Oxidative olefination of anilides with unactivated alkenes catalyzed by an (electron-deficient η5-cyclopentadienyl)rhodium(III) complex under ambient conditions

Article abstract of DOI:10.1002/chem.201501232

The oxidative olefination of sp² C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η⁵-cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-defici

Full text of DOI:10.1002/chem.201501232

DOI: 10.1002/chem.201501232
Communication
&
CÀH Bond Functionalization
Oxidative Olefination of Anilides with Unactivated Alkenes
Catalyzed by an (Electron-Deficient h5-
Cyclopentadienyl)Rhodium(III) Complex Under Ambient
Conditions
Yuji Takahama,[b] Yu Shibata,[a] and Ken Tanaka*[a, b, c]
On the other hand, our research group established that the
Abstract: The oxidative olefination of sp2 CÀH bonds of
use of ethoxycarbonyl-substituted cyclopentadienyl-RhIII com-
anilides with both activated and unactivated alkenes
plex 1, [{CpERhCl2}2],[17a] in place of [{Cp*RhCl2}2] as a precatalyst
using an (electron-deficient h5-cyclopentadienyl)rhodi-
enables the CÀH bond functionalization of electron-rich arenes
um(III) complex is reported. In contrast to reactions using
under ambient conditions with the broad substrate scope pre-
this electron-deficient rhodium(III) catalyst, [Cp*RhCl2]2
sumably due to electron-deficient nature of 1.[17–20] For exam-
showed no activity against olefination with unactivated al-
ple, in the oxidative annulation of anilides with internal al-
kenes. In addition, the deuterium kinetic isotope effect
kynes, although the use of the [{Cp*RhCl2}2] precatalyst re-
quired elevated temperature as well as a stoichiometric CuII ox-
(DKIE) study revealed that the CÀH bond cleavage step is
thought to be the turnover-limiting step.
idant (or oxygen atmosphere) and afforded a product from an
aliphatic alkyne in moderate yield,[21] the use of 1 instead of
[{Cp*RhCl2}2] allowed the reactions to proceed under ambient
Transition-metal-catalyzed oxidative sp2 CÀH bond olefination
conditions and afforded products from aliphatic alkynes in
high yields.[17a,b] Similarly, in the oxidative olefination of anilides
reactions of arenes with alkenes are efficient and atom-eco-
nomical methods for the synthesis of vinylarene derivatives.[1]
with alkenes using the [{Cp*RhCl2}2] precatalyst, elevated tem-
Following the pioneering work by Fujiwara–Moritani,[2]
a number of reliable methods have been reported to date.[3–5]
However, applicable alkenes were limited to “activated” ones
(e.g., acrylates and styrenes).[6–9] Recently, “unactivated” aliphat-
ic alkenes have been successfully employed in the PdII-cata-
lyzed olefination of dialkoxybenzene[10] and N-(8-quinolinyl)-
phenylacetamide,[11] the IrI-catalyzed olefination of furans,[12]
and the RhIII-catalyzed olefination of aryl oximes,[13] N-(1-naph-
thyl)sulfonamides,[14] and isoquinolones.[15] However, these ex-
amples required stoichiometric external oxidants (or hydrogen
acceptors) and/or elevated temperature. Consequently the de-
velopment of the transition-metal-catalyzed oxidative sp2 CÀH
bond olefination of arenes with unactivated alkenes that pro-
ceeds under ambient conditions (at room temperature using
air as a terminal oxidant) remains a challenge.[16]
perature as well as the stoichiometric CuII oxidant were re-
quired and available alkenes were limited to activated ones.[4e]
Herein we report the oxidative olefination of anilides with
both activated and unactivated alkenes using 1 as the precata-
lyst under ambient conditions.
We first examined the reaction of acetanilide (2a) with 1-
octene (3a, 1.1 equiv) in the presence of a cationic RhIII/CpE
catalyst, generated in situ from 1, AgSbF6, and [Cu(OAc)2] at
room temperature under air. Pleasingly, the desired oxidative
olefination proceeded to give mono-olefinated acetanilides
(linear isomer 4aa and branched isomers 5aa/6aa) in 41%
yield along with diolefinated product 7aa in 9% yield (Table 1,
entry 1). Importantly, no reaction was observed when using
[{Cp*RhCl2}2] instead of 1 (entry 2). Screening of solvents (en-
tries 3–6) revealed that the use of tAmylOH (entry 3) improves
the yield of 4–7aa. In order to avoid the formation of the dio-
lefinated acetanilide 7aa, we tested the reactions of 2a
(2 equiv) and 3a in acetone and tAmylOH (entries 7 and 8). As
a result, the use of operationally more convenient acetone sol-
vent afforded 4–6aa in the highest yield (entry 7).
The scope of alkenes and anilides is shown in Scheme 1. Pri-
mary and secondary alkyl-substituted alkenes 3a–c smoothly
reacted with 2a to give olefinated acetanilides in good yields.
Under the optimized reaction conditions, only a trace amount
of olefinated acetanilides were generated when using
[{Cp*RhCl2}2] instead of 1. Increasing the steric bulk of alkyl
groups improved linear/branch selectivity (4/5+6). On the
other hand, the reaction of vinyltrimethylsilane (3d) and 2a
proceeded with moderate linear/branch selectivity (4ad/5ad).
[a] Dr. Y. Shibata, Prof. Dr. K. Tanaka
Department of Applied Chemistry
Graduate School of Science and Engineering
Tokyo Institute of Technology, Ookayama
Meguro-ku, Tokyo 152-8550 (Japan)
E-mail: ktanaka@apc.titech.ac.jp
Homepage: http://www.apc.titech.ac.jp/~ktanaka/
[b] Y. Takahama, Prof. Dr. K. Tanaka
Department of Applied Chemistry, Graduate School of Engineering
Tokyo University of Agriculture and Technology
Koganei, Tokyo 184-8588 (Japan)
[c] Prof. Dr. K. Tanaka
JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 (Japan)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201501232.
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Table 1. Optimization of reaction conditions for rhodium-catalyzed oxida-
tive olefination of acetanilide (2a) with 1-octene (3a).[a]
Entry
Solvent
2a/3a
Yield [%][b]
(4aa/5aa/6aa)
7aa
1
acetone
acetone
tAmylOH
(CF3)2CHOH
CH3CN
DMF
acetone
tAmylOH
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
2:1
41 (72:19:9)
0
55 (68:19:13)
<5
0
0
9
0
8
0
0
0
2
2
2[c]
3
4
5
6
7[d]
8[d]
80 (76:16:8)
76 (75:15:10)
2:1
[a] 1 (0.0050 mmol), AgSbF6 (0.020 mmol), Cu(OAc)2·H2O (0.040 mmol), 2a
(0.20 mmol), 3a (0.22 mmol), and solvent (1.0 mL) were used. [b] Deter-
mined by 1H NMR spectroscopy. [c] [{Cp*RhCl2}2] was used instead of 1.
[d] 1 (0.010 mmol), AgSbF6 (0.040 mmol), Cu(OAc)2·H2O (0.080 mmol), 2a
(0.40 mmol), 3a (0.20 mmol), and solvent (1.0 mL) were used.
Functionalized alkenes 3e–g could also be employed, and al-
lylbenzyl ether (3h) and vinyl acetate (3i)[22] reacted with 2a to
give linear products 4ah and 4ai. Importantly, activated al-
kenes 3j and 3k were also able to react with 2a to give linear
products 4aj and 4ak in higher yields than the use of the
[{Cp*RhCl2}2] precatalyst. With respect to anilides, a variety of
methoxy- and methyl-substituted acetanilides 2b–g reacted
with 3a to give olefinated acetanilides in good yields. It is
worth mentioning that 2-methylacetanilide (2g), which
showed poor reactivity in the Cp*RhIII-catalyzed oxidative olefi-
nation with 3j,[4e] reacted with 3a in good yield. 4-Haloacetani-
lides 2h,i and 1-acetamidenaphthalene (2j) were also able to
react with 3a in good yields. Not only acetanilides but also
propioanilide (2k) and pivaloanilide (2l) could equally be em-
ployed. The major linear isomers 4 could be isolated in pure
forms, although 4ja and 5ja were isolated as a mixture.
The large-scale reaction of 2a with 3a proceeded under the
same conditions without significant yield loss as shown in
Scheme 2.
Scheme 1. Scope of anilides 2 and alkenes 3. Reactions were conducted
using 1 (0.0050 mmol), AgSbF6 (0.020 mmol), Cu(OAc)2·H2O (0.040 mmol), 2
(0.40 mmol), 3 (0.20 mmol), and acetone (1.0 mL). The cited yields are of the
isolated products. [a] [{Cp*RhCl2}2] was used instead of 1. [b] Trace amounts
Chemoselectivity between an alkyne vs. an alkene was ex-
amined as shown in Scheme 3. The reaction of 2a with enyne
3l gave the corresponding indole 8 exclusively without forma-
tion of olefinated product 4al.
1
of 5 were detected in the crude mixture by H NMR.
Unsymmetrically diolefinated anilides could be synthesized
by the sequential olefination as shown in Scheme 4. The reac-
tions of mono-olefinated anilide 4aa with alkenes 3c, 3j, and
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Scheme 6. Competition experiment between electron-rich and electron-defi-
cient anilides.
Scheme 2. Large-scale reaction of 2a with 3a.
Scheme 7. Intermolecular competition experiment between 2a and 2a-[D5].
Scheme 3. Chemoselectivity between alkyne vs. alkene.
Scheme 8. Deuterium kinetic isotope effect obtained from individual reac-
tions of 2a and 2a-[D5].
Scheme 4. Synthesis of unsymmetrically diolefinated anilides 9aac, 9aaj, and
9aak by olefination of 4aa with alkenes 3c,j,k.
measured.[23] The intermolecular competition experiment be-
tween 2a and 2a-[D5] in the presence of 3a revealed a DKIE
value of 3.3 (Scheme 7), which is the almost the same value as
that of our previously reported oxidative annulation of 1a with
diphenylacetylene (DKIE value=3.5).[17b] A DKIE value, mea-
sured by comparing the initial rates obtained from individual
reactions of 2a and 2a-[D5] with 3a, was 2.8 (Scheme 8). Im-
portantly, as almost no loss of deuterium from both 1a-[D5]
and 3aa-[D5] was observed, the metalation of the anilide was
found to be irreversible using 1 as the precatalyst. These re-
sults indicate that the CÀH bond cleavage step is thought to
be the turnover-limiting step.[24]
3k proceeded to give unsymmetrically diolefinated anilides
9aac, 9aaj, and 9aak, respectively, in good to high yields.
It was speculated that highly electrophilic nature of the elec-
tron-deficient complex 1 would facilitate the CÀH bond func-
tionalization of not electron-poor arenes but electron-rich
arenes. Indeed, not the benzamide CÀH bond, but the anilide
CÀH bond of 2m was olefinated with 3a to give 4ma without
formation of 10 (Scheme 5). Similarly, the competition experi-
ment between electron-rich anilide 2c and electron-deficient
anilide 2i revealed the preference for olefination across 2c
over 2i (Scheme 6).
In order to gain mechanistic insights into the CÀH bond acti-
vation step using the electron-deficient complex 1, a deuterium
kinetic isotope effect (DKIE) of olefination of 2a with 3a was
In conclusion, we have established that a dinuclear (elec-
tron-deficient h5-cyclopentadienyl)RhIII complex is a highly
active precatalyst for the oxidative sp2 CÀH bond olefination of
anilides with both activated and unactivated alkenes under
ambient conditions (at room temperature under air). In con-
trast, a commonly employed RhIII precatalyst, [{Cp*RhCl2}2],
showed no activity against olefination with unactivated al-
kenes. Competition experiments ensured highly electrophilic
nature of complex 1 toward aromatic CÀH bond functionaliza-
tion. The study of deuterium kinetic isotope effects indicated
that the CÀH bond cleavage step is thought to be the turn-
over-limiting step. This paper clearly demonstrated that the
use of the electron-deficient RhIII catalyst [CpERhIII] realizes not
only mild reaction conditions but also significant expansion of
the substrate scope.
Scheme 5. Competition experiment between benzamide and anilide CÀH
bonds.
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Acknowledgements
This work was supported partly by a Grant-in-Aid for Scientific
Research (No 20675002) from the Ministry of Education, Cul-
ture, Sports, Science and Technology (MEXT, Japan), and ACT-C
from Japan Science and Technology Agency (JST, Japan). We
thank Umicore for generous support in supplying rhodium(III)
chloride.
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[8] Oxidative olefination with cyclic aliphatic alkenes has been reported;
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[11] A. Deb, S. Bag, R. Kancherla, D. Maiti, J. Am. Chem. Soc. 2014, 136,
13602.
Keywords: alkenes · anilides · CÀH bond functionalization ·
olefination · rhodium
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Received: March 28, 2015
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COMMUNICATION
&
CÀH Bond Functionalization
Y. Takahama, Y. Shibata, K. Tanaka*
&& – &&
Oxidative Olefination of Anilides with
Unactivated Alkenes Catalyzed by an
(Electron-Deficient h5-
Cyclopentadienyl)Rhodium(III)
Complex Under Ambient Conditions
It takes two: It has been established
that a dinuclear (electron-deficient h5-
cyclopentadienyl)RhIII complex is
kenes under ambient conditions (at
room temperature under air; see
scheme). In contrast, a commonly em-
ployed RhIII precatalyst, [{Cp*RhCl2}2],
showed no activity against olefination
with unactivated alkenes.
a highly active precatalyst for the oxida-
tive sp2 CÀH bond olefination of anilides
with both activated and unactivated al-
Chem. Eur. J. 2015, 21, 1 – 5
www.chemeurj.org
5
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers! ÞÞ