did not occur in the absence of any catalyst in
1H NMR (300 MHz, CDCl3) δ 10.24 (s, 1H), 8.41 (d,
J = 15.9 Hz, 1H), 8.00 (d, J = 2.1 Hz, 1H), 7.73 (dd,
J = 8.3, 2.1 Hz, 1H), 7.50 (d, J = 8.3 Hz, 1H), 6.38
(d,
J =
15.9 Hz, 1H), 3.83 (s, 3H). 13C NMR
(75 MHz, CDCl3) δ 190.1, 166.4, 139.8, 136.8, 135.3,
134.9, 134.6, 129.5, 124.3, 123.3, 52.0. HRMS (ESI):
Calcd for C11H9BrNaO3 [M + Na]+ 290.9627; Found:
290.9636.
DCE
(1,2‐dichloroethane)
(entry
1).
Although
[RhCp*Cl2]2 afforded the desired product 3a in 7%
NMR yield, other catalysts including Rh(OOCCF3)2,
RhCl3, [RuCl2(p‐Cymene)]2, and Pd(OAc)2 were ineffec-
tive for this reaction (entries 2 ~ 6). Pleasingly, the yield
increased to 20% and 11%, respectively, when AgSbF6 or
AgBF4 were employed as an additive (entry 7 and 8).
Reaction in other solvents such as DMF (N,N‐
dimethylformamide), DMSO (dimethyl sulfoxide), THF
(tetrahydrofuran), dioxane, toluene and acetic acid pro-
vided only trace amount of the desired product (entries
9 ~ 14). Further studies showed that the choice of oxi-
dants was vital for this reaction (entries 15 ~ 22). Only
trace amount of the product was obtained in the absence
of any oxidant. Switching the oxidant to Cu(OAc)2•H2O
or Cu(OTf)2 delivered product 3a in 37% and 29% yields,
respectively. The use of other oxidants including AgOAc,
Ag2CO3, BQ (benzoquinone) and oxygen, however,
afforded rather poor yields. Moreover, decreasing the
catalyst to 2 mol% led to a lower yield (24%), while
increasing the catalyst to 10 mol% did not promote the
reaction further. Finally, slight decrease in the yield
was observed when the reaction was performed under
nitrogen (21%, entry 22).
2.3.8 | Dimethyl 3,3′‐(5‐chloro‐2‐formyl‐
1,3‐phenylene)(2E,2′E)‐diacrylate (4b)
1H NMR (300 MHz, CDCl3) δ 10.84 (s, 1H), 8.53 (d,
J = 15.8 Hz, 2H), 7.88 (s, 2H), 6.66 (d, J = 15.8 Hz, 2H),
4.16 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 190.4, 166.0,
140.4, 139.7, 139.5, 130.5, 129.2, 124.5, 52.1. HRMS (ESI):
Calcd for C15H13ClNaO5 [M + Na]+ 331.0344; Found:
331.0349.
2.3.9 | Dimethyl 3,3′‐(5‐bromo‐2‐formyl‐
1,3‐phenylene)(2E,2′E)‐diacrylate (4c)
1H NMR (300 MHz, CDCl3) δ 10.50 (s, 1H), 8.18 (d,
J = 15.8 Hz, 2H), 7.71 (s, 2H), 6.32 (d, J = 15.8 Hz, 2H),
3.83 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 190.6, 166.0,
140.4, 139.4, 132.1, 130.9, 128.3, 124.5, 52.1. HRMS (ESI):
Calcd for C15H13BrNaO5 [M + Na]+ 374.9839; Found:
374.9847.
SCHEME 2 Evaluation of various
transient directing groupsa

LIU ET AL.
5 of 7
With these preliminary results in hand, we next turned
Various aromatic aldehydes were then subjected to the
standard conditions to determine the scope and limita-
tions of the present method. The results are summarized
in Scheme 3. In general, all the reactions were ortho‐selec-
tive and gave the mono‐olefinated aldehydes as the major
products. For the para‐substituted aldehydes, a series of
functional groups such as methyl, methoxy, chloro,
bromo, and fluoro were well tolerated to give the desired
products in moderate to good yields (3b ~ 3 g,
62 ~ 79%). Notably, p‐nitrobenzaldehyde which is usually
problematic in C‐H activation reactions also survived the
reaction conditions to give product 3 h in 47% yield.
Ortho‐substituted aldehydes reacted with methyl acrylate
smoothly, affording products 3i ~ 3 k in good yields. Steric
our attention to other transient directing groups
(Scheme 2). Without any TDG, the reaction took place
sluggishly to afford 3a in only 17% yield. Switching glycine
(L1) to other amino acids L2 ~ L8 still gave the desired
product in poor yields (9% ~ 25%). Different anilines were
then tried, and among which, electron‐deficient anilines
(L9 and L10) gave much better yields (45% and 62%,
respectively). Aliphatic amine such as benzyl amine was
also tested, however, an inferior yield was obtained (L11,
27%). Pleasingly, addition of p‐toluenesulfonamide
(TsNH2, L12) as the TDG provided 3a in 71% yield. The
hydrazides such as TsNHNH2 and AcNHNH2, however,
showed less efficiency (L13 and L14).
SCHEME 3 Reaction scope for aryl aldehydesa

6 of 7
LIU ET AL.
hindrance influence was observed for meta‐substituted
aldehydes, and the reactions occurred selectively at the less
hindered site (3 l ~ 3n). Heterocyclic aldehyde such as 1‐
methylindole‐3‐carboxaldehyde and 3‐formylthiophene
were also compatible for the present reaction, giving the
desired product 3o and 3p in 45% and 43% yields, respec-
tively. When 2‐formylthiophene was used as the substrate,
messy products were obtained. Moreover, pyridine‐4‐
carboxaldehyde was tested, however, no desired product
was observed. The di‐olefination reaction was also tried
using excess of methyl acrylate (3 equiv) at a prolonging
time (24 h). Under this reaction condition, products
4a ~ 4c could be obtained in good yields, albeit the mono‐
olefination product was still observed.
Furthermore, some alkene derivatives were evaluated
(Scheme 4). Reactions of different olefins including ethyl
acrylate, n‐butyl acrylate and tert‐butyl acrylate proceeded
smoothly to provide the corresponding products in good
yields (3 s ~ 3w). In addition, extention of olefin substrate
to styrene could afford the desired product 3x in 60% yield.
Kinetic isotope effect (KIE) experiment was then per-
formed to gain more detailed information about the pres-
ent reaction (Scheme 5). An equimolar mixture of 1a and
1a’ reacted with 2a under standard procedure for 3 h, and
a significant kinetic isotope effect (kH/kD = 5.2) was
observed determined by 1H NMR analysis.[15m] This result
suggested that the C‐H bond cleavage was the rate‐deter-
mining step for this reaction.
A plausible mechanism is proposed in Scheme 6. Ini-
tially, a Rh(III) complex A is generated from [RhCp*Cl2]2
and AgSbF6, which activates the imine B (in situ formed
from aldehyde and TsNH2) to give the intermediate C.
Then, coordination of olefin 2 to intermediate C affords
intermediate D, which is transformed into seven‐mem-
bered rhodacycle E via migratory insertion of olefin 2.
SCHEME 4 Olefination with alkene derivativesa
SCHEME 5 KIE experiment
SCHEME 6 Proposed reaction
mechanism

LIU ET AL.
7 of 7
[4] F.‐L. Zhang, K. Hong, T.‐J. Li, H. Park, J.‐Q. Yu, Science 2016,
351, 252.
Subsequently, β‐hydride elimination of intermediate E
takes place to release the olefinated product G and Rh(I)
Cp*.[18,19] Finally, Rh(III) complex A is regenerated via
reoxidation of Rh(I) by Cu(OAc)2•H2O, and hydrolysis
of product G delivers the final product 3.
[5] K. Yang, Q. Li, Y. Liu, G. Li, H. Ge, J. Am. Chem. Soc. 2016, 138,
12775.
[6] X. Liu, H. Park, J. Hu, Y. Hu, Q. Zhang, B. Wang, B. Sun, K.
Yeung, F. Zhang, J. Yu, J. Am. Chem. Soc. 2017, 139, 888.
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4 | CONCLUSION
[9] D. Mu, X. Wang, G. Cheng, G. He, J. Org. Chem. 2017, 82, 4497.
[10] Y. Liu, H. Ge, Nat. Chem. 2016, 9, 26.
In summary, we have developed a Rhodium(III)‐cata-
lyzed ortho‐C‐H olefination of aromatic aldehydes utiliz-
ing inexpensive TsNH2 as a transient directing group. A
series of functional groups were tolerated, affording the
desired products in moderate to good yields. Both acry-
lates and styrenes were compatible under the standard
reaction conditions. KIE experiment showed that the C‐
H bond cleavage was the rate‐determining step. Impor-
tantly, the present protocol provides a straightforward
access to olefinated aromatic aldehydes using aldehydes
as the simple starting materials.
[11] Y. Xu, M. Young, C. Wang, D. M. Magness, G. Dong, Angew.
Chem. Int. Ed. 2016, 55, 9084.
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ACKNOWLEDGEMENTS
We gratefully acknowledge the National Natural Science
Foundation of China (21302014), the Jiangsu Key Labora-
tory of Advanced Catalytic Materials and Technology
(BM2012110), and the Priority Academic Program Devel-
opment (PAPD) of Jiangsu Higher Education Institutions
for the financial support.
ORCID
Liang Wang http://orcid.org/0000-0002-5367-1516
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How to cite this article: Liu X, Wang Z, Chen Q,
He M, Wang L. Rhodium‐catalyzed ortho‐C‐H
olefination of aromatic aldehydes employing
transient directing strategy. Appl Organometal
Chem. 2017;e4039. https://doi.org/10.1002/aoc.4039