Cobalt(III)-Catalyzed and Dimethyl Sulfoxide-Involved Cross-Coupling of Ketones and Amides for Direct Synthesis of β-Amino Ketones

Article abstract of DOI:10.1002/adsc.201900717

A straightforward synthesis of β-amino ketones has been realized by employing ketones and amides as the substrates via cobalt(III)-catalyzed and dimethyl sulfoxide-involved cross-coupling reaction. Experimental investigations revealed that the β-methylsul

Full text of DOI:10.1002/adsc.201900717

Title: Cobalt(III)-Catalyzed and Dimethyl Sulfoxide-Involved Cross-
Coupling of Ketones and Amides for Direct Synthesis of β-Amino
Ketones
Authors: Feng Xu, Zhi Zhou, Zhipin Wang, Xinna Ma, Xin Chen, Xu
Zhang, Xiyong Yu, and Wei Yi
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900717
Link to VoR: http://dx.doi.org/10.1002/adsc.201900717

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Cobalt(III)-Catalyzed and Dimethyl Sulfoxide-Involved Cross-
Coupling of Ketones and Amides for Direct Synthesis of β-
Amino Ketones
Xuefeng Xu,+a Zhi Zhou,+b Zhipin Wang,a Xinna Ma,a Xin Chen,a Xu Zhang,a,* Xiyong
Yub,* and Wei Yia,b,*
a
Engineering Technology Research Center of Henan Province for Solar Catalysis, College of Chemistry and
Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, China
Fax: (+86)-20-37104196); phone: (+86)-20-37104196
E-mail: yiwei@gzhmu.edu.cn; zhangxuedu@126.com
Key Laboratory of Molecular Target and Clinical Pharmacology & State Key Laboratory of Respiratory Disease,
b
School of Pharmaceutical Sciences & the Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou,
Guangdong 511436, China
E-mail: yuxycn@aliyun.com
These authors contributed equally to this work.
+
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A straightforward synthesis of β-amino ketones has and cyclicamides) with various substitution patterns were
been realized by employing ketones and amides as the found to be applicable to this transformation,
substrates via cobalt(III)-catalyzed and dimethyl sulfoxide- demonstrating a broad substrate scope and excellent
involved cross-coupling reaction. Experimental investigations functional group tolerance.
revealed that the β-methylsulfide ketone species might be
involved as the active intermediate. Diverse ketones (e.g. Keywords: Cobalt(III) catalysis; Dimethyl sulfoxide;
acetophenone and its derivatives, heteroaryl methyl ketones Ketones; Amides; β-Amino ketones.
and dibenzoylmethane) and amides (e.g. aromatic, aliphatic
manner.[4-6]
Although
numerous
versatile
Introduction
protocols have been disclosed by second-row
transition metals, most of these methods mainly
relied on the activation of ketones to enamines
and/or enones which employed single electron
β-Amino ketones have played an important role
in organic chemistry and drug discovery owing to
their
unique
properties
and
potential
pharmaceutical applications.[1] Consequently,
tremendous efforts have been focused on
exploring the efficient methodologies toward
their synthesis.[2-3] By reviewing these
developments, two classic procedures for the
construction of β-amino ketones have been stood
out (Scheme 1a),[2] namely: (1) the aza-Michael
reaction involving the addition of nitrogen
nucleophiles on α,β-unsaturated carbonyl
compounds, (2) the Mannich reaction between
imines and enolates. However, the two methods
usually not only require the highly functionalized
starting materials, harsh conditions as well as the
corrosive reagents but also give relatively poor
yields or limited substrate scope.
To
overcome
the
above
mentioned
disadvantages, recently developed direct C-H
amination has emerged as one of the most
powerful tools for the construction of β-amino
ketones in a highly step- and atom-economic
Scheme 1. Strategies for building the β-amino ketone
framework.
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
oxidation and conjugated addition, respectively,
synthesis of β-amino ketones from ketones,
as the key step. For example, Su and co-workers amides and DMSO via a tandem in situ β-
reported the copper-catalyzed direct β- methylsulfide generation/cobalt(III)-catalyzed C-
functionalization of saturated ketones, in which
the ketones were initially desaturated by
N reductive elimination process (Scheme 1c).
Mechanistic studies validated that DMSO was
stoichiometric TEMPO, followed by a catalytic used as the carbon source to involve the
conjugated addition (Scheme 1b-1).[5] A similar formation of the β-methylsulfide intermediate
work was reported by Kuwano and co-workers, in followed by cobalt(III)-catalyzed facile amination.
which the nickel-catalyzed formation of the C-N
bond at the β-position of propiophenone was
Results and Discussion
involved and the α,β-unsaturated ketone species
were employed as the active intermediate
(Scheme 1b-2).[6] Moreover, the use of PMe3
ligand together with an additional reduction step
was inevitable for achieving the β-amino ketones
in their work, which limited the utility potential
of such reactions. Therefore, the development of
more step- and atom-economic synthetic strategy
to build the β-amino ketones is still highly desired.
Over the past decades, exploring the
environmental friendly protocol for the efficient
synthesis of structurally diverse and complex
compounds from simple raw materials
represented one of the most challenging tasks.
For this topic, the cheap and commercially
available polar aprotic solvents with relatively
low toxicity, such as DMF,[7] DMA,[8] MeOH,[9]
and DMSO,[10] have shown great potential being
used as the versatile synthons in organic synthesis.
Accordingly, such strategy has been applied in
constructing β-amino ketones via cobalt(II)-
To test the feasibility of the proposed concept,
we first investigated the model reaction by
choosing the simple and cheap Co(acaac)3 as the
catalyst. To our delight, the treatment of
acetophenone (1a) with benzamide (2a) in the
presence of AgNTf2 and K2S2O8 furnished the
desired
β-amination
product
N-(2-
benzoylallyl)benzamide (3a) and N-(3-oxo-3-
phenylpropyl)benzamide (3aa) in 41% and 17%
yields, respectively (Table 1, entry 1).
Encouraged by this promising result and
considering the meaningful structure of 3a
(belong to allyl amine species) that was difficult
to synthesize via conventional reactions, we
further screened several parameters including
peroxides, silver sources and the cobalt catalysts
systemically to establish the optimized conditions
for the direct synthesis of 3a. The results revealed
that other peroxides such as (NH4)2S2O8, Na2S2O8
as well as TBHP were less effective (entries 2-4).
After a number of trials to screen different silver
salts, AgOAc was found to be superior to other
candidates (entries 5-9), increasing the yield of 3a
up to 76% with excellent selectivity (no 3aa was
detected). Further investigation showed that no
desired product was found in changing AgOAc to
either NaOAc or CsOAc (entries 10-11),
suggesting that the introduction of the AgOAc
species was essential for the Co(III)-catalyzed
reaction. Switching the solvent from DMSO to
other reaction media also gave inferior results
(entries 12-13). The control experiment
demonstrated that either the cobalt(III) catalyst or
AgOAc/K2S2O8 additives was essential for this
transformation (entries 14-16). Other cobalt
species resulted in the sharp reduction on both the
yield and the selectivity or completely inhibited
the process (entries 17-20). Especially, the
Cp*Co(III) species that had shown a good
catalytic activity in our previous work[18] was
failed to provide the desired product 3a (entry 15),
instead, 2-((methylthio)methyl)-1-phenylprop-2-
en-1-one was obtained as the main products with
85% yield.[19] Taken together, the results revealed
that the type and nature of the ligand attached in
catalyzed
α-methoxymethylation
and
α-
aminomethylation, in which MeOH was used as
the carbon source (Scheme 1b-3). Compared to
MeOH, DMSO can provide not only the
methylene (-CH2-) synthon, but also other
functional groups including -O,[11] -SMe,[12]
-
CH2SMe,[13] -SO2Me,[14] -Me,[15] -CN[16] and -
CHO.[17] Noteworthily, in view of the good
leaving effect of the -SMe moiety, utilizing
DMSO to install -CH2SMe has selected as a
powerful strategy to elongate the carbon chain
through the formation of the weak C-S bond. In
the course of our studies focusing on the
development of earth-abundant and inexpensive
cobalt-catalyzed C-H functionalization, we have
developed a cobalt(III)-catalyzed C-H activation
strategy for one-pot construction of the quinoline
framework using DMSO as the C1 source, which
further highlighted the compatibility and
application of DMSO-involved system in
cobalt(III)-catalyzed C-N coupling reactions.[18]
On the basis of these advances, we envisaged
that the easily formed β-methylsulfide ketones,
derived from the coupling of enols/enolates and
DMSO in the presence of external oxidant, could
be readily converted into β-amino ketones via
cobalt(III)-catalyzed transformation with amides
to form the C-N bond. Therefore, we herein
would like to disclose a novel strategy for the
Co(III) metal played
a
decisive role in
determining the reaction outcome, and in current
cases, the acac ligand was optimal. Subsequently,
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
Scheme 2. Scope of ketones and amides.[a]
the effect of the reaction temperature was
investigated. The results showed that the coupling
at 130 °C gave the most satisfying result (entries
8, 21 and 22), revealing that a balance between
the decomposition of the substrate and the
formation of the product might exist in the
reaction. In addition, lowering the loading of
K2S2O8 to 1.0 equiv led to a significant decrease
in the product yield (entry 23). No distinct
difference in product yield was observed when
the amount of K2S2O8 was extended to 3.0 equiv
(entry 24).
Table 1. Optimization of reaction conditions.[a]
Yield[b] (%)
entry
catalyst
additive
oxidant
3a
3aa
1
AgNTf2
AgNTf2
AgNTf2
AgNTf2
Ag2SO4
AgNO3
Ag2CO3
AgOAc
AgOTf
NaOAc
CsOAc
AgOAc
AgOAc
AgOAc
/
41
17
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
/
K2S2O8
(NH4)2S2O8
Na2S2O8
TBHP
[a]Reaction conditions: ketone
mmol), Co(acac)3 (5 mol %), AgOAc (10 mol %) and
K2S2O8 (2.0 equiv) in DMSO (2 mL) at 130 °C for 12 h
under air; isolated yields were reported.
1 (0.5 mmol), amide 2 (0.6
0
11
0
0
0
2
3
0
4
0
0
5
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
/
proceeded to investigate the substrate scope of
this transformation with respect to the use of
diverse aryl ketones. As enumerated in Scheme 2,
a variety of acetophenone analogues bearing
either electron-donating or electron-withdrawing
groups were initially evaluated. The results
displayed that these substrates were fully
compatible to the reaction conditions to give the
desired products in moderate to good yields,
revealing that the electronic and steric effects of
the substituents on the aryl ring had no obvious
influence on the reaction outcome. Various
commonly encountered functional groups
6
31
0
0
7
0
76
51
0
0
8
0
9
0
10
11
12[c]
13[d]
14
15
16
17
18
19[e]
20
21[f]
22[g]
23[h]
24[i]
0
0
0
0
0
0
0
0
0
0
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
including halogens (3b
3i) and phenyl (3j) were well tolerated
regardless of the substituted position on the
phenyl ring (3k ). In addition, the disubstituted
aryl ketones were found to be viable substrates
3o ), affording the corresponding products in
-e), alkyl (3f-h), methoxy
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
14
16
21
0
0
(
69
14
0
Co(acac)2
Co(OAc)2
Cp*Co(CO)I2
CoI2
-n
(
-r
0
0
excellent yields (86-91%). Interestingly, this
protocol could also be extended to polyaromatic
naphthyl ketones, furnishing the desired β-
58
62
49
78
0
Co(acac)3
Co(acac)3
Co(acac)3
Co(acac)3
0
amination products in 79% (3s) and 88% (3t
)
0
yields, respectively. It was worth noting that the
heteroaryl methyl ketone 1-(thiophen-3-yl)ethan-
1-one was also compatible to this transformation,
producing the desired product 3u in 77% yield.
Gratifyingly, further examination indicated that
this reaction was not limited to the methyl ketone
substrates. When 1,2-diphenylethanone was
subjected to the standard conditions, the
corresponding product 3v was obtained smoothly
in 82% yield. Moreover, benzamides bearing
different substituents on the phenyl ring also
reacted efficiently with acetophenone 1a to
deliver the corresponding products in moderate to
0
[a]Reaction conditions: acetophenone 1a (0.5 mmol), benzamide
2a (0.6 mmol), catalyst (5 mol %), additive (10 mol %) and
oxidant (2.0 equiv) in DMSO (2 mL) at 130 °C for 12 h under air.
[b]Isolated yield after chromatography.
[c]In DMF.
[d]In DMA.
[e]For details, see reference 19.
[f]At 110 oC.
[g]At 150 oC.
[h]With 1.0 equiv of K2S2O8.
[i] With 3.0 equiv of K2S2O8.
With the optimized conditions in hand, we
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
good yields
(
3w
-
y
), illustrating the good was used as both the solvent and two carbon
substrate compatibility of the Co(III)-catalyzed synthons in this reaction. Subsequently, the
system.
Scheme 4. Mechanistic studies.
Scheme 3. Scope of amides with the reaction of
dibenzoylmethane.[a]
[a]Reaction conditions: ketone
1 (0.5 mmol), amide 2 (0.6
mmol), Co(acac)3 (5 mol %), AgOAc (10 mol %) and
K2S2O8 (2.0 equiv) in DMSO (2 mL) at 130 °C for 12 h
under air; isolated yields were reported.
Inspired by the above mentioned results, the
scope of amides was further investigated with the
reaction of a new diketone substrate under the
optimized reaction conditions (Scheme 3).
Fortunately, various benzamides bearing different
electronic properties reacted smoothly with
reaction was performed in the absence of benzamide
under standard conditions for 2 h, generating the
intermediate 6 in 87% yield. Further treatment of 6
with benzamide 2a led to the desired β-amination
product 3a in 74% yield (Scheme 4b). Taken together,
these results provided clear evidence that 6 should be
an active intermediate involved in this transformation.
Next, the reaction of dibenzoylmethane with DMSO
in the absence of benzamide under the otherwise
identical conditions was also carried out. As
predicted, the similar β-methylsulfide intermediate 7
was obtained smoothly in 91% yield, which could be
further converted into β-amino ketone 4a in the
presence of 2a (Scheme 4c). No desired product was
observed when either 6 or 7 was treated with 2a
without adding any cobalt(III) catalyst or K2S2O8
(Schemes 4b-c), revealing that both the catalyst and
the oxidant were crucial for the two reaction system.
Control experiment revealed that no aza-Michael
addition product was detected with 1-phenylprop-2-
en-1-one substrate under the standard conditions
(Scheme 4d), which further confirmed the vital role
of the β-methylsulfide ketone species in this
transformation.
dibenzoylmethane
(
1w)
to
yield
the
corresponding products 4a-d in high yields (74-
92%). Moreover, 2,6-difluorobenzamide could be
totally transformed to the desired product in a
synthetically useful yield (4e), indicating good
steric tolerance of the developed Co(III)-
catalyzed system. Notably, cyclic amides and
aliphatic amides could also be accommodated
with the reaction conditions to give the
corresponding products in good yields (4f-h).
Remarkably, several amides derived from the
natural products and biological active molecules,
including adamantane-1-carboxamide, coumarin-
3-carboxamide and N-phthaloyl-L-phenylalanine
derivative, also reacted with 1w smoothly to yield
the desired β-amino ketones (4i-k) in good yields,
which illustrated profound potentials for the rapid
synthesis of novel analogs of such motifs.
Given the effective synthetic routes for the
facile construction of β-amino ketone derivatives,
we were next intrigued to conduct a series of
experimental investigations to probe the reaction
mechanism (Scheme 4). Firstly, deuterium-
labeling experiment was carried out, which
To further reveal the role of the Co catalyst,
several reactions were then designed in the
Co(acac)2-catalyzed system. Firstly, treatment of 1a
in the absence of 2a for 4 h gave 6 in 17% yield
(Schemes 4e). Moreover, the treatment of 2a in the
resulted in the formation of deuterated product
5
with more than 99% incorporation of deuterium
at the two methylene positions in the presence of
DMSO-d6 (Scheme 4a), revealing that DMSO
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
Scheme 5. Proposed catalytic cycle.
presence of K2S2O8 and DMSO provided the
methylenebisamide species 8 in good yield (Schemes
4f). Finally, the cross-coupling was easily achieved
by heating 1a and 8 with Co(acac)2, K2S2O8 and
AgOAc in DMSO for 12 h to deliver 3aa as the final
product in decent yield (Schemes 4g). To sum up,
these
results
suggested
that:
(a)
the
methylenebisamide species (8) might act as the active
intermediate to involve this transformation for the
synthesis of 3aa, and (b) two independent, side-by-
side, and competitive reactions from 1a and the
generated 6 with 8 might exist in the Co(II) catalysis,
thereby yielding the mixed 3a and 3aa as the final
products, which was in consistent with our
experimental observation in conditions optimization.
On the basis of our experimental results and
literature precedents,[10,18,20,21] two plausible cobalt-
catalyzed oxidative reaction pathways for the tunable
synthesis of 3a and 3aa were depicted in Scheme 5.
Initially, the DMSO is oxidized by K2S2O8 to yield
intermediate A, which is attacked by the enolate
intermediate 1aa derived from the ketone 1a, thus
giving the bisalkylsulfurized intermediate D via
intermediates B and C. Then, D delivers α-
methylene-β-methylsulfide ketone species 6 with the
emission of MeSH. On the other hand, A can also be
attacked by the amide substrate (2a) to produce the
intermediate B', which further reacts with an
additional 2a via a classical nucleophilic substitution
to provide the methylenebisamide 8, followed by the
Conclusion
In summary, we have developed, for the first
time, a cobalt(III)-catalyzed and DMSO-involved
cross-coupling of ketones with amides to give
direct access of β-amino ketones, in which
DMSO was employed as both the solvent and the
one or two carbon building block. The
remarkable features of this methodology include
the simple and readily available starting materials,
excellent substrate/functional group tolerance,
mild reaction conditions and high efficiency,
thereby rendering it as a highly versatile and
atom-economical alternative to the existing
cleavage of the C-N bond to give G and H. The protocols for building the β-amino ketone
framework. Through a set of mechanistic
investigations, the β-methylsulfide ketone species
was identified as the active intermediate and a
possible reaction pathway was rationally derived.
Systematic studies on the mechanism and
application of such transformation are in progress
in our laboratories.
cobalt(III) species is coordinated with G in the
presence of 6 to provide the intermediate E via the
cleavage of the second C-S bond. Subsequent
reductive elimination of the C-N bond gives the
intermediate F. Finally, protodemetallation of F
provides the final product 3a. Alternatively, the
reaction of H with the cobalt(II) catalyst gives the
five-membered cobalt(III) species I. The insertion of
1aa into the C-Co bond gives a seven-membered
metalacycle (J), which undergoes β-hydride
elimination/protonolysis to give the final product 3aa
via the intermediate K. However, more investigations
are still needed to authenticate the above proposed
mechanism.
Experimental Section
General procedure for the synthesis of β-amino ketones
A reaction flask (25 mL) was charged with ketone 1 (0.5
mmol, 1.0 equiv), amide 2 (0.6 mmol, 1.2 equiv),
Co(acac)3 (9.0 mg, 5.0 mol %), AgOAc (8.4 mg, 10.0
mol %) and K2S2O8 (1.0 mol, 270 mg, 2.0 equiv), then the
DMSO (4 mL) was added. The mixture was stirred at 130
oC for 12 hours under an atmosphere of air. After the
reaction finished, the resulted mixtures were diluted with
20 mL of dichloromethane and washed with 20 mL of H2O.
The aqueous layer was extracted twice with
dichloromethane (10 mL) and the combined organic phase
was dried over Na2SO4. After evaporation of the solvents,
the residue was purified by silica gel chromatography
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
Dai, H. B. Mei, J. L. Han, V. A. Soloshonok, Y.
Pan, Chem. Commun. 2015, 51, 9149; f) C. Xie, L.
J. Zhang, W. X. Sha, V. A. Soloshonok, J. L. Han,
Y. Pan, Org. Lett. 2016, 18, 3270; g) J. Wen, Y. L.
Luo, H. Z. Zhang, H. H. Zhao, C. H. Zhou, G. X.
Cai, Chin. Chem. Lett. 2016, 27, 391.
(hexane/AcOEt = 15 : 1 - 8 : 1) to yield the corresponding
β-amino ketone product 3.
[4] a) A. Alanthadka, E. S. Devi, A. T. Selvi, S.
Nagarajan, V. Sridharan, C. U. Maheswari, Adv.
Synth. Catal. 2017, 359, 2369; b) K. Sun, X. Wang,
Y. Jiang, Y. Lv, L. Zhang, B. Xiao, D. Li, Z. Zhu,
L. Liu, Chem. Asian J. 2015, 10, 536; c) R. Tao, Y.
Yin, Y. Duan, Y. Sun, Y. Sun, F. Cheng, J. Pan, C.
Lu, Y. Wang, Tetrahedron 2017, 73, 1762; d) P.
Qian, Y. Deng, H. Mei, J. Han, Y. Pan, Chem.
Commun. 2017, 53, 2958; e) K. Sun, Z. Zhu, J. Sun,
L. Liu, X. Wang, J. Org. Chem. 2016, 81, 1476; f)
A reaction flask (25 mL) was charged with diketone 1w
(0.5 mmol, 1.0 equiv), amide 2 (0.6 mmol, 1.2 equiv),
Co(acac)3 (9.0 mg, 5.0 mol %), AgOAc (8.4 mg, 10.0
mol %) and K2S2O8 (1.0 mol, 270 mg), then the DMSO (4
o
mL) was added. The mixture was stirred at 130 C for 12
hours under an atmosphere of air. After the reaction
finished, the resulted mixtures were diluted with 20 mL of
dichloromethane and washed with 20 mL of H2O. The
aqueous layer was extracted twice with dichloromethane
(10 mL) and the combined organic phase was dried over
Na2SO4. After evaporation of the solvents, the residue was
purified by silica gel chromatography (hexane/AcOEt =
10 : 1 - 3 : 1) to yield the corresponding N-(2-benzoyl-3-
oxo-3-phenylpropyl) amide derivative 4.
N. Fu, L. Zhang, S. Luo, Org. Biomol. Chem. 2018
16, 510; g) S. Avidan-Shlomovich, H. Ghosh, A.
M. Szpilman, ACS Catal. 2015, 5, 336.
,
[5] X. Jie, Y. Shang, X. Zhang, W. P. Su, J. Am. Chem.
Soc. 2016, 138, 5623.
[6] S. Ueno, R. Shimizu and R. Kuwano, Angew.
Chem. Int. Ed. 2009, 48, 4543.
[7] a) Y. Li, D. Xue, W. Lu, C. Wang, Z. T. Liu, J.
Xiao, Org. Lett. 2014, 16, 66; b) A. Borah, L.
Goswami, K. Neog and P. Gogoi, J. Org. Chem.
2015, 80, 4722; c) F. Pu, Y. Li, Y. H. Song, J. Xiao,
Z. W. Liu, C. Wang, Z. T. Liu, J. G. Chen, J. Lu,
Adv. Synth. Catal. 2016, 358, 539; d) S. Mondal, S.
Samanta, S. Santra, A. K. Bagdi, A. Hajra, Adv.
Synth. Catal. 2016, 358, 3633.
Acknowledgements
We thank the National Natural Science Foundation of
China (21502100 and 21877020), the Science and
Technology Programs of Guangdong Province
(2015B020225006), Natural Science Funds for
Distinguished Young Scholar (2017A030306031),
[8] a) P. Kaswan, N. K. Nandwana, B. DeBoef, A.
Kumar, Adv. Synth. Catal. 2016, 358, 2108; b) A.
Modi, W. Ali, B. K. Patel, Adv. Synth. Catal. 2016
,
358, 2100; c) M. L. Deb, P. J. Borpatra, P. J.
Saikiab, K. Baruah, Org. Biomol. Chem. 2017, 15,
1435; d) M. Itoh, K. Hirano, T. Satoh, M. Miura,
Org. Lett. 2014, 16, 2050; e) J. Liu, H. Yi, X.
Zhang, C. Liu, R. Liu, G. Zhang, A. Lei, Chem.
Commun. 2014, 50, 7636; f) J. Chen, J. B. Feng, K.
Natte, X. F. Wu, Chem.-Eur. J. 2015, 21, 16370; g)
C. Wang, S. Lei, H. Cao, S. Qiu, J. Liu, H. Deng, C.
Yan, J. Org. Chem. 2015, 80, 12725; h) R. B.
Sonawane, N. K. Rasal, S. V. Jagtap, Org. Lett.
2017, 19, 2078.
Medical
Scientific
Research
Foundation
of
Guangdong Province (A2018421), and Natural
Science Foundation Research Team of Guangdong
Province (2018B030312001) for financial support on
this study.
References
[9] a) S. Kim, S. H. Hong, Adv. Synth. Catal. 2017
359, 798; b) M. Mastalir, E. Pittenauer, G.
Allmaier, K. Kirchner, J. Am. Chem. Soc. 2017
,
[1] a) B. Stanovnik, J. Svete, Chem. Rev. 2004, 104,
2433; b) M. Arend, B. Westermann, N. Risch,
Angew. Chem. Int. Ed. 1998, 37, 1044; c) F. F.
Blicke, Org. React. 1942, 1, 303; d) M. Tramontini,
,
139, 8812; c) K. Natte, H. Neumann, M. Beller, R.
V. Jagadeesh, Angew. Chem. Int. Ed. 2017, 56,
6384; d) L. K. M. Chan, D. L. Poole, D. Shen, M.
P. Healy, T. J. Donohoe, Angew. Chem. Int. Ed.
2014, 53, 761; e) D. Shen, D. L. Poole, C. C.
Shotton, A. F. Kornahrens, M. P. Healy, T. J.
Donohoe, Angew. Chem. Int. Ed. 2015, 54, 1642; f)
X. Quan, S. Kerdphon, P. G. Andersson, Chem.-
Eur. J., 2015, 21, 3576; g) S. Ogawa and Y. Obora,
Chem. Commun. 2014, 50, 2491; h) T. T. Dang, A.
M. Seayad, Adv. Synth. Catal. 2016, 358, 3373; i)
Z. Liu, Z. Yang, X. Yu, H. Zhang, B. Yu, Y. Zhao,
Z. Liu, Org. Lett. 2017, 19, 5228; j) K. Polidano, B.
D. W. Allen, J. M. J. Williams, L. C. Morrill, ACS
Catal. 2018, 8, 6440; k) J. Yang, S. Chen, H. Zhou,
C. Wu, B. Ma, J. Xiao, Org. Lett. 2018, 20, 6774.
[10] a) X. Wu, J. J. Zhang, S. Liu, Q. H. Gao, A. X. Wu,
Adv. Synth. Catal. 2016, 358, 218; b) Y. F. Liu, X.
Zhan, P. Y. Ji, J. W. Xu, Q. Liu, W. P. Luo, T. Q.
Chen, C. C. Guo, Chem. Commun. 2017, 53, 5346;
c) Y. F. Liu, P. Y. Ji, J. W. Xu, Y. Q. Hu, Q. Liu,
W. P. Luo, C. C. Guo, J. Org. Chem. 2017, 82,
7159; d) Z. K. Wen, X. H. Liu, Y. F. Liu, J. B.
Chao, Org. Lett. 2017, 19, 5798.
Synthesis 1973
, 703; e) M. Tramontini, L.
Angiolini, Tetrahedron 1990, 46, 1791; f) S.
Kobayashi, H. Ishitani, Chem. Rev. 1999, 99, 1069;
g) S. Kobayashi, K. Kakumoto, M. Sugiura, Org.
Lett. 2002, 4, 1319.
[2] For selected reviews, see: a) J. M. M. Verkade, L. J.
C. van Hemert, P. J. L. M. Quaedflieg, F. P. J. T.
Rutjes, Chem. Soc. Rev. 2008, 37, 29; b) S.
Kobayashi, Y. Mori, J. S. Fossey, M. M. Salter,
Chem. Rev. 2011, 111, 2626; c) H. Pellissier, Chem.
Rev. 2016, 116, 14868; d) L. Hong, W. Sun, D.
Yang, G. Li, R. Wang, Chem. Rev. 2016, 116, 4006;
e) J. P. Reid, L. Simon, J. M. Goodman, Acc. Chem.
Res. 2016, 49, 1029.
[3] For representative examples, see: a) J. Z. Chan, W.
Yao, B. T. Hastings, C. K. Lok, M. Wasa, Angew.
Chem. Int. Ed. 2016, 55, 13877; b) H. Zhang, B.
Yang, Z. Yang, H. Lu, G. Li, J. Org. Chem. 2016
,
81, 7654; c) L. Parise, L. Pellacani, F. Sciubba, L.
Trulli, S. Fioravanti, J. Org. Chem. 2015, 80, 8300;
d) H. N. Yuan, S. Li, J. Nie, Y. Zheng, J. A. Ma,
Chem.-Eur. J. 2013, 19, 15856; e) C. Xie, Y. L.
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
[11] a) S. Song, X. Huang, Y. F. Liang, C. Tang, X. Li,
[16] K. Zheng, B. Liu, S. Y. Chen, F. Chen,
N. Jiao, Green Chem. 2015, 17, 2727; b) Q. Gao, X.
Tetrahedron Lett. 2013, 54, 5250.
Wu, S. Liu, A. X. Wu, Org. Lett. 2014, 16, 1732; c) [17] a) H. Fei, J. Yu, Y. Jiang, H. Guo, J. Cheng, Org.
R. Tomita, Y. Yasu, T. Koike, M. Akita, Angew.
Chem. Int. Ed. 2014, 53, 7144; d) Y. Ashikari, T.
Nokami, J. Yoshida, J. Am. Chem. Soc. 2011, 133,
11840; e) R. Xu, J. P. Wan, H. Mao, Y. Pan, J. Am.
Chem. Soc. 2010, 132, 15531.
Biomol. Chem. 2013, 11, 7092; b) J. Qian, Z.
Zhang, Q. Liu, T. Liu, G. Zhang, Adv. Synth. Catal.
2014, 356, 3119; c) Z. Zhang, Q. Tian, J. Qian, Q.
Liu, T. Liu, L. Shi, G. Zhang, J. Org. Chem. 2014
,
79, 8182; d) H. Cao, S. Lei, N. Li, L. Chen, J. Liu,
H. Cai, S. Qiu, J. Tan, Chem. Commun. 2015, 51,
1823; e) G. Chu, Z. Yu, F. Gao, C. Li, Synth.
Commun. 2013, 43, 44.
[12] a) F. L. Liu, J. R. Chen, Y. Q. Zou, Q. Wei, W. J.
Xiao, Org. Lett. 2014, 16, 3768; b) K. Mal, A.
Sharma, P. R. Maulik, I. Das, Chem.-Eur. J., 2014
,
20, 662; c) Q. H. Gao, X. Wu, Y. H. Li, S. Liu, X.
G. Meng, A. X. Wu, Adv. Synth. Catal. 2014, 356,
2924; d) L. L. Chu, X. Y. Yue, F. L. Qing, Org.
Lett. 2010, 12, 1644; e) G. D. Yin, B. H. Zhou, X.
G. Meng, A. X. Wu, Y. J. Pan, Org. Lett. 2006, 8,
2245. f) F. Luo, C. D. Pan, L. P. Li, F. Chen, J.
Cheng, Chem. Commun. 2011, 47, 5304.
[18] X. Xu, Y. Yang, X. Zhang, W. Yi, Org. Lett. 2018
20, 566.
,
[19] When the Cp*Co(CO)I2 species was employed to
replace Co(acac)3 as the Co(III) catalyst, treatment
of 1a and 2a under otherwise identical conditions
gave the 2-((methylthio)methyl)-1-phenylprop-2-
en-1-one as the dominant products, in which 3a
was not detected. For detailed information, please
see below:
[13] a) G. Hu, J. X. Xu, P. F. Li, Org. Lett. 2014, 16,
6036; b) J. Liu, X. X. Wang, H. Guo, X. K. Shi, X.
Y. Ren, G. S. Huang, Tetrahedron 2012, 68, 1560;
c) T. Shen, X. Q. Huang, Y. F. Liang, N. Jiao, Org.
Lett. 2015, 17, 6186.
[14] a) G. Q. Yuan, J. H. Zheng, X. F. Gao, X. W. Li, L.
B. Huang, H. G. Chen, H. F. Jiang, Chem.
Commun. 2012, 48, 7513; b) Y. J. Jiang, T. P. Loh,
Chem. Sci. 2014, 5, 4939; c) X. F. Gao, X. J. Pan, J.
Gao, H. W. Huang, G. Q. Yuan, Y. W. Li, Chem.
Commun. 2015, 51, 210.
[15] a) X. Ren, J. Chen, F. Chen, J. Cheng, Chem.
Commun. 2011, 47, 6725; b) J. Jia, Q. Jiang, A.
Zhao, B. Xu, Q. Liu, W. P. Luo, C. C. Guo,
Synthesis 2016, 48, 421; c) G. Chu, Z. Yu, F. Gao,
C. Li, Synth. Commun. 2013, 43, 44; d) Z. G.
Zhang, Q. Tian, J. J. Qian, Q. F. Liu, T. X. Liu, L.
Shi, G. S. Zhang, J. Org. Chem. 2014, 79, 8182.
[20] a) F. Xiao, C. Liu, S. Yuan, H. Huang, G.-J. Deng,
J. Org. Chem. 2018, 83, 10420; b) F. Xiao, C. Liu,
D. Wang, H. Huang, G.-J. Deng, Green Chem.
2018, 20, 973.
[21] a) Q. Wang, L. Sun, Y. Jiang, C. Li, Beilstein J.
Org. Chem. 2008, 4, 51; b) P. S. Mahajan, S. D.
Tanpure, N. A. More, J. M. Gajbhiye, S. B.
Mhaske. RSC Adv. 2015, 5, 101641.
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900717
Advanced Synthesis & Catalysis
FULL PAPER
Cobalt(III)-Catalyzed and Dimethyl Sulfoxide-
Involved Cross-Coupling of Ketones and Amides
for Direct Synthesis of β-Amino Ketones
Adv. Synth. Catal. Year, Volume, Page – Page
Xuefeng Xu, Zhi Zhou, Zhipin Wang, Xinna Ma,
Xin Chen, Xu Zhang,* Xiyong Yu* and Wei Yi*
8
This article is protected by copyright. All rights reserved.