Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C?H Activation

Article abstract of DOI:10.1002/chem.201701703

A Cp*Rh^III-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C?H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center i

Full text of DOI:10.1002/chem.201701703

A Journal of
Accepted Article
Title: Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-
Disubstituted Alkenes Triggered by C-H Activation
Authors: Yang Li, Yuhai Tang, Xin He, Dandan Shi, Jun Wu, and
Silong Xu
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To be cited as: Chem. Eur. J. 10.1002/chem.201701703
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Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-
Disubstituted Alkenes Triggered by C-H Activation
Yang Li*, Yuhai Tang, Xin He, Dandan Shi, Jun Wu and Silong Xu*
Abstract:
A
Cp*RhIII-catalyzed annulative carbooxygenation of
carbooxygenation of alkenes triggered by C-H activation has
been rarely investigated.[9] Consequently, developing new and
efficient carbooxygenations of alkenes via C-H activation
remains an important objective, which provides a promising
approach for difunctionalization of alkenes with C-O bond
challenging 1,1-disubstituted alkenes triggered by C-H activation of
N-aryloxyacetamides has been established, which affords 2,3-
dihydrobenzofuran derivatives with a quaternary carbon center in
good to excellent yields under mild redox-neutral conditions. An
amide group on the alkenes is essential for the process, which may
inhibit the β-H elimination from C(sp3)-Rh species by coordinatively
saturating the rhodium center. Furthermore, mechanistic insights
obtained from control experiments suggest a most likely mechanism
involving a RhIII-RhV-RhIII catalytic cycle.
formation.[10] Herein, we report
a
Cp*RhIII-catalyzed
carbooxygenation of 1,1-disubstituted alkenes with N-
aryloxyacetamides to afford 2,3-dihydrobenzofuran derivatives
with a quaternary carbon center in good to excellent yields under
mild redox-neutral conditions (Scheme 1d).
Transition-metal-catalyzed C-H functionalization has been
developed as an economical and straightforward synthetic
approach for the synthesis of a variety of complex core
structures that are occurring in natural products, bioactive
compounds as well as pharmaceuticals.[1] Among a wide range
of synthetic methods involving C-H functionalization, alkenes are
widely used as a coupling partner via Heck-type approaches.[2]
However, difunctionalization of alkenes triggered by transition-
metal-catalyzed C-H activation is still a challenge due to the
competitive β-H-elimination from the resulting C(sp3)-metal-
species.[2-3] Recently, C-H functionalization employing a redox-
neutral strategy with oxidizing directing groups has been
elegantly demonstrated.[1h, 4] In particular, with oxidizing directing
groups (N-OR), rhodium(III)-catalyzed intra- and intermolecular
carboamination of alkenes or allenes triggered by C-H activation
has been developed for the synthesis of N-heterocyclic
compounds.[5] In 2015, Rovis group[6] published the first
Cp*tBuRhIII-catalyzed carboamination of 1,2-disubstituted alkenes
Scheme 1. Transition-metal-catalyzed difunctionalization of alkenes triggered
with N-enoxyphthalimides
affording acyclic products with
by C-H activaton.
excellent syn-selectivities, in which the β-H-elimination could be
inhibited by coordinatively saturating the C(sp3)-rhodium-
intermediate with an in situ generated bidentate directing group
Inspired by the fact that a coordinative functional group on
alkenes is essential for obtaining high enantioselectivities in RhI-
catalyzed asymmetric hydrogenation of functionalized alkenes
due to the coordination with rhodium center in a chelating
mode,[11] we proposed that a coordinative functional group on
alkenes may also be helpful to inhibit the β-H-elimination in
transition-metal-catalyzed difunctionalization of alkenes, by
coordinatively saturating the C(sp3)-metal-intermediate. We
were also interested in employing 1,1-disubstituted alkenes as
substrates for the difunctionalization, which were expected to
(Scheme 1a). With
a similar strategy, by employing N-
aryloxyacetamides as precursors, Liu and co-workers[7] reported
the Cp*RhIII-catalyzed carboamination of N-alkoxyacrylamides
(Scheme 1b). Subsequently, Glorius group[8] developed the
carboamination of acrylates with N-aryloxyacetamides and they
found that Cp*CoIII catalyst demonstrated unique reactivity
compared with Cp*RhIII in the transformation (Scheme 1c). In
contrast to the carboamination strategies, the corresponding
generate
a
quaternary carbon center in the products.
Noteworthy is that 1,1-disubstituted alkenes represent a type of
challenging and rarely-applied coupling partner for C-H
functionalizations.[5g-h, 12] To test the proposed strategy, methyl 2-
acetamidoacrylate (2a) was employed as a coupling alkene in
the transition-metal-catalyzed C-H functionalization of N-
phenoxyacetamide (1a) (Table 1). After an initial screening of
catalysts, to our delight, [Cp*RhCl2]2 afforded an annulative
carbooxygenation product 2,3-dihydrobenzofuran[13] (3aa) in
72% yield, without any β-H-elimination products detected (Table
1, entries 1-3). Screening of several bases revealed CsOAc as
the optimal choice giving 3aa in 83% yield (entries 3-5).
[*]
Y. Li*, Y. Tang, J. Wu, D. Shi, and S. Xu*
Department of Chemistry, School of Science
Xi’an Jiaotong University
Xi’an 710049, P. R. China
E-mail: yanglee@mail.xjtu.edu.cn
silongxu@mail.xjtu.edu.cn
X. He
Department of Medicinal Chemistry, School of Pharmacy
Xi’an Jiaotong University
Xi’an 710049, P. R. China
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under: http://www.xxxxxxx
or from the author.
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However, higher temperature exerted no effect on the reaction
(entry 6). Solvents dramatically affected the yields and DCE
emerged as the best solvent affording the product 3aa in 91%
yield (entries 7-10). Further optimization of the reaction
conditions demonstrated that the carbooxygenation reaction was
best performed in DCE in the presence of 50 mol% CsOAc, with
2.5 mol% [Cp*RhCl2]2 as the catalyst at room temperature for 16
hours (entry 10).
yloxy)acetamide, the corresponding product was isolated in 82%
yield (3la). To assess the efficiency and potential for applications
of this method, we carried out a scale-up experiment and
products 3aa and 3ba are obtained in 89% and 92% yields,
respectively. The absolute molecular structures for 3ea and 3la
were confirmed by X-ray crystallography (see Scheme 2 and the
Supporting Information). Furthermore, acetyl-substituted N-
vinylacetamide (2b) was investigated in the reaction, which
could also afford the corresponding carbooxygenation products
(3ab, 3bb), albeit with moderate yields. However, trisubstituted
alkene 2c was incompatible under the optimized conditions,
probably due to the bulkiness that impeded the binding to the Rh
center.
Table 1. Optimization of the reaction conditions.[a]
entry
1
catalyst
solvent
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
CF3CH2OH
dioxane
THF
additive
NaOAc
NaOAc
NaOAc
KOAc
yield (%)[b]
trace
n.r
[Cp*IrCl2]2
2
[RuCl2(p-cymene)]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
3
72
4
60
5
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
83
6[c]
7
82
trace
42
8
9
26
10
11[d]
DCE
91
DCE
91
[a] Unless specified, the reactions were carried out using 2.5 mol% catalyst,
50 mol% additive, 1.0 equiv of N-phenoxyacetamide 1a (0.2 mmol) and 1.2
equiv of methyl 2-acetamidoacrylate 2a (0.24 mmol) in 2 mL solvent at rt
under N2 for 16 h. [b] Isolated yield. [c] 60 C. [d] 1.5 equiv of 2a. n.r = no
reaction.
With the optimized reaction conditions in hand, we
investigated the scope of the Cp*RhIII-catalyzed annulative
carbooxygenation of 1,1-disubstituted functionalized alkenes
(Scheme 2). Various N-aryloxyacetamides were tested in the
reaction with 2-acetamidoacrylate (2a) and the corresponding
products could be isolated in good to excellent yields (3aa-la,
68-92%). Aryloxyacetamides with para-electron-donating groups
gave 2,3-dihydrobenzofuran products in excellent yields (3ba,
3ca), while those with para-electron-withdrawing groups could
not proceed the reaction, probably due to their poor solubility in
DCE. However, using MeOH instead of DCE as the solvent, the
reaction occurred smoothly affording the corresponding products
in 80-87% yields (3da-ga). Meta-substituted aryloxyacetamides
delivered the corresponding products in good yields as a single
regioisomer (3ha-ja) with the C-H activation taken place at the
less hindered C-H bond of aryloxyacetamides. The ortho-
methylphenoxyacetamide afforded product 3ka in a good yield
of 70% under standard conditions, while using MeOH as the
solvent the yield increased to 92%. For N-(naphthalen-1-
Scheme 2. The scope of the carbooxygenation reaction. Isolated yields are
given. Reaction conditions: 1 (0.2 mmol, 1.0 equiv), 2 (0.24 mmol, 1.2 equiv),
[Cp*RhCl2]2 (2.5 mol%), CsOAc (0.1 mmol, 0.5 equiv) and DCE (2 mL) were
sealed in a 25 mL Schlenk tube at rt for 16 h under N2. [a] MeOH (2 mL) was
used as solvent. [b] Both 1a and 2c were recovered. [c] 1 mmol scale.
Scheme 3. Carbooxygenation of alkenes with N-aryloxyamides bearing
different amide groups
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To further demonstrate the scope and at the same time
clarify the source of the amide group in products, reactants with
different amide groups were employed. Under standard reaction
conditions, when N-phenoxypivalamide (1a’) was tested in the
reaction with alkene 2a, product 3aa was generated in 80% yield
without the incorporation of the pivalamido group (PivNH-)
(Scheme 3a). On the other hand, the reaction of methyl 2-
propionamidoacrylate 2d with N-phenoxyacetamide 1a produced
the product 3ad with a propionamido group (EtCONH-) in 79%
yield (Scheme 3b). These results indicate that the amide group
in annulative products come from the alkenes rather than the N-
aryloxyamides, which, intriguingly, also provides an important
clue for the reaction mechanism (vide infra).
intermediate A, which is followed by alkene insertion, forming a
7-membered rhodacycle intermediate B with a C(sp3)-Rh bond.
In the C(sp3)-Rh species, rhodium center could be
coordinatively saturated by the oxygen atom of the amide group
on the alkene.[5-7] As a result, β-H elimination is suppressed
avoiding C-H olefination products. This is followed by an
oxidative addition step which breaks the O-N bond and forms a
high oxidation state RhV-nitrenoid intermediate C, which then is
coordinated by a molecule of HOAc to generate a RhV-
intermediate D. The formation of the RhV-intermediate could be
supported by recent computational studies by Houk and Wu,[14]
which showed that the oxidative addition to the O-N bond of
oxidizing directing group is much more favorable than the
reductive elimination.[15] This RhV-intermediate D subsequently
undergoes a C-O bond reductive elimination to give intermediate
E, which affords the products 3 and regenerates the catalyst by
ligand exchange with HOAc. An alternative way (path b) that
intermediate B undergoes an intramolecular substitution to give
product 3 cannot be ruled out,[4s] however, this type of cleavage
of the O−N bond in N-aryloxyacetamides usually proceeds under
acidic conditions.[7]
To further shed light on the mechanism of the reaction, a
deuterium-labeling study was conducted by performing the
reaction of 1a and 2a in CD3OD under otherwise identical
conditions. The deuterium product 3aa-D was obtained in 78%
yield with 57% deuterium incorporated on the benzene ring at
the ortho-position of the directing group, and 24% deuterium on
the methyl group by transesterfication (Scheme 4a). This result
indicates that the step of C-H activation is reversible under the
reaction conditions. The absence of deuterium at the β-position
of 2,3-dihydrobenzofuran product (3aa-D) also implies that β-H
elimination is not involved in the reaction mechanism. In addition,
methyl methacrylate (2e) was applied in the reaction with 1a
under standard conditions, but no product was detected
(Scheme 4b). It suggests that the amide group in alkenes is
crucial for the carbooxygenation and is believed to coordinate
with rhodium center in the reaction.
Scheme 4. Mechanistic studies.
Scheme 5. Proposed mechanism for the carbooxygenation.
Based on the above results, the generally accepted C-H
functionalization mechanism involving a RhIII-RhI-RhIII catalytic
cycle[1-5] is supposed to be unlikely for the Cp*RhIII-catalyzed
annulative carbooxygenation. By this mechanism, the reactants
bearing two different amide groups would deliver either mixed
products or single product with amide group derived from N-
aryloxyamides through a reductive elimination/oxidative addition
pathway.[14] However, this is contradicted by the observation that
single products are obtained with the amide groups originating
from the coupling alkenes (Scheme 3). Taking into consideration
the above results, a most likely RhIII-RhV-RhIII catalytic cycle
(path a) is proposed in Scheme 5. The catalytically active
species Cp*Rh(OAc)2 is generated by anion exchange with
CsOAc, then a facile and reversible C-H activation of N-
In conclusion, an efficient intermolecular Cp*RhIII-catalyzed
annulative carbooxygenation of 1,1-disubstituted functionalized
alkenes with N-aryloxyacetamides has been established, which
affords 2,3-dihydrobenzofuran derivatives with a quaternary
carbon center in good to excellent yields under mild redox-
neutral conditions. By strategically installing an amide group on
the alkenes, the β-H elimination from C(sp3)-Rh species has
been prohibited probably due to the amide coordinatively
saturating the rhodium center. In addition, in contrast with the
generally accepted RhIII-RhI-RhIII mechanism, a most likely RhIII-
RhV-RhIII catalytic cycle is proposed based on mechanistic
studies for the annulative carbooxygenation. Further studies to
elucidate the mechanism and exploit this new transformations
triggered by transition-metal-catalyzed C-H activations are
undergoing in this lab.
aryloxyacetamides
1
affords
a
5-membered rhodacycle
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Acknowledgements
We thank the National Natural Science Foundation of China
(Nos. 21602167, 21402149), the Natural Science Basic
Research Plan in Shaanxi Province of China (Nos. 2016JQ2019,
2015JQ2050), the China Postdoctoral Science Foundation (Nos.
2015M580830,
2014M550484,
2015T81013),
and
the
Fundamental Research Funds for the Central Universities.
Keywords: C-H activation • Cp*Rh(III) catalysis • annulation •
carbooxygenation • 1,1-disubstituted alkenes
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Information.
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10.1002/chem.201701703
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Y. Li*, Y. Tang, X. He, D. Shi, J. Wu and
S. Xu*
Page No. – Page No.
Rhodium(III)-Catalyzed Annulative
Carbooxygenation of 1,1-Disubstituted
Alkenes Triggered by C-H Activation
Carbooxygenation of 1,1-disubstituted alkenes: An efficient Cp*RhIII-catalyzed
annulative carbooxygenation of challenging 1,1-disubstituted functionalized alkenes
with N-aryloxyacetamides triggered by C-H activation is established. An amide
group on alkenes is strategically introduced by inhibiting β-H elimination from
C(sp3)-Rh species. Mechanistic investigations suggest a most likely mechanism
involving a RhIII-RhV-RhIII catalytic cycle.
This article is protected by copyright. All rights reserved.