UV Assisted High-Efficient Synthesis of α-Ketoamides using Air Promoted by A Non-Metal Catalyst in Aqueous Solution

Article abstract of DOI:10.1002/cctc.201801365

Presented here is the first example of UV (λ=210 nm) promoted procedure proceeding in aqueous media at room temperature using ambient air as the oxidant for efficient synthesis of an array of α-ketoamides of all types using a non-metal catalyst N-iodosuccinimide with a loading of 20 mol%. With UV, oxygen in the air was efficiently utilized as the green oxidant, some control experiments were carried out and a plausible mechanism was proposed, disclosing that in aqueous solution, the oxidation process was actually triggered by dioxygen radical anion (O₂^.?), while not molecular oxygen. A variety of secondary amines and primary amines as well as ammonia were employed as the amine moieties, and the desired product primary-, secondary-, and tertiary α-ketoamides were afforded in good to excellent yields of up to 96 %.

Full text of DOI:10.1002/cctc.201801365

Accepted Article
Title: UV Assisted High-efficient Synthesis of α-Ketoamides Using Air
Promoted by A Non-metal Catalyst in Aqueous Solution
Authors: Jianhui Li, Shaopo He, Kuan Zhang, Ziyi Quan, Qiheng Shan,
Zhongliang Sun, and Bo Wang
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10.1002/cctc.201801365
ChemCatChem
FULL PAPER
UV Assisted High-efficient Synthesis of α-Ketoamides Using Air
Promoted by A Non-metal Catalyst in Aqueous Solution
Jianhui Li,[a]† Shaopo He,[a]† Kuan Zhang,[a]† Ziyi Quan,[a] Qiheng Shan,[a] Zhongliang Sun,[a] and Bo
Wang*[a,b,c]
Dedication ((optional))
Abstract: Presented here is the first example of UV (λ = 210 nm)
promoted procedure proceeding in aqueous media at r.t. using
ambient air as the oxidant for efficient synthesis of an array of α-
non-metal catalysts, in most conditions, large excess of oxidant
were needed, and high costs and environmental problems are
therefore associated when using metal catalysts or non-metal
ones requiring large excess of chemical oxidants, for instance
tert-butyl hydroperoxide (TBHP).
Molecular oxygen (air contains about 21% oxygen) is an ideal
oxidant, and the utilization of ambient air for the construction of
valuable oxygen-containing organic compounds is of greater
interest over pure oxygen in both academia and industry due to
its economic and environmentally benign properties, and also for
the consideration of safety problems as the latter needs
pressure vessels to transport and high-pressure reactor for
reaction process.
ketoamides of all types using
a
non-metal catalyst N-
iodosuccinimide with a loading of 20mol%. With UV, oxygen in the
air was efficiently utilized as the green oxidant, some control
experiments were carried out and a plausible mechanism was
proposed, disclosing that in aqueous solution, the oxidation process
was actually triggered by dioxygen radical anion (O2·-), while not
molecular oxygen. A variety of secondary amines and primary
amines as well as ammonia were employed as the amine moieties,
and the desired product primary-, secondary-, and tertiary α-
ketoamides were afforded in good to excellent yields of up to 96%.
(a）metal catalyst promoted reactions
O
O
R2
R1 NH
R1
R2
H
OH
+
R3
N
+
Ar
Ar
Introduction
O
O
α-Ketoamides and their related derivatives are a class of key
structural skeletal scaffold in a plethora of natural products, as
well as biologically relevant molecules useful precursors for
functional group transformations.1,2 Because of their wide
applications, the development of practical approaches for
synthesizing α-ketoamides has recently attracted considerable
attentions, and there have been numerous methods developed
for the synthesis of α-ketoamides starting from varied substrates,
for instance, ethylarenes,3 terminal alkenes,4 terminal alkynes,5
aryl methyl ketones,6 aryl acetaldehydes,7 2-oxo aldehydes,8 1-
arylethanols,9 2-arylethanols,10 2-oxo alcohols,11 and etc. The
most important factors in successful α-ketoamide synthesis are
the oxidants and catalysts, including metal12 and non-metal ones
(Figure 1).13 For those procedures with metal catalysts, harsh
reaction conditions are usually required, and for those using
Ag2CO3/K2S2O8
120o
AuBr3/air
60o
C
O
R1
C
i)
ii)
N
Ar
Ar
R2
iii)
v)
air, 120o
C
O
[Pd]
base
Br
CO3
,
nBu N
Fe(OAc)2-TEMPO
O2, 120o
Cs2
4
iv)
C
R1
N
O
R1
R2
OH
+
HN
+ CO +Ar
X
Ar
R2
O
(b)
(c)
non-metal catalyst promoted reactions
1) TBHP/(I2, NIS, nBu4NI)
O
2) I2/DMSO
O
N
3）O2/(I2, KI, nBu4NI)
i)
+
HN
Ar
Ar
CH3
O
reactions using O2 or air
1)CuI, CuBr/NIS
2) (nBu4N+)2(Cu2I4)=
O
O
Ar
R1
N
R2
3) SBA-16-pro-Cu(I)
i)
+
HN air/O
+
2
Ar
Ar
CH3
R2
R2
[a]
Mr. J. Li, Mr. S. He, Mr. K. Zhang, Mis Z. Quan, Mr. Q. Shan, Prof.
Z. Sun, Prof. Dr. B. Wang
Key Laboratory of Advanced Materials of Tropical Island Resources
(Hainan University), Ministry of Education
Hainan University
R1
O
O
O
R1
N
1) Cu2O/AcOH,CuO+I2)
ii)
+
DMF+air/O2
CH3
Ar
O
No.58 Renmin AVE. Haikou 570228, P.R. China.
E-mail: wangbo@hainu.edu.cn, bo.wang@hainu.edu.cn (Prof. B.
Wang)
Figure 1. Selected examples of synthetic approaches for α-ketoamides
[b]
[c]
There have been several recent publications focused on
molecular oxygen (air or O2) oxidized protocols for the
preparation of α-ketoamides from varied substrates14,15
(Figure 1), though great achievements have been made, there
still remains some to be solved such as involving metal catalyst,
using large excess of chemical oxidants, limited substrate
scopes (the majority of the developed methods could only
produce one kind of α-ketoamide, tertiary α-ketoamides, some
No.58 Renmin AVE. Haikou 570228, P.R. China.
Institute of Chemical Engineering, College of Materials and
Chemical Engineering
No.58 Renmin AVE. Haikou 570228, P.R. China.
These authors made equal contribution to this work.
†
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/cctc.201801365
ChemCatChem
FULL PAPER
could afford one or two types of α-ketoamides, secondary-
or/and tertiary- α-ketoamides. The one applicable for all three
types α-ketoamides (primary-, secondary- and tertiary- α-
ketoamides), especially those proceeding in aqueous solution at
mild conditions, has been less studied), the employment of
organic solvent, and low product yields.
provided respectively, it should be noted that these three organic
solvents were used as purchased. Continuous work using water
instead of organic solvent was performed and evaluated, to our
satisfied that when use air as the oxidant, the proposed product
3aa was obtained in the yield of 96%, and with O2, the yield was
97% (Entry 8,9, Table 1), a slight increase in product yield. For
the consideration of meeting more principles of green chemistry
and economic problems, air was chosen as the ideal oxidant
(though a slight increase in product yield was achieved when
using O2) for further evaluations due to its abundant source and
low cost. Higher temperatures were also tested, nevertheless,
the respective lower yields of 87%, and 75% were obtained
when carried out at 40oC and 50oC (Entry 15,16, Table 1),
indicating that a higher temperature would not make positive
contributions to product formation. Simply increasing the
concentrations of substrates would not bring a better conversion,
on the contrary, there was a slight decrease (from 87% to 82%)
in the yield of product 3aa (Entry 17,18, Table 1).
We have recently published some paper on the synthesis of
α-ketoamides starting from different substrates.3,13c,16 And as a
continuous work on clean synthesis of α-ketoamide and inspired
by the formation of ozone in the air with O2 and UV light from the
sun,18 and the fact that ozone can decompose into O2 and O2·-
when meeting H2O,17 we envisioned an UV-assisted formation of
ozone using air and further generation of O2·- in water, and the
application of which for efficient and clean synthesis of α-
ketoamides.
Table 1 Optimization of reaction conditionsa
Scheme 1 UV-assisted aerobic oxidative of methyl ketones and amines or
aqueous ammonia
Entry
Catalyst
Oxidant
Solvent
Temp.
(oC)
Yield
(%)
Herein, we present a UV-assisted metal-free aerobic oxidative
synthetic protocol for the preparation of an array of α-
ketoamides in aqueous media, N-iodosuccinimide (NIS) was
used as the catalyst, both primary- and secondary amines, and
as well as ammonia (dissolved in water) were employed as the
amine moieties. All reactions were proceeded smoothly well in
water at room temperature (Scheme 1). To the best of our
knowledge, this represents the first example of UV assisted
metal-free approach proceeding in water at r.t. using air as the
green oxidant to provide α-ketoamides of all types.
1
I2
O2
Air
N2
N2
O2
Air
Air
Air
O2
Air
Air
Air
Air
Air
Air
Air
Air
Air
H2O
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
40
50
r.t.
r.t.
31b
25b
n.d.
n.d.
85
2
I2
H2O
3
I2
H2O
4
NIS
I2
H2O
5
H2O
6
I2
H2O
82
7
nBu4NI
NIS
NIS
KI
H2O
23
Results and Discussion
8
H2O
96
Initial evaluations for suitable reaction conditions were
performed on a 2mL scale employing acetophenone (1a) and
morpholine (2a) as the model substrates. Reaction parameters,
such as solvent (H2O, DMSO, ethanol (neat), toluene, and
CH3CN), catalyst (I2, NIS, KI, and nBu4NI), oxidant (air, and O2)
and temperatures (r.t., 40oC, and 50oC) were investigated and
the results were summarized in Table 1. When reactions were
carried out under N2 (here we use N2 to avoid the possible
contact between air/O2 and substrates to test whether NIS or I2
can be used as the oxidant) firstly in water，both I2 and NIS
were tested. However, the proposed product 3aa was not
detected (Entries 3,4, Table 1) during or after reactions,
indicating that both I2 and NIS was incapable of oxidizing
substrate 1a to form product 3aa, therefore they could not be
used as the oxidant. When we replaced N2 with air or O2, and
ran these reactions in varied organic solvents, to our interested,
product 3aa was detected and confirmed though not satisfied
results were provided (Entries 11-14, Table 1), it should be
noted that when the reaction was carried out in neat organic
solvent ethanol (Entry 12, Table 1), only trace of product 3aa
were generated, however, when performing reaction in toluene,
DMSO, or CH3CN, poor yields of 25%, 12%, and 19% were
9
H2O
97
10
11
12
13
14
15
16
17
18
H2O
27
NIS
NIS
NIS
NIS
NIS
NIS
NIS
NIS
DMSO
C2H5OH
Toluene
CH3CN
H2O
12
trace
25
19
87
H2O
75
H2O
87c
82d
H2O
aReaction conditions: 1a (0.1 mmol), 2a (0.25 mmol), catalyst (20 mol%),
solvent (2 ml), reaction time, 16h. Yield was determined by HPLC analysis.
bReaction was carried out with no UV. c1a (0.5 mmol), 2a (1.25 mmol). d1a (1
mmol), 2a (2.5 mmol).
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10.1002/cctc.201801365
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With all the optimized conditions in hand, some methyl
ketones and secondary amines listed in Table 2 were subjected,
and the results were summarized in Table 2. All these reactions
were proceeded well and the desired product α-ketoamides
were obtained with yields in good to excellent of up to 96%.
Results indicated that in most conditions, when aryl methyl
ketone bearing an electron-rich substituent(s) on aromatic ring,
the corresponding secondary α-ketoamide could be afforded in
better yields than those carrying an electron-deficient group(s)
(3ca, 3da, 3ga, 3ha, 3ia, 3ja, 3cb, 3bb, Table 2). It seems that
steric hinderance could also make negative affections on
product yields, more steric hindered amines usually resulted in
lower conversions (3aa, 3ca, 3bb, 3bc, 3cb, 3cc, Table 2). Two
heterocyclic ketones were also tested to check the generality of
this procedure, to our delighted, satisfied results were afforded
(3ka, 3la, Table 2), the yields of product 3ka and 3la were 92%
and 75%, respectively.
Encouraged by efficient synthesis of an array of tertiary α-
ketoamides using secondary amines as the amine moieties, we
would like to extend the possible scope of substrate by
employing eight primary amines and ammonia. To the best of
our knowledge, there has been limited examples for the
synthesis of primary- (ammonia as the amine moiety) and
secondary (primary amine as the amine moiety) α-ketoamides.
For such purpose, some reactions were carried out under the
same conditions. As expected, most of the reactions proceeded
well and the results were summarized in Table 3. Results
indicated that more steric hindered substrates usually resulted in
lower product yields (4a-h, Table 3) when using ammonia,
similar to those reactions for tertiary α-ketoamides synthesis,
and when employ primary amines, in most conditions, similar
results were provided as well. The generality of this procedure
was also tested by employing two heterocyclic methyl ketones
(5g, 5h, Table 3), and the corresponding products were afforded
in the yields of 88% and 71%, respectively.
Table 2 Synthesis of tertiary α-ketoamides using secondary
amine as the amine moietya
Table 3 Synthesis of secondary/primary α-ketoamides using
methyl ketones and primary amines/ammoniaa.
aConditions: 1a (0.1 mmol), 2a (0.25 mmol), catalyst (20 mol%) and water (2
ml), reaction time, 16h. Yields was determined by HPLC analysis, and the yields
in brackets were isolated ones.
Based on the above results and some relevant
publications,13a,14a-c,16 a plausible mechanism was proposed, as
shown in Figure 3. With UV at λ = 210nm, molecular oxygen in
the air was transformed to ozone (O3), which then underwent
gradual dissolution in aqueous media, and decomposed
immediately upon meeting with hydroxyl anion (OH-) to form
aConditions: 1a (0.1 mmol), 2a (0.25 mmol), catalyst (20 mol%) and water (2
ml), reaction time, 16h. Yields was determined by HPLC analysis, and the
yields in brackets were isolated ones.
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10.1002/cctc.201801365
ChemCatChem
FULL PAPER
superoxide radical anion (O2·-), see Figure 2. Acetophenone 1
was attacked by amine to form the intermediate 3 in water, and
the intermedia 3 reacted with NIS molecule to form the
intermediate 4. Then intermediate 5 was formed by the attack of
O2·- and, then the cleavage of an O-O bond of 5 took place to
form aryl glyoxal 6, which react with amine 2 to give an
intermediate 8. Finally, the intermedia 8 was oxidized with O2
promoted by NIS to fast form the desired product.
without UV) were not the same mechanism as the latter
provided less products along with more by-products. And then,
O
O
O
H
N
N
N
NIS, air, hv
H2O
CH3
+
+
(a)
(b)
O
O
96%
O
O
O
H
N
air, hv
H2O
CH3
O
O
trace
O
O
O
O
O
H
N
N
N
NIS, air
H2O
CH3
+
+
(c)
(d)
O
O
21%
O
H
N
NIS, Ozone
H2O
CH3
O
O
97%
Figure 2. The formation of O2·- assisted by UV in water
O
O
O
O
O
H
N
N
N
NIS, TEMPO, air, hv
H2O
CH3
+
+
(e)
(f)
H
N
O
O
R2
R1
R1
Ph
R2
N
n.d.
CH2
O
H
N
O
Ph
CH3
NIS, TEMPO, air
H2O
CH3
R1
Ph
R2
O
uv
N
O
I
n.d.
O2
O3
O3
OH-
O3
-
O
R1
+
+
+
HO2
OH
O2
O
O
O
-
H
N
N
-
HO2
+
O2
O
+
2
R2
N
O
NIS, TEMPO, Ozone
H2O
CH3
+
(g)
NIS
O
O
H2
O
n.d.
R2
H
R1
NIS/O2
N
O
O
O
O
O
H
N
O
O
I
Ph
O
R1
N
N
N
NIS, air, hv
DMSO
CH3
CH3
+
+
(h)
(i)
Ar
R2
H
N
OH
O
O
R2
R1
12%
O
H
N
OH
O
+ H2O
Ph
Ph
NIS, air, hv
DMSO(dry)
OH
H
-H2
O
O
O
O
O
n.d.
O
O
O
H
N
Figure 3. The proposed mechanism for UV promoted reactions
N
NIS, N2
H2O
CH3
+
(j)
O
O
n.d.
To verify the mechanism proposed here, twelve control
experiments were carried out using acetophenone/aryl glyoxal
and morpholine as the model substrates (Scheme 2). When
reactions were carried out in the absence of NIS, there was
basically no products were generated (Entries a,b, Scheme 2),
and when with NIS, the yield was boosted to 96%, indicating that
NIS was dispensable for successful transformation to the
desired product, acting as the catalyst, while not as the oxidant.
However, when UV was removed from the reaction system, the
yield of product decreased from 96% to 21% (Entry c, Scheme
2), while the conversion was about 29%, there was still product
formations occurred though there was more by-product
generated. It was assumed that even without UV, there reaction
could still be feasible, however it seems that they (with or
O
O
O
O
O
H
N
H
N
N
NIS, air, hv
H2O
+
+
(k)
(l)
O
O
O
O
95%
O
H
N
H
air, hv
H2O
O
O
8%
Scheme 2 Control experiments
we performed a reaction using ozone (Entry d, Scheme 2) as
the oxidant, as expected, an almost identical yield (97%) of
product 3aa were obtained. And next, we used 2,2,6,6-
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10.1002/cctc.201801365
ChemCatChem
FULL PAPER
tetramethylpiperidinooxy (TEMPO) to selectively capture the
generated O2·- during reaction (Entries e,f,g Scheme 2) and
misfunctioned it, to our excited, in all reactions with or without
UV, or solo using ozone, we did not detect the formations of the
desired product, indicating that the actual oxidant was ozone,
and also the reaction was triggered by O2·-, while not O2, and
another fact was that in the presence of NIS, the dissolved O2
could be converted to O2·-,17 that is why even with no UV, no
formation of O3, there was still some products generated. And
another proof was that, when we tried to conduct the reaction in
organic solvent, for instance, dry DMSO, no product formation
was observed (Entry i, Scheme 2), however, when use
commercial dimethylsulfoxide (DMSO) as the solvent, a yield of
12% was detected (Entry h, Scheme 2), it was found that there
was actually some water dissolved in DMSO with a moisture
measuring instrument, proved that water played a vital role in
the formation of O2·- from O3, which was well agreed with the
fact that O3 was decomposed to O2·- when dissolved in water,16
and the formed O2·- further react with substrate methyl ketones
to form α-ketoamides. When use aryl glyoxal, intermediate 6 in
the reaction mechanism, to react with morpholine, a high yield of
95% was detected (Entry k, Scheme 2), which means aryl
glyoxal is the intermediate, indeed. These results agreed well
with those from the optimization in Table 1.
Keywords: UV • superoxide radical anion • α-ketoamide • air of
1atm • non-metal catalyst
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In summary, we have developed an efficient metal-free
approach to prepare an array of primary-, secondary-, and
tertiary α-ketoamides using NIS as the catalyst and ambient air
as the oxidant in water. Reactions could be proceeded smoothly
well under UV at λ = 210nm at room temperature. Easily
commercial obtainable ketones were as the keto moiety, and
primary-/secondary- amines or aqueous ammonia are used as
the amine moieties. The desired products could be provided in
good to excellent yields of up to 96%. Some control experiments
were carried out, which disclosed that water played an essential
role in successful product formation, and the oxidation was
actually initiated by dioxygen radical anion generated in water,
while not molecular oxygen. Based on these results, we
proposed a plausible mechanism to explain how the desired
products formed. This protocol represents the first UV-assisted
example with a broad substrate scope using non-metal catalyst
and air for efficient and clean synthesis of primary-, secondary-,
and tertiary α-ketoamides, and therefore is potential for practical
and sustainably industrial applications. Further investigations
into the application scope of UV triggered O2·- formation, O2·-
formation in the presence of NIS from O2, and the synthetic
applications are undergoing in our lab.
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Acknowledgements
Financial support from the National Natural Science
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Entry for the Table of Contents (Please choose one layout)
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The first example of UV promoted
procedure proceeding in aqueous
media at r.t. using ambient air as the
Jianhui Li, Shaopo He, Kuan Zhang, Ziyi
Quan, Qiheng Shan, Zhongliang Sun,
and Bo Wang*
UV (λ = 210nm)
✠43 examples
Air
✠yields up to 96%
✠applicable for full types of α-ketoamide
oxidant for efficient synthesis of an
array of α-ketoamides of all types
using a non-metal catalyst N-
iodosuccinimide with a loading of
20mol%. A variety of α-ketoamides
were afforded in good to excellent
yields of up to 96%.
✠abundant air as the oxidant
✠H2O as the solvent
✠mild conditions
O3
Page No. – Page No.
AIR
H2
O
-
O2
UV Assisted High-efficient Synthesis
of α-Ketoamides Using Air Promoted
by A Non-metal Catalyst in Aqueous
Solution
+ O2
R1
N
O
O
NIS
r.t.
R1NHR2
+
CH3
R
R2
✠non-metal catalyst
R
O
This article is protected by copyright. All rights reserved.