Access to Branched Allylarenes via Rhodium(III)-Catalyzed C-H Allylation of (Hetero)arenes with 2-Methylidenetrimethylene Carbonate

Article abstract of DOI:10.1021/acs.orglett.1c01832

A rhodium(III)-catalyzed C-H allylation of (hetero)arenes by using 2-methylidenetrimethylene carbonate as an efficient allylic source has been developed for the first time. Five different directing groups including oxime, N-nitroso, purine, pyridine, and pyrimidine were compatible, delivering various branched allylarenes bearing an allylic hydroxyl group in moderate to excellent yields.

Full text of DOI:10.1021/acs.orglett.1c01832

pubs.acs.org/OrgLett
Letter
Access to Branched Allylarenes via Rhodium(III)-Catalyzed C−H
Allylation of (Hetero)arenes with 2‑Methylidenetrimethylene
Carbonate
Shang-Shi Zhang,* Yi-Chuan Zheng, Zi-Wu Zhang, Shao-Yong Chen, Hui Xie, Bing Shu, Jia-Lin Song,
Yan-Zhi Liu, Yao-Fu Zeng,* and Luyong Zhang*
Cite This: Org. Lett. 2021, 23, 5719−5723
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ABSTRACT: A rhodium(III)-catalyzed C−H allylation of
(hetero)arenes by using 2-methylidenetrimethylene carbonate as
an efficient allylic source has been developed for the first time. Five
different directing groups including oxime, N-nitroso, purine,
pyridine, and pyrimidine were compatible, delivering various
branched allylarenes bearing an allylic hydroxyl group in moderate
to excellent yields.
Scheme 1. Cp*Rh(III)-Catalyzed C−H Allylation of Arenes
with 5-Methylene-1,3-dioxan-2-one
he allylic alcohol motif is one of the most widely used
synthons, and its transformations into diverse functional
T
groups are of fundamental importance in synthetic chemistry.1
Besides, allylarenes bearing a hydroxyl group at the allylic
position are considered as privileged scaffolds found in many
biological compounds.2 Consequently, various approaches
have been developed to access this useful scaffold. The classic
method for the synthesis of allylarenes bearing an allylic
hydroxyl group was Friedel−Crafts-type allylation using vinyl
epoxide as the coupling partner.3 An alternative is via cross
coupling of organometallic reagents with vinyl epoxide
electrophiles.4 However, harsh reaction conditions, poor
regioselectivity, and substrate specificity limited their applica-
tions.
In recent years, transition-metal-catalyzed C−H functional-
ization provides a convenient pathway for allyl arene synthesis.
Direct C−H allylation of arenes bearing a directing group
could be achieved in the presence of various transition metals,
such as Rh,5 Ru,6 Co,7 Ni,8 Mn,9 and others.10 Among them,
the Rh(III)-catalyzed C−H/C−O activation strategy, which
mainly includes the continuous reaction process of C−H
activation, olefin insertion, and β-O elimination, has received
increasing popularity owing to its distinct superiorities for
assembly of allyl arenes with more convenience and efficiency
(Scheme 1a).11 Until now, various allylic reagents including
allyl carbonates,11b−d allyl acetates,11e,f allylic alcohols,11g
methyleneoxetanones,11h−j vinyl benzoxazinanones,11k and
others11l,m have been proved to be effective coupling partners
in Rh(III)-catalyzed allylation reactions. Despite these achieve-
ments, the methods for the synthesis of allylarenes bearing an
allylic hydroxyl group are still rare. In 2014, Li and co-workers
reported a Rh(III)-catalyzed allylation of arenes with 2-
vinyloxiranes for the synthesis of allylic alcohols (Scheme
1b).12 Subsequently, by using vinyl-1,3-dioxolan-2-ones as
Received: June 2, 2021
Published: July 21, 2021
https://doi.org/10.1021/acs.orglett.1c01832
© 2021 American Chemical Society
Org. Lett. 2021, 23, 5719−5723
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a b
,
novel allylic precursors, Wang’s group developed a Rh(III)-
catalyzed C−H allylation of benzamides for highly chemo- and
stereoselective synthesis of allylic alcohols (Scheme 1b).13
However, the allylarenes obtained were featured with linear
allylic alcohol, while the methods for the synthesis of branched
allylarenes bearing an allylic hydroxyl group were not reported.
2-Methylidenetrimethylene carbonates were effective build-
ing blocks in cycloaddition reactions.14 They underwent
decarboxylation to afford zwitterionic π-allylpalladium species
which could serve as three-atom or four-atom synthons to
deliver the cycloaddition products (Scheme 1c). However, to
the best of our knowledge, they have not been utilized as novel
allylic reagents in transition-metal-catalyzed C−H allylation
reactions. Based on our continuable research interest in
Rh(III)-catalyzed C−H functionalization and previous work,15
we herein disclose the first example of Rh(III)-catalyzed C−H
allylation of (hetero)arenes by employing 2-methylidenetri-
methylene carbonate as an efficient allyl precursor (Scheme
1d). This practical and scalable protocol proceeds under redox-
neutral conditions and displays broad substrate scope (total of
72 examples, up to 95% yield, five different directing groups
including oxime, N-nitroso, purine, pyridine, and pyrimidine
were explored), mild reaction conditions, and high functional
group compatibility.
Scheme 2. Synthesis of Products 7 and 8
Initially, by using 2-methylidenetrimethylene carbonate as an
allylic reagent and (Cp*RhCl2)2 as the catalyst, we screened
several directing groups (see the Supporting Information for
details). Delightfully, the allylic alcohol product was obtained
in 64% yield when oxime ether was utilized as the directing
group in CF3CF2OH at 45 °C (see SI, Table 1, entry 1), and
arenes bearing the N-nitroso directing group could also be
transformed into the allylation product when 1,4-dixoane was
used as the solvent and HOAc as the additive at 45 °C (see SI,
Table 1, entry 2). Notably, 6-phenylpurine was also compatible
when the allylation reaction was conducted in MeOH with
adamantoic acid as the additive at 80 °C (see SI, Table 1, entry
3). Besides, it was found that 2-phenypyridine and N-(2-
pyrimidinyl)-indole could successfully couple with 2-methyl-
idenetrimethylene carbonate under modified conditions,
delivering the corresponding allylic alcohols with yields of
95% (see SI, Table 1, entry 4) and 81% (see SI, Table 1, entry
5), respectively.
With the optimized conditions in hand, we then explored
the substrate scope of oxime ethers in this allylation reaction,
and the results were displayed in Scheme 2. Gratifyingly, both
electron-donating functional groups such as methyl (7b, 7k),
methoxyl (7c, 7i), and phenyl (7d) and electron-withdrawing
groups such as halogen (7e, 7f, 7j, 7k), trifluoromethyl (7g),
and trifluoromethoxy (7h) in arenes could be well tolerated,
affording the allylic alcohols with yields ranging from 45% to
88%. The allylation occurred at the less hindered site for the
meta-substituted oxime ethers (7k, 7l). Besides, various
carbonyl O-methyl oximes were also compatible (7n−7u).
The reaction was also applied to the benzothiophene
heterocycle substrate, furnishing the target product 7m in
50% yield. Unfortunately, the ortho-substituted oximes showed
no reactivities due to the steric hindrance between the
directing group and substitute (7v). Delightfully, N-nitroani-
lines have also been proved to be effective substrates, and the
desired products were obtained in 63%−95% yields (8a−8d).
6-Arylpurines served as privileged scaffolds that possess a
wide spectrum of pharmacological activities. Therefore,
developing novel methods to modify 6-arylpurines is of vital
a
Reaction Conditions: 1 (0.2 mmol), 6 (1.5 equiv), (Cp*RhCl2)2
(2.5 mol %), AgSbF6 (10.0 mol %), Na2CO3 (1.0 equiv), CF3CH2OH
b
(0.2 M), 45 °C, 12 h. Reaction Conditions: 2 (0.2 mmol), 6 (1.5
equiv), (Cp*RhCl2)2 (2.5 mol %), AgSbF6 (10.0 mol %), HOAc (1.0
c
equiv), 1,4-dioxane (0.2 M), 45 °C, 12 h. 48 h.
importance. In this regard, various 6-arylpurines were
subjected to allylation reaction, and the results were
summarized in Scheme 3.
In general, commonly encountered functional groups such as
methoxyl (9b, 9g), methyl (9h, 9i), phenyl (9c), phenoxyl
(9d), and halogen (9e−9i) were all compatible. Besides,
several heterocyclic compounds including benzothiophene
(9j), benzofuran (9k), dibenzofuran (9m), and benzo[d]-
[1,3]dioxole (9n) could be smoothly allylated, albeit with a
decreased yield. The substituent at the N-9 position did not
affect the reaction efficiency (9o−9r), especially for the
substrate 9s bearing a glycosidic substitutional group.
Subsequently, the scope of 2-phenylpyridines was also
examined under the same conditions. It was observed that
the electronic properties of the substituents have no obvious
effect on the products’ formation (10a−10g). Notably, 2-
phenylpyridine bearing a substituent at the ortho position was
amenable to the reaction system, affording the allylic alcohol
product in 62% yield (10h). Meanwhile, heteroarenes such as
benzo[d][1,3]dioxole (10j), dibenzofuran (10k), and benzo-
furan (10l) were also compatible in standard conditions.
To further expand the scope of this rhodium-catalyzed
allylation reaction, we turned our attention to the indole
substrates. As shown in Scheme 4, N-pyrimidylindole
derivatives bearing various substituents such as formyl (11b),
methyl (11g), halogen (11c−11e, 11h, 11i), trifluoromethyl
(11j), ester (11k), nitryl (11f), and 4-methoxy phenyl (11l) at
C4, C5, and C6 positions could be smoothly transformed into
allylic alcohol products in 25%−90% yields. Besides, C5- and
C6-disubstituted indole substrates could be well tolerated and
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a
Scheme 3. Synthesis of Products 9 and 10
Scheme 5. Control Experiments
a
Reaction conditions: 3 (0.2 mmol), 6 (1.1 equiv), (Cp*RhCl2)2 (2.5
mol %), AgSbF6 (10.0 mol %), adamantoic acid (1.0 equiv), MeOH
(0.2 M), 80 °C, 12 h. 110 °C.
b
a
Scheme 4. Synthesis of Product 11
ing to the previous literature procedure16 (Scheme 5, eq 4) and
subjected to the same conditions for the coupling of 3a and 6,
and the desired product 9a was isolated in 55% yield (Scheme
5, eq 5). These above two experiments indicated that the
allylation reaction likely took place via a C−H activation
mechanism. Furthermore, a kinetic isotope effect value of 1.1
was obtained, suggesting that the C−H bond activation is not
involved in the turnover-limiting step (Scheme 5, eq 6).
Based on the mechanistic investigations and literature
precedents,11 a plausible mechanism was proposed for the
allylation reaction (Scheme 6). First, cyclometalated rhodium
complex II was formed via C−H activation between active
catalyst I and substrates 1. Subsequently, coordination of II
with alkene 6 followed by a migratory insertion generated
intermediate IV, which underwent β-oxygen elimination and
a
Reaction conditions: 5 (0.2 mmol), 6 (1.5 equiv), (Cp*RhCl2)2 (2.5
mol %), AgSbF6 (10.0 mol %), PivOH (1.0 equiv), PhCl (0.2 M), 60
°C, 12 h. 80 °C.
b
Scheme 6. Mechanistic Proposal
generated the allylated products with satisfactory yields (11n,
11o). Of note, the pyrrole derivative could also couple with 6
at elevated temperature and give the product in 69% yield
(11p).
To demonstrate the synthetic applications, the scales for the
synthesis of products 7a (Scheme 5, eq 1) and 11a (Scheme 5,
eq 2) were extended to 1.0 mmol, and the products 7a and 11a
were isolated in 75% and 87% yield, respectively. Next, some
control experiments were carried out to probe the reaction
mechanism. Coupling of N-pyrimidylindole 5a with 6 using
cyclometalated rhodium complex A as the catalyst afforded the
allylic alcohol 11a in 75% yield (Scheme 5, eq 3). Besides,
cyclometalated rhodium complex 12 was synthesized accord-
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then released one molecule of CO2. The allylic alcohol
products 7−11 were formed via protodemetalation accom-
panied by regenerating the active rhodium catalyst.
Yan-Zhi Liu − Center for Drug Research and Development,
Guangdong Pharmaceutical University, Guangzhou 510006,
P. R. China
In conclusion, we have developed the rhodium(III)-
catalyzed C−H allylation reaction of (hetero)arenes by using
2-methylidenetrimethylene carbonate as an efficient allylic
source. Five different directing groups including oxime, N-
nitroso, purine, pyridine, and pyrimidine were applicable to the
reaction catalytic system. Various branched allylarenes bearing
an allylic hydroxyl group were obtained in moderate to
excellent yields, and gram-scale synthesis and mechanistic
studies were also accomplished. To the best of our knowledge,
2-methylidenetrimethylene carbonate was employed as an
efficient allyl precursor for the first time in transition-metal-
catalyzed direct C−H allylation reactions. Further efforts for
strengthening the application of this transformation and
developing other transition-metal-catalyzed cross-coupling
reactions are in progress in our laboratory.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01832
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by a Start-up Grant from Guangdong
Pharmaceutical University (Grant No. 51377002), the Na-
tional Natural Science Foundation of China (22001044), and
Youth Innovation Talents Project of Colleges and Universities
in Guangdong Province (Grant No. 51377201).
REFERENCES
■
ASSOCIATED CONTENT
* Supporting Information
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■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c01832.
Reaction condition screening tables, detailed exper-
imental procedures, and characterization data for all
1
products including H and 13C NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
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Shang-Shi Zhang − Center for Drug Research and
Development, Guangdong Pharmaceutical University,
Guangzhou 510006, P. R. China; orcid.org/0000-0002-
9247-1373; Email: zhangshangshi@gdpu.edu.cn
Yao-Fu Zeng − Institute of Pharmacy and Pharmacology,
Hunan Provincial Key Laboratory of Tumor
Microenvironment Responsive Drug Research, University of
South China, Hengyang 421000, P. R. China; orcid.org/
0000-0003-2133-378X; Email: zengyf@usc.edu.cn
Luyong Zhang − Center for Drug Research and Development,
Guangdong Pharmaceutical University, Guangzhou 510006,
P. R. China; Email: lyzhang@cpu.edu.cn
Authors
Yi-Chuan Zheng − Center for Drug Research and
Development, Guangdong Pharmaceutical University,
Guangzhou 510006, P. R. China
Zi-Wu Zhang − School of Chemistry and Chemical
Engineering and Guangdong Cosmetics Engineering &
Technology Research Center, Guangdong Pharmaceutical
University, Zhongshan 528458, P. R. China
Shao-Yong Chen − School of Chemistry and Chemical
Engineering and Guangdong Cosmetics Engineering &
Technology Research Center, Guangdong Pharmaceutical
University, Zhongshan 528458, P. R. China
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Bing Shu − School of Pharmacy, Guangdong Pharmaceutical
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Jia-Lin Song − Center for Drug Research and Development,
Guangdong Pharmaceutical University, Guangzhou 510006,
P. R. China
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