Manganese-Catalyzed Hydroarylation of Unactivated Alkenes

Article abstract of DOI:10.1002/anie.202003830

Transition-metal-catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8-aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese-catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese-catalysis regime. The method features earth-abundant manganese catalysis, easily available substrates, broad functional-group tolerance, and excellent regioselective control.

Full text of DOI:10.1002/anie.202003830

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Accepted Article
Title: Manganese-Catalyzed Hydroarylation of Unactivated Alkenes
Authors: Ting Liu, Yunhui Yang, and Congyang Wang
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10.1002/anie.202003830
Angewandte Chemie International Edition
COMMUNICATION
Manganese-Catalyzed Hydroarylation of Unactivated Alkenes
Ting Liu, Yunhui Yang and Congyang Wang*
Dedication to the 100th birthday of Professor Youqi Tang, Peking University.
varied diarylation products of terminal alkenes.[4f-i] Among
hydroarylation of unactivated alkenes,[2,7] reactions using
Abstract: Transition-metal-catalyzed hydroarylation of unactivated
alkenes with strategic use of remote coordinating functional groups
has received significant attentions recently in order to address the
arylboronic acids featured readily available substrates, practical
issues of both low reactivity and poor selectivity. A bidentate 8-
ease of handling and well tolerance of functionality. In 2010,
aminoquinoline amide group is the most successfully adopted in
Lautens and coworkers realized the Rh-catalyzed hydroarylation
unactivated alkenes for Pd- and Ni-catalysis. Herein, we describe
of terminal allyl sulfones/amines with arylboronic acids,[2f,2g]
the first manganese-catalyzed hydroarylation of unactivated alkenes
where linear hydroarylation products were obtained through β-H
bearing diverse simple functionalities with arylboronic acids. A series
elimination/M-H migratory re-insertion mechanism (Scheme 1a).
of δ- and γ-arylated amides, ketones, pyridines, and amines was
Since 2018, Engle and Zhao have reported Pd- and Ni-catalyzed
accessed with excellent regioselectivity and in high yields.
hydroarylation of unactivated alkenes respectively, both utilizing
Hydroalkenylation of unactivated alkenes was also proved nicely
the bidentate AQ directing groups to stabilize the C(sp3)-M
applicable under this manganese-catalysis regime. The protocol
intermediates (Scheme 1b).[2h-j] In this context, alternative
features earth-abundant manganese catalysis, easily available
catalytic systems that enable precise hydroarylation of
unactivated alkenes bearing diverse functional groups are still in
urgent need.
substrates, diverse functional group tolerance, and excellent
regioselective control.
Alkenes are among the most important building blocks in organic
synthesis and can be largely prepared from industry. Transition-
metal-catalyzed functionalization of alkenes has emerged as a
powerful and practically useful tool kit for efficient construction of
C-C bonds.[1] However, precise functionalization such as
hydroarylation of unactivated alkenes is far less explored
compared with activated alkenes because of the low reactivity
and poor selectivity control on the non-biased C=C bond of the
unactivated alkenes. Moreover, from a mechanistic perspective,
the in situ formed C(sp3)-M intermediates prefer often to undergo
β-H elimination and give Heck-type products, which adds further
challenges for controlling the desired selectivity. Recently, a
novel coordination-assistance strategy has been developed for
transition-metal-catalyzed
arylative
functionalization
of
unactivated alkenes.[2-6] Great progress has been achieved
through prevailing Pd- and Ni-catalysis and a bidentate 8-
aminoquinoline (AQ) amide group was commonly adopted to
suppress β-H elimination of the intermediate C(sp3)-M species
benefitting from its rigid and bidentate coordination. In a few
cases, monodentate coordinating groups were utilized to deliver
Scheme 1. Transition-metal-catalyzed hydroarylation of unactivated alkenes
with boronic acids.
Manganese, as an earth-abundant transition metal, is a
potential candidate for new catalyst development in sustainable
chemistry.[8] So far, manganese-catalyzed hydroarylation of
alkynes via arylmanganese intermediates resulted from either C-
H activation of arenes[9] or transmetallation of arylboronic
acids[10] has been well developed since 2013. Also, manganese-
catalyzed hydroarylation of activated alkenes has been reported
since 2014.[11] However, the reactivity of arylmanganese species
to unactivated alkenes is surprisingly inert with only one report
from our group in 2018,[12] in which an aryl ketone was
necessitated to facilitate formation of five-membered
manganacycle and the ensuing olefination process with alkenes
via intramolecular H-transfer mechanism. As far as we are
aware, no manganese-catalyzed hydroarylation of unactivated
alkenes has been achieved so far. As our continued efforts on
manganese-catalysis, we herein describe the first manganese-
catalyzed hydroarylation of unactivated alkenes with boronic
acids (Scheme 1c), which features diverse functionalities such
[*]
T. Liu, Dr. Y. Yang, Prof. Dr. C. Wang
Beijing National Laboratory for Molecular Sciences, CAS key
Laboratory of Molecular Recognition and Function, CAS
Research/Education Center for Excellence in Molecular Sciences,
Institute of Chemistry, Chinese Academy of Sciences
Beijing 100190 (China)
E-mail: wangcy@iccas.ac.cn
Homepage: http://wangcy.iccas.ac.cn/
T. Liu, Dr. Y. Yang, Prof. Dr. C. Wang
University of Chinese Academy of Sciences
Beijing 100049 (China)
Dr. Y. Yang, Prof. Dr. C. Wang
Physical Science Laboratory, Huairou National Comprehensive
Science Center
Beijing 101400 (China)
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.

10.1002/anie.202003830
Angewandte Chemie International Edition
COMMUNICATION
as amide, imine, pyridine, amine, and ketone of unactivated
alkenes and excellent γ- or δ-regioselectivity complementary to
previous Rh-, Pd- or Ni-catalyzed reactions.
We initiated our study with internal alkene 1a and phenyl
boronic acid 2a as model substrates. After optimizing the
reaction parameters,[13] it turned out that γ-arylative product 3aa
were obtained in 95% isolated yield with excellent
regioselectivity under the conditions of MnBr(CO)5 (10 mol%),
o
K2CO3 (1.0 equiv.), THF (0.2 M), 100 C, and 12 h (Scheme 2).
Of note, control experiments without manganese catalysts gave
no product and the yield of 3aa decreased to 23% without base.
Among bases screened, the potassium ones demonstrated the
best performance. In addition, the substrate ratios had no
significant influence on the reaction yields. We then explored the
substrates scope of aryl boronic acids. Electron-varied
substituents on the benzene ring were well tolerated and gave
the corresponding products (3ab-ao) in good yields and
excellent regioselectivity. Functional groups like halogens, CF3,
ester, cyano, nitro, ketone, aldehyde, amine, phenol, and amide
were compatible and delivered an array of γ-arylated amides
successfully, which provided handles for further downstream
synthetic modifications. Reactions of meta- and ortho-
substituted arylboronic acids also proceeded with ease (3ap-as).
Naphthyl and heterocyclic boronic acids including furan,
thiophene, and indole moiety were all well tolerated (3at-aw). Of
particular note, a representative example of alkenylboronic acid
was also applicable successfully and delivered the
hydroalkenylation product (3ax) in a nearly quantitative yield
with excellent regio- and E/Z-selectivity. Next, the scope of
alkenes was investigated using phenylboronic acid (2a) as a
model reactant (Scheme 3). Alkenes bearing a series of N-free
and -substituted amide groups were compatible with the reaction
conditions and gave the corresponding products with success
(3ba-fa). Other internal alkenes with varied R1 groups delivered
the expected products smoothly (3ga, 3ha). In addition, terminal
alkenes and 1,1-disubstituted alkenes were well tolerated in the
reaction (3ia, 3ja).
Scheme 3. Scope of alkenes in γ-selective hydroarylation of alkenes with
amide groups. Reaction conditions: 1 (0.5 mmol), 2a (1.0 mmol), MnBr(CO)5
(0.05 mmol), K2CO3 (0.5 mmol), THF (2.5 mL), 100 oC, 12 h. Yields of the
isolated products were given. Ratios of 3/4 in crude reaction mixture were
determined by GC-MS and showed in the parenthesis. [a] The other regio-
isomer was not detected by 1H NMR. [b] 16 h. [c] 24 h. [d] 80 oC, 24 h.
To further extend the chemical space of this manganese-
based protocol, we tested the reactions of γ,δ-unsaturated
imines 5 with arylboronic acids 2 under the similar regime
(Scheme 4). It turned out that the reactions worked well and
tolerated diverse functional groups on arylboronic acids. Thus,
various δ-arylated ketones were delivered successfully after
hydrolysis (6aa-aj). Electron-deficient arylboronic acids
seemingly required higher temperature compared with those of
electron-rich ones (6ah-aj). In addition, meta-substituted aryl
and naphthalen-2-yl boronic acids gave the corresponding
products in good yields (6ak-an). Exemplificative variations of
imines proved also fine and the expected δ-arylated ketones
were approached without difficulty (6ba-ea).
MnBr(CO)5 (10 mol%)
R'
NEt2
NEt2
K2CO3 (1.0 equiv.)
THF, 100 oC, 12 h
NEt2
+
R'B(OH)2
R'
O
O
R
O
1a
2
3
4
3ah
, R = CF3, 94% (98/2)
R
3aa
, R = H, 95% (97/3)
3ab, R = Me, 93% (98/2)
3ai
, R = CO2Me, 92% (99/1)
3aj, R = CN, 98% (99/1)
3ac, R = OMe, 86% (96:4)
3ak
, R = COCH3, 99% (93/7)
[a]
NEt2
3ad
, R = Ph, 92%
3al
, R = NMe2, 82% (99/1)
3ae, R = F, 91% (98/2)
3af, R = Cl, 99% (99/1)
3ag
, R = Br, 93% (99/1)
O
NEt2
3am, R = CHO, 80% (97/3)
3an
3ao
[a]
3ap
, R = OMe, 93% (99/1)
3aq, R = Me, 91% (99/1)
, R = NO2, 91% (99/1)
, R = OH, 88%
O
, R = CONH2, 44% (98/2)
3ar
NH
X
Ph
NEt2
N
NEt2
NEt2
Scheme 4. Scope of δ-selective hydroarylation of alkenes with imine groups.
Reaction conditions: 5 (0.5 mmol), 2 (1.0 mmol), MnBr(CO)5 (0.05 mmol),
KOtBu (0.35 mmol), 4Å MS (100 mg), THF (2.5 mL), 100 oC, 12 h. Yields of
isolated products were given. Other regio-isomers were not detected by 1H
NMR. [a] 24 h. [b] 120 oC.
NEt2
O
[b]
O
, 89% (97/3)
O
O
O
[a]
3au
, X = S, 79%
3as
3at
, 96%
3av, X = O, 81%[b]
3aw
, 90% (97/3)
3ax
, 97% (99/1)
Scheme 2. Scope of boronic acids in γ-selective hydroarylation of alkenes
Another three representative functionalities for unactivated
alkenes in regio-selective hydroarylation were demonstrated in
Scheme 5. The pyridine functionality worked well and the
reactions gave the δ-arylated pyridines exclusively in high yields
(8fa, 8fb). We then tested the amenability of challenging
with amide groups. Reaction conditions: 1a (0.5 mmol),
2 (1.0 mmol),
MnBr(CO)5 (0.05 mmol), K2CO3 (0.5 mmol), THF (2.5 mL), 100 oC, 12 h.
Yields of the isolated products were given. Ratios of 3/4 in crude reaction
mixture were determined by GC-MS and showed in the parenthesis. [a] The
other regio-isomer was not detected by 1H NMR. [b] 36 h.
homoallylic amine
9
bearing simple unprotected amine
functionality upon our protocol (Scheme 5b). Fortunately, the
linear hydroarylation product 10 was accessed in excellent
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10.1002/anie.202003830
Angewandte Chemie International Edition
COMMUNICATION
MnBr(CO)5 (10 mol%)
K2CO3 (1.0 equiv.)
Ph
regioselectivity, which was in contrast to those cases using
protected amines in Pd-,[2e] Ni-,[5c] and Rh-catalysis[2f]. Simple
ketone functionality could also be applied in this manganese-
based regime and the expected hydroarylation products 12aa
and 12ba were afforded successfully from allyl phenyl and alkyl
ketone respectively (Scheme 5c). It should be noted that the
homoallyl ketone barely gave the corresponding product under
the current protocol.
NEt2
a)
b)
NEt2
+
(PhBO)3
neat, 100 oC, 12 h
O
O
1a
(0.1 mmol)
3aa
, 55%
(0.1 mmol)
Ph
K2CO3
(1.0 equiv.)
MnBr(CO)5
+
1a
+
(PhBO)3
3aa
NEt2
Mn-Ia, N.D.
THF
(CO)4Mn
100 oC, 12 h
92%
O
(0.1 mmol) (0.1 mmol) (0.1 mmol)
quenched
0.22 D
MnBr(CO)5 (10 mol%)
K2CO3 (1.0 equiv.)
Ph H3
H1
NEt2
NEt2
+
+
(PhBO)3
c)
d)
H3
D2O (3.0 equiv.)
O
H2
THF, 100 oC, 12 h
O
1a
(0.1 mmol)
0.1 D
(0.1 mmol)
3aa, 83%
MnBr(CO)5 (10 mol%)
K2CO3 (1.0 equiv.)
H3
Ph
H1
NEt2
NEt2
PhB(OH)2
H3
D2O (x equiv.)
THF, 100 oC, 12 h
O
H2
O
3aa
1a (0.1 mmol)
2a (0.2 mmol)
D of H1
D of H2
D of H3
D2O (x equiv.)
Yield (%)
2.0 equiv.
5.0 equiv.
10.0 equiv.
84
97
93
0
0
0
0.16
0.26
0.34
0.15
0.15
0.13
Scheme 6. Mechanistic experiments. 1H NMR yields and ratios were shown.
A plausible reaction mechanism is depicted in Scheme 7.
The reaction starts with the formation of ArMn(CO)5 from
MnBr(CO)5 and arylboronic acid 2 with the assistance of base
through a transmetallation process.[10] The release of CO ligands
and coordination of alkene 1 with ArMn(CO)5 delivers the
manganacycle Mn-II. Migratory insertion of the olefin moiety into
the C-Mn bond in Mn-II gives the manganacycle Mn-I. The ease
of forming different ring sizes of Mn-I was speculated to
determine the reaction regioselectivity. Protonation and further
transmetallation of Mn-I with arylboronic acid 2 afford Mn-III
species, which undergoes a ligand exchange with alkene 1
releasing the hydroarylation product and regenerating the
intermediate Mn-II.
Scheme 5. Alkenes with representative functionalities in manganese-
catalyzed hydroarylation. The isolated yields and regioselectivity of reactions
were given.
Experiments were further conducted to shed light on the
possible reaction mechanism. Firstly, we conducted the reaction
of 1a with (PhBO)3 under neat conditions, and to our surprise,
the product 3aa was formed in 55% NMR yield (Scheme 6a).
This result suggested that the possible manganacycle
intermediate Mn-Ia (vide infra) was susceptible to the small
amount of residual water in the reaction system. To further test
this, a stoichiometric reaction of MnBr(CO)5, alkene 1a, and
(PhBO)3 was carried out (Scheme 6b). After completion of the
reaction, Mn-Ia and 1a were not detected and instead 3aa was
observed in crude NMR analysis, which confirmed our
assumption. Then, external D2O was added to the reaction
system and product 3aa was obtained in higher yield with partial
deuteration of H2 and H3 (Scheme 6c). Similar results were
observed for the reactions using phenylboronic acid 2a and
increasing the amount of D2O in the reactions led to a higher
extent of deuteration on H2 (Scheme 6d), which suggested the
intermediacy of Mn-Ia. Of note, the deuteration of H3 might
originate from base-promoted H/D scrambling.[2i]
ArB(OH)
base
2 2
Ar
MnBr(CO)5
ArMn(CO)5
FG
R
R
- 2CO
R
(CO)4Mn
X
1
favored
FG
R
product + CO
CO
Mn
Ar
(CO)3
1
Ar
Ar
X
Mn
Mn-II
(CO)4
less
favored
Ar
Ar
FG
FG
Mn
(CO)4
Mn-I
R
H
Mn(CO)4
Ar
R
R
Mn-III
X
Mn
(CO)4
H+, ArB(OH)2
unfavored
Scheme 7. A tentative reaction mechanism.
In conclusion, the first manganese-catalyzed hydroarylation of
unactivated alkenes with arylboronic acids has been developed
through a diverse functionality-coordination strategy. A series of
δ- or γ-arylated amides, ketones, pyridines, and amines was
accessed in excellent regioselectivity. Hydroalkenylation with
olefinic boronic acids was also amenable to this manganese-
based protocol. The reactions featured earth-abundant
manganese catalysis, easily available substrates, diverse
functional group tolerance, and excellent regioselective control.
This article is protected by copyright. All rights reserved.

10.1002/anie.202003830
Angewandte Chemie International Edition
COMMUNICATION
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Further explorations on manganese-catalyzed functionalization
of unsaturated hydrocarbons are underway in our laboratory.
Acknowledgements
[6]
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Financial support from Beijing Municipal Science & Technology
Commission (project No. Z191100007219009), the National
Natural Science Foundation of China (21772202, 21831008),
and Beijing National Laboratory for Molecular Sciences
(BNLMS-CXXM-201901) are gratefully acknowledged. We also
thank the Alexander von Humboldt Foundation for the
Equipment Subsidy.
Keywords: Manganese • Alkenes • Hydroarylation •
Hydroalkenylation • Homogeneous Catalysis
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10.1002/anie.202003830
Angewandte Chemie International Edition
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Ting Liu, Yunhui Yang and Congyang Wang*
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Manganese-Catalyzed Hydroarylation of
Unactivated Alkenes
The first manganese-catalyzed hydroarylation of unactivated alkenes bearing
diverse simple functionalities with arylboronic acids was developed. A series of
δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with
excellent regioselectivity and in high yields. Hydroalkenylation with olefinic
boronic acids was also amenable to this manganese-based protocol.
This article is protected by copyright. All rights reserved.

10.1002/anie.202003830
Angewandte Chemie International Edition
COMMUNICATION
This article is protected by copyright. All rights reserved.