Green and Practical Oxidative Deoximation of Oximes to Ketones or Aldehydes with Hydrogen Peroxide/Air by Organoselenium Catalysis

Article abstract of DOI:10.1002/adsc.201601353

Organoselenium-catalyzed oxidative deoximations afforded ketones and aldehydes under mild conditions. The reactions employ hydrogen peroxide and air as clean oxidants and lead to a waste-free and metal-free deprotection protocol for carbonyl protection strategies as well as the green synthesis of ketones and aldehydes. The mechanisms of this interesting organoselenium-catalyzed reaction have been investigated by control experiments as well as the selenium 77 nuclear magnetic resonance (⁷⁷Se NMR) tests. This novel reaction largely expands the application scope of organoselenium catalysis. (Figure presented.).

Full text of DOI:10.1002/adsc.201601353

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DOI: 10.1002/adsc.201601353
Green and Practical Oxidative Deoximation of Oximes to
Ketones or Aldehydes with Hydrogen Peroxide/Air by
Organoselenium Catalysis
Xiaobi Jing,a Dandan Yuan,a and Lei Yua,*
a
Jiangsu Co-Innovation Center for Prevention and Control of Important Animal Infectious Diseases and Zoonoses, School
of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Peopleꢀs Republic of China
Fax : (+86)-514-8797-5244; phone: (+86)-136-6529-5901; e-mail: yulei@yzu.edu.cn
Received: December 8, 2016; Revised: February 11, 2017; Published online: && &&, 0000
Supporting information for this article is available under http://dx.doi.org/10.1002/adsc.201601353.
Abstract: Organoselenium-catalyzed oxidative deoxi- investigated by control experiments as well as the se-
mations afforded ketones and aldehydes under mild lenium 77 nuclear magnetic resonance (77Se NMR)
conditions. The reactions employ hydrogen peroxide tests. This novel reaction largely expands the applica-
and air as clean oxidants and lead to a waste-free tion scope of organoselenium catalysis.
and metal-free deprotection protocol for carbonyl
protection strategies as well as the green synthesis of
ketones and aldehydes. The mechanisms of this inter- Keywords: aldehydes; deoximation; ketones; organo-
esting organoselenium-catalyzed reaction have been selenium catalysis; oximes
Introduction
On the other hand, since oximes are stable and
easily prepared, oximation–deoximation strategies has
Organoselenium catalysis is a distinctive research been frequently employed in protection, characteriza-
topic just unfolding during the last decade.[1] In com- tion, and purification of carbonyl compounds.[10] This
parison with many transition metals, selenium is a me- protocol has also been widely employed in synthesis
tabolizable element that will not accumulate in the including the total synthesis of erythronolide A.[11]
body and is thus safer for both organisms and the en- Moreover, because oximes can also be obtained from
vironment.[2] Selenium is especially rich in China and non-carbonyl compounds,[12] the deoximation strategy
therefore less expensive than many noble metals. can provide efficient approaches to transform other
Moreover, organoselenium compounds are usually functionalities into the carbonyl moiety. The produc-
less toxic than inorganic selenium compounds. Some tion of the spice carvone is a typical example
of them such as diphenyl diselenide and the anti-in- (Scheme 1) in the field.[13] However, although deoxi-
flammatory analgesic drug ebselen [2-phenylbenziso- mation has become a more and more important trans-
selenazol-3(2H)-one][3] show only moderate toxicity. formation in organic chemistry,[10,14] the current deoxi-
Therefore, the emerging of organoselenium catalysis mation methods usually require the use of metal or
brings unprecedented opportunities for organic chem- non-metal chemical reagents that can generate large
ists to discover new synthetic reactions,[4] especially in amounts of waste,[15] halogen- or nitro group-contain-
green preparations of the industrial-oriented chemi-
cals owing to the green features of organoselenium
catalysis.[5–8] In addition, many organoselenium cata-
lysts are robust and can be recycled and reused many
times without obvious deactivation.[5a,7,8] Our group
aims to develop heterogeneous[8,9] or homogeneous[6,7]
catalytic technologies with application potential in in-
dustry. During the past few years, we have reported
a series of recoverable and scalable organoselenium-
catalyzed green transformations.[6–8]
Scheme 1. Synthesis of carvone from non-carbonyl starting
materials via deoximation.
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ing solvents or additives,[16] or expensive metal cata- cyclohexane, toluene and petroleum ether were all
lysts.[17] To solve the above mentioned issues and with unfavorable for the reaction (Table 1, entries 5–7).
the rapid developments in materials chemistry, some Reduced H2O2 dosages depressed the reaction
nano catalysts were also developed and used in deoxi- (Table 1, entries 8–10), but using more than 30% of
mation reactions under greener and milder condi- H2O2/1a did not improve the product yield as expect-
tions.[18] In our own cases, during the continuing stud- ed (Table 1, entries 11 vs. 3). It was then found that
ies on organoselenium catalysis,[6–8] we observed an 608C was the preferable reaction temperature, giving
unexpected deoximation method. The reaction is 2a in 85% yield (Table 1, entries 14 vs. 3, 12 and 13).
metal-free, additive-free and employs H2O2/air as the
Under the optimized conditions, as series of ketox-
clean oxidant. The organoselenium catalyst was easily imes 1 was employed to synthesize the corresponding
available[19] and sufficiently robust to be recycled and ketones 2. Catalyzed by (PhCH2Se)2, the deoximation
reused. Herein, we wish to report our findings.
of acetophenone oxime 1a gave 2a in 82% isolated
yield (Table 2, entry 1). The reaction of 1-phenylbu-
tan-1-one oxime 1b led to butyrophenone 2b in 67%
yield (Table 2, entry 2). After introducing electron-
donation groups, the reactions of substrates 1c–e were
Results and Discussion
The deoximation of acetophenone oxime 1a was ini- restrained and resulted in the reduced product yields
tially chosen as the model reaction to optimize the (Table 2, entries 3–5). The deoximation reactions of
conditions. On heating 1 mmol of 1a with 0.3 mmol of electron-deficient substrates 1f–i occurred smoothly
H2O2 in the presence of 0.025 mmol of (PhCH2Se)2 in to give 2f–i in 70–76% yields (Table 2, entries 6–9).
2 mL of ethanol at 808C in open air for 24 h, the de- The protocol was also favorable for the deoximations
sired product 2a was generated in only 37% GC yield of diarylmethanone oximes 1j–n (Table 2, entries 10–
(Table 1, entry 1). The reaction performed in water 14) and electron-deficient substrates afforded higher
was also tested, but led to poor product yield as well product yields than did the electron-enriched ones
(Table 1, entry 2). Using MeCN as solvent, the yield (Table 2, entries 13 and 14 vs. 11 and 12). The bulky
of 2a was enhanced to 68% (Table 1, entry 3). The re- phenyl-fused substrate 3,4-dihydronaphthalen-1(2H)-
action in 1,4-dioxane led to 2a in reduced 65% yield oxime 1o could also led to a moderate product yield
(Table 1, entry 4) while the non-polar solvents such as
Table 2. Deoximation of ketoximes.[a]
Table 1. Optimization of the reaction conditions for the de-
oximation of 1a.[a]
Entry
Solvent
H2O2/1a[b]
T [oC]
2a [%][c]
1
2
3
4
5
6
7
8
EtOH
H2O
30%
30%
30%
30%
30%
30%
30%
15%
19%
26%
40%
30%
30%
30%
80
80
80
80
80
80
80
80
80
80
80
20
40
60
37
35
68
65
20
16
18
26
37
59
67
32
71
85
MeCN
1,4-dioxane
cyclohexane
toluene
PE[d]
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
9
10
11
12
13
14
[a]
Reaction conditions: 1 mmol of 1a, 0.025 mmol of
(PhCH2Se)2, 30% H2O2 (weight concentration) and 2 mL
of solvent were employed.
Molar ratio of H2O2 vs. 1a.
GC yields based on 1a.
[b]
[c]
[d]
[a]
[b]
Reactions were performed under the optimized condi-
tions described in Table 1, entry 13.
Isolated yields based on substrate 1.
Petroleum ether (bp 90–1208C).
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in
the
organoselenium-catalyzed
deoximation Using 45 mol% of H2O2 led to the excellent product
(Table 2, entry 15).
yield of 99% with 4a selectivity at 96% (Table 3,
We then tried to employ the organoselenium-cata- entry 12). The reaction was hardly improved with in-
lyzed deoximation reaction on aldoximes and benzal- creased H2O2 dosages (Table 3, entry 13).
dehyde oxime 3a was selected as the model substrate
A series of aldoximes 3 was then treated with H2O2
for optimization oft he conditions. Considering that in the presence of (PhCH2Se)2 catalyst. Benzaldehyde
the product benzaldehyde 4a might be oxidized into oxime 3a led to the deoximation product benzalde-
benzoic acid under oxidative conditions, the reaction hyde 4a in excellent yield (Table 4, entry 1). Sub-
was initially performed with less H2O2 and at a lower strates bearing electron-donation groups, 3b, 3c result-
temperature. Heating 3a with 22.5 mol% of H2O2 in ed in decreased product yields (Table 4, entries 2 and
the presence of (PhCH2Se)2 catalyst in MeCN at 3). The electron-enriched substrates 3d, 3e even af-
408C afforded the product 4a and by-product benzo- forded nitriles as the major products (Table 4, en-
nitrile 5a in 68% total yield, with a 4a/5a ratio of tries 4 and 5). The reactions of electron-deficient sub-
38:62 (Table 3, entry 1). To reduce the dehydration strates 3f–i gave aldehydes 4f–i in moderate yields,
by-product, we performed the reaction in water, but while the dehydration by-products were not observed
this led to the generation of 5a as the overwhelming (Table 4, entries 6–9). Bulky substrates 3j, 3k were
major product (Table 3, entry 2). Reaction in 1,4-diox- also tested and the 2-substituted substrate 3k was ob-
ane resulted in poor product yield (Table 3, entry 3). viously preferable for the deoximation reaction
Interestingly, petroleum ether was found to be favora- (Table 4, entries 11 vs. 10). The protocol could be ap-
ble solvent for the reaction, giving an excellent yield plied to heterocycle-containing substrates and the de-
of product, in which the 4a/5a ratio was 87:13 oximation of thiophene-2-carbaldehyde oxime 3l oc-
(Table 3, entry 4). Reaction performed at 608C led to curred to produce 4l (Table 4, entry 12).
increased product yield and 4a selectivity (Table 3,
It is notable that this organoselenium-catalyzed oxi-
entry 5). But further elevated reaction temperature dative deoximation is very practical and the catalyst is
obviously promoted the dehydration as well as other sufficiently robust to be recycled and reused. A
side reactions (Table 3, entries 6 and 7 vs. 5). Both scaled-up reaction with 50 mmol of 1a was tested,
product yield and 4a selectivity decreased with re- giving 4.5 g of 2a (in 75% yield) after distillation
duced H2O2 dosages (Table 3, entries 8–10 vs. 5, 11). under reduced pressure. The residue, which contained
Table 4. Deoximation of aldoximes.[a]
Table 3. Optimization of the reaction conditions for the de-
oximation of 3a.[a]
Entry Solvent
H2O2/3a[b] T [oC] Yield [%] (4a/5a)[c]
1
2
3
4
5
6
7
8
MeCN
H2O
1,4-dioxane 22.5%
22.5%
22.5%
40
40
40
40
60
80
100
60
60
60
60
60
60
68
75
41
91
95
93
65
72
75
89
96
99
99
(38:62)
(5:95)
(39:61)
(87:13)
(94:6)
(85:15)
(37:63)
(48:52)
(70:30)
(87:13)
(95:5)
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
PE[d]
22.5%
22.5%
22.5%
22.5%
7.5%
15%
20%
30%
45%
60%
9
10
11
12
13
(96:4)
(97:3)
[a]
[b]
Unless specially annotated, the reactions were performed
under the optimized conditions described in Table 3,
entry 12.
Isolated yields based on substrate 3; values in the paren-
theses are the molar ratios of aldehyde/nitrile in the
product.
[a]
Reaction conditions: 1 mmol of 3a, 0.025 mmol of
(PhCH2Se)2, 30% H2O2 (weight concentration) and 2 mL
of solvent were employed.
[b]
[c]
Molar ratio of H2O2 vs. 3a.
Total GC yields of 4a and 5a based on 3a; values in pa-
rentheses are the molar ratios of 4a/5a in the product.
Petroleum ether (bp 90–1208C).
[c]
[d]
60% of H2O2/3 was employed.
Reaction performed at 808C.
[d]
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Table 5. Control experiments.[a]
the organoselenium catalytic species, could be reused
directly in the next reaction run, revealing the possi-
bility for catalyst recycle and reuse in large-scale pro-
duction with industrial purposes in near future
(Figure 1).
En Conditions[b]
try
2a
[%][c]
1
2
(PhSe)2 (2.5%), H2O2 (30%), open air
(PhSe)2 (2.5%), Yb(OTf)3 (0.5%), H2O2
(30%), open air
66
73
3
4
(4-FC6H4Se)2 (2.5%), H2O2 (30%), open air 60
[3,5-(CF3)2C6H4Se]2 (2.5%), H2O2 (30%),
open air
52
5
6
7
8
(1-C10H7Se) (2.5%), H2O2 (30%), open air
(PhCH2Se)2 (2.5%), H2O2 (30%), N2
PhSe(O)OH (100%), without H2O2, N2
(PhCH2Se)2 (2.5%), without H2O2, open air
36
15
64
no reac-
tion
18
9
PhSe(O)OH (5%), without H2O2, open air
[a]
Reaction conditions: 1 mmol of 1a and 2 mL of MeCN
were employed.
Molar ratio vs. 1a in the parentheses.
Isolated yields based on 1a.
[b]
[c]
tion were also investigated through control experi-
ments (Table 5, entries 6–9): Reactions under N2 pro-
tection led to 2a in very poor yield (Table 5, entry 6),
but with sufficient chemical oxidant such as
100 mol% of PhSe(O)OH, the reaction without air or
H2O2 also produced 2a in moderate yield (Table 5,
entry 7), showing that air was an essential oxidant for
Figure 1. Catalyst recycle and reuse for scaled-up reaction.
Control experiments were performed for a mecha- the reaction. Although performed in open air, the re-
nism study. Reactions with a series of different disele- action could not happen without H2O2 when using the
nides as catalyst were initially tested to examine their diselenide catalyst (Table 5, entry 8). In contrast, use
substituent effects (Table 5, entries 1–5): The reaction of similar reaction conditions led to 2a in 18% yield
using (PhSe)2 as the catalyst with a similar electronic with the commercially available organoseleninic acid
effect to (PhCH2Se)2 gave rise to a decreased product PhSe(O)OH as catalyst (Table 5, entry 9). These phe-
yield (Table 5, entry 1 vs. Table 2, entry 1), probably nomena suggested that diselenide was inactive for the
due to its larger steric hindrance that impeded the reaction, but in the presence of H2O2, it could be oxi-
catalytic Se sites approaching to the substrates. The dized to the organoseleninic acid, which was the real
same reaction could be improved with catalytic catalytic species. Because organoseleninic acid was
Yb(OTf)3, a Lewis acid that could activate oxime sub- easily reduced to diselenides and lost activity,[6b,d]
strates (Table 5, entries 2 vs. 1). Reactions using an a certain amount of H2O2 was necessary for the reac-
electron-deficient diselenide (4-FC6H4Se)2 or [3,5- tion to maintain sufficiently oxidative conditions, al-
(CF3)2C6H4Se]2 as catalyst gave further depressed though the reaction could employ air as oxidant.
product yields (Table 5, entries 3 and 4), although
On the basis of the experimental results as well as
their steric hindrances were similar to that of (PhSe)2. references, a plausible mechanism was supposed
The typical bulky catalyst (1-C10H7Se)2 was unfavora- (Scheme 2). The pre-catalyst diselenides was initially
ble for the reaction and led to an even lower product oxidized to the organoseleninic acid 6 by H2O2, which
yield than (PhSe)2 (Table 5, entries 5 vs. 1). The above then reacted with the substrates 1 or 3 through a nu-
experimental results indicated that a nucleophilic cleophilic addition and gave the intermediate 7.[7a–c]
attack of organoselenium catalytic species to the posi- Because of the nucleophilic addition step, the elec-
tive carbon center of the substrate might occur first in tron-enriched catalysts with low steric hindrance were
the mechanism course, like that in Baeyer–Villiger re- preferable for the reaction (Table 2, entry 1 vs.
actions.[7a–c] The catalytic selenium species of the reac- Table 5, entries 5 and 7–9). At this step, electron-defi-
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Scheme 2. Possible mechanisms.
cient substrates possess strongly positive carbon cen-
ters, and are favorable for the reaction, in accordance
with the experimental results in Table 2, entries 6–9
vs. 3–5, entries 13, 14 vs. 11, 12 and Table 4, entries 6–
9 vs. 4, 5. Since the nitrogen of the oxime could coor-
dinated with a Lewis acid metal which enhanced the
electron positivity of its adjacent carbon, the addition
of Yb(OTf)3 improved the reaction (Table 5, entries 6
vs. 5). The nitrogen transfer in 7 released the deoxi-
mation products 2 or 4 and led to the intermediate 8,
which decomposed to HNO and RSeOH 9 through
a selenoxide syn-elimination process.[20] Since RSeOH
was an active species, it could be oxidized by air or
H2O2 to regenerate the organoseleninic acid 6 and re-
start the catalytic cycle.
Figure 2. 77Se NMR spectra: (a) reaction of (PhSe)2 with an
equivalent of H2O2 under N2 protection; (b) exposure of
PhSeOH under air.
Compared with the substrate amount, the em-
ployed amount of H2O2 was insufficient to complete
the whole reaction. Therefore, oxidation of RSeOH 9
by air to regenerate RSe(O)OH 6 should be very im- cess of oxidation of PhSeOH by air to regenerate
portant step in the mechanism circle. 77Se NMR anal- PhSe(O)OH in the catalytic circle. Thus, although this
ysis was used to support the hypothesis [Eq. (1)]. We mechanism remains to be fully clarified and alterna-
tive processes may also exist, Scheme 2 should be the
most likely mechanism based on the above tests and
the related literature reports.
Conclusions
employed (PhSe)2 for a test because the data of relat-
ed organoselenium species had been reported and In conclusion, we have reported an organoselenium-
could be employed for comparison with our results. catalyzed deoximation. The reaction employs H2O2/
On treating (PhSe)2 with an equivalent of H2O2 under air as green oxidant and generates no wastes. The
N2 protection, the signal of PhSeOH at 1056 ppm findings provide new tools for organic synthesis and
could be observed (Figure 2a); In comparison, the largely expand the application scope of organoseleni-
same reaction exposed to air only led to PhSe(O)OH, um catalysis, which is a unique subject with industrial
as indicated by the signal at 1181 ppm (Fig- application potential. More investigations in the field
ure 2b).[6c,21] The results clearly demonstrated the pro- are ongoing in our laboratory.
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Experimental Section
Characterization of the Products
Acetophenone (2a): Oil; IR (film): n=3063, 1685, 1596,
1449, 1360, 1266, 965, 760, 691, 569, 530 cmÀ1 1H NMR
General Methods
;
(600 MHz, CDCl3, TMS): d=7.96 (d, J=6.6 Hz, 2H), 7.55(s,
1H), 7.45 (s, 2H), 2.59 (s, 3H); known compound.[22]
Butyrophenone (2b): Oil; IR (film): n=2962, 2930, 1686,
Reagents were purchased from commercial sources with pu-
rities of more than 98% and were directly used as received.
Solvents were of analyticallx pure grade (AR) and directly
used without any special treatment. Melting points were
measured by a WRS-2A digital instrument. IR spectra were
measured on a Bruker Tensor 27 infrared spectrometer.
1H NMR spectra were recorded on Bruker Avance 600/400
instruments (600 or 400 MHz) using CDCl3 as the solvent
and Me4Si as the internal standard. Chemical shifts for
1H NMR are referred to internal Me4Si (0 ppm) and J
values are shown in Hz.77 Se NMR spectra were recorded on
a Bruker Avance 600 instrument (114.4 MHz).
1597, 1495, 1215, 693 cmÀ1 1H NMR (600 MHz, CDCl3,
;
TMS): d=7.97 (d, J=7.8 Hz, 2H), 7.56 (t, J=7.2 Hz, 1H),
7.47 (t, J=7.8 Hz, 2H), 2.96 (d, J=7.2 Hz, 2H), 1.80 (m,
2H), 1.02 (t, J=7.8 Hz, 3H); known compound.[22]
1-(p-Tolyl)ethan-1-one (2c): Oil; IR (film): n=3004, 2825,
1930, 1683, 1608, 1424, 1359, 1267, 1182, 1118, 1021, 955,
1
816, 672, 585, 461 cmÀ1; H NMR (600 MHz, CDCl3, TMS):
d=7.85 (d, J=8.4 Hz, 2H), 7.25 (d, J=7.8 Hz, 2H), 2.56 (s,
3H), 2.39 (s, 3H); known compound.[22]
1-(m-Tolyl)ethan-1-one (2d): Oil; IR (film): n=2924,
1685, 1594, 1431, 1359, 1277, 1192, 1087, 960, 789, 693, 594,
466 cmÀ1 1H NMR (600 MHz, CDCl3, TMS): d=7.77–7.75
;
Typical Procedure for the Deoximation of Ketoxime
(m, 2H), 7.37–7.35 (m, 2H), 2.59 (s, 3H), 2.41 (s, 3H);
In a reaction tube, 0.025 mmol of (PhCH2Se)2 (2.5 mol%),
0.3 mmol of H2O2 (30 w/w%) and 2 mL of MeCN were
stirred at 608C for 1 h. 1 mmol of ketoxime 1 was then
added. The mixture was stirred at 608C in the open air for
24 h and cooled to room temperature. The solvent was
evaporated under vacuum and the residue was separated by
preparative TLC (eluent: petroleum ether:EtOAc=15:1) to
afford the corresponding products 2.
known compound.[22]
1-(4-Methoxyphenyl)ethan-1-one (2e): Solid, mp 36.0–
37.68C (lit. 36–388C); IR (KBr): n=3065, 3004, 2959, 2842,
2571, 2054, 1941, 1676, 1598, 1510, 1424, 1359, 1298, 1174,
1
1116, 1076, 1026, 958, 835, 677, 579, 504, 456 cmÀ1; H NMR
(600 MHz, CDCl3, TMS): d=7.95 (d, J=8.4 Hz, 2H), 6.94
(d, J=8.4 Hz, 2H), 3.87 (s, 3H), 2.56 (s, 3H); known com-
pound.[22]
1-(4-Chlorophenyl)ethan-1-one (2f): Oil; IR (film): n=
3090, 3006, 1687, 1569, 1486, 1427, 1396, 1358, 1260, 1094,
Typical Procedure for the Deoximation of Aldoxime
3a
1
1012, 958, 829, 761, 524 cmÀ1; H NMR (600 MHz, CDCl3):
d=7.89 (d, J=7.8 Hz, 2H), 7.43 (d, J=7.8 Hz, 2H), 2.58 (s,
In a reaction tube, 0.025 mmol of (PhCH2Se)2 (2.5 mol%),
0.45 mmol of H2O2 (30 w/w%) and 2 mL of petroleum ether
(bp 90–1208C) were stirred at 608C for 1 h. 1 mmol of al-
doxime 3 was then added. The mixture was stirred at 608C
in open air for 24 h and cooled to room temperature. The
solvent was evaporated under vacuum and the residue was
separated by preparative TLC (eluent: petroleum ether:
EtOAc=15:1) to afford the corresponding product 4.
3H); known compound.[22]
1-(3-Chlorophenyl)ethan-1-one (2g): Oil; IR (film): n=
3071, 3007, 1690, 1572, 1473, 1423, 1358, 1251, 1166, 1078,
961, 897, 792, 680, 591, 471 cmÀ1
;
1H NMR (600 MHz,
CDCl3, TMS): d=7.93 (t, J=1.8 Hz, 1H), 7.84 (d, J=
7.8 Hz, 1H), 7.54–7.52 (m, 1H), 7.42 (t, J=7.8 Hz, 1H), 2.60
(s, 3H); known compound.[22]
1-(2-Chlorophenyl)ethan-1-one (2h): Oil; IR (film): n=
3067, 3006, 2926, 2315, 1698, 1589, 1430, 1358, 1280, 1242,
1096, 1041, 961, 759, 670, 591, 534, 464 cmÀ1 1H NMR
;
Detailed Procedure for Catalyst Recycle and Reuse
in a Scaled-Up Reaction
(600 MHz, CDCl3, TMS): d=7.56–7.54 (m, 1H), 7.43–7.38
(m, 2H), 7.34–7.31 (m, 1H), 2.65 (s, 3H); known com-
pound.[22]
To a 250-mL round-bottom flask, 0.43 g of (PhCH2Se)2
(1.25 mmol), 8.5 g of 30% H2O2 and 100 mL of MeCN were
added. After stirring the mixture at 608C for 1 h, 6.75 g of
acetophenone oxime 1a (50 mmol) were added. The mixture
was stirred at 608C in the open air for 24 h. The solvent was
evaporated on a rotary evaporator and the residue was
transferred to a 25-mL round-bottom flask and distilled
under reduced pressure to give product 2a; yield: 4.5 g; bp
75–828C/10 mm Hg. The residue was collected and reused
as the catalyst in the next reaction run.
1-(4-Nitrophenyl)ethan-1-one (2i): Solid, mp 74.3–78.98C
(lit. 75–788C); IR (KBr): n=3105, 2923, 2858, 2313, 1822,
1689, 1606, 1521, 1437, 1344, 1251, 960, 852, 741, 684, 592,
1
503 cmÀ1; H NMR (600 MHz, CDCl3, TMS): d=8.33 (d, J=
9.0 Hz, 2H), 8.14 (d, J=8.4 Hz, 2H), 2.70 (s, 3H); known
compound.[22]
Benzophenone (2j): solid, mp 47.3–49.68C (lit. 47–498C);
IR (KBr): n=3061, 1659, 1597,1447, 1316, 1277, 1000, 929,
1
809, 763, 700, 639 cmÀ1; H NMR (600 MHz, CDCl3, TMS):
d=7.79 (d, J=7.8 Hz, 4H), 7.56 (t, J=7.2 Hz, 2H), 7.45 (t,
J=7.8 Hz, 4H); known compound.[22]
Detailed Procedure for 77Se NMR Studies
Di-p-tolylmethanone (2k): Solid, mp 89.3–94.28C (lit. 90–
938C); IR (KBr): n=3042, 2922, 2311, 1646, 1603, 1451,
1 mmol of (PhSe)2 and 1 mmol of H2O2 were stirred in 1 mL
of MeCN under N2 protection for 0.5 h. The mixture was
then dissolved in DMSO-d6 and sent to 77Se NMR analysis
immediately to provide the spectrum in Figure 2a. In com-
parison, the same reaction performed in air led to the spec-
trum in Figure 2b.
1351, 1281, 1171, 928, 826, 748, 677, 583, 467 cmÀ1; H NMR
1
(600 MHz, CDCl3, TMS): d=7.70 (d, J=8.4 Hz, 4H), 7.27
(d, J=8.4 Hz, 4H), 2.42 (s, 6H); known compound.[22]
Bis(4-methoxyphenyl)methanone (2l): Solid, mp 140.6–
147.18C (lit. 141–1468C); IR (KBr): n=2919, 2851, 2311,
Adv. Synth. Catal. 0000, 000, 0 – 0
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1638, 1601, 1503, 1460, 1317, 1255, 1161, 1019, 975, 844, 765,
3-Chlorobenzaldehyde (4g): Oil; IR (film): n=3069, 2836,
1
676, 587, 512 cmÀ1; H NMR (600 MHz, CDCl3, TMS): d=
2729, 2234, 1702, 1576, 1473, 1434, 1375, 1278, 1197, 1027,
1
889, 789, 683, 566 cmÀ1; H NMR (600 MHz, CDCl3, TMS):
7.80 (d, J=7.8 Hz, 4H), 6.97 (d, J=7.2 Hz, 4H), 3.89 (s,
6H); known compound.[22]
d=9.98 (s, 1H), 7.85 (d, J=1.2 Hz, 1H), 7.77 (d, J=7.8 Hz,
1H), 7.61 (t, J=7.2 Hz, 1H), 7.50–7.48 (m, 1H); known
compound.[22]
Bis(4-chlorophenyl)methanone (2m): Solid, mp 143.2–
147.88C (lit. 144–1478C); IR (KBr): n=3081, 2920, 2311,
1924, 1650, 1583, 1481, 1285, 1153, 1087, 968, 840, 752, 665,
2-Chlorobenzaldehyde (4h): Oil; IR (film): n=3069, 2866,
2753, 1656, 1647, 1550, 1446, 1288, 1203, 1127, 1046, 824,
504, 458 cmÀ1 1H NMR (600 MHz, CDCl3, TMS): d=7.74
;
1
758, 709, 634, 564 cmÀ1; H NMR (600 MHz, CDCl3, TMS):
(d, J=6.6 Hz, 4H), 7.48 (d, J=7.2 Hz, 4H); known com-
pound.[22]
d=10.47 (s, 1H), 7.92–7.90 (m, 1H), 7.54–7.51 (m, 1H), 7.45
(d, J=7.8 Hz, 1H), 7.39 (t, J=7.2 Hz,1H); known com-
pound.[22]
Bis(4-fluorophenyl)methanone (2n): Solid, mp 100.9–
104.68C (lit. 102–1058C); IR (KBr): n=3064, 2922, 2313,
1922, 1646, 1591, 1502, 1297, 1230, 1152, 1101, 967, 850, 762,
4-Nitrobenzaldehyde (4i): Solid; mp 102.0–107.38C (lit.
103–1068C); IR (KBr): n=3061, 2646, 1706, 1607, 1533,
1
671, 583, 542, 495 cmÀ1; H NMR (600 MHz, CDCl3, TMS):
1348, 1206, 1008, 814, 735, 673, 568 cmÀ1
;
1H NMR
d=7.82 (s, 4H), 7.19 (t, J=7.2 Hz, 4H); known com-
(600 MHz, CDCl3, TMS): d=10.17 (s, 1H), 8.41 (d, J=
8.4 Hz, 2H), 8.10–8.08 (m, 2H); known compound.[22]
1-Naphthaldehyde (4j) and 1-naphthonitrile (5j): Oil; IR
(4j and 5j, film): n=3097, 2923, 2727, 2222, 1688,1635, 1578,
pound.[22]
3,4-Dihydronaphthalen-1(2H)-one (2o): Oil; IR (film):
n=3064, 2942, 2876, 1685, 1601, 1451, 1328, 1286, 1226,
1
1185, 1119, 1025, 963, 900, 764, 645, 555, 487 cmÀ1; H NMR
1
1509, 1344, 1216, 882, 772, 708, 690, 563, 452 cmÀ1; H NMR
(600 MHz, CDCl3, TMS): d=8.04 (d, J=7.8 Hz, 1H), 7.48
(t, J=7.2 Hz, 1H), 7.32 (t, J=7.8 Hz, 1H), 7.26 (d, J=
8.4 Hz, 1H), 2.98 (t, J=6.6 Hz, 2H), 2.67 (t, J=6.6 Hz, 2H),
2.17–2.12 (m, 2H); known compound.[22]
(4j, 600 MHz, CDCl3, TMS): d=10.37 (s, 1H), 9.25 (d, J=
8.4 Hz, 1H), 8.07 (d, J=8.4 Hz, 1H), 7.96–7.95 (m, 1H),
7.90–7.87 (m, 1H), 7.68–7.65 (m, 1H), 7.61–7.56 (m, 2H);
1H NMR (5j, 600 MHz, CDCl3, TMS): d=8.22 (d, J=
8.4 Hz, 1H), 8.04 (d, J=8.4 Hz, 1H), 7.90–7.87 (m, 2H),
7.68–7.65 (m, 1H), 7.61–7.56 (m, 1H), 7.49–7.47 (m, 1H);
known compounds.[22]
Benzaldehyde (4a): Oil; IR (film): n=3066, 2819, 2737,
2697, 1703, 1598, 1455, 1392, 1204, 826, 747, 688, 650,
451 cmÀ1 1H NMR (600 MHz, CDCl3, TMS): d=10.03 (s,
;
1H), 7.90 (t, J=7.2 Hz, 2H),7.65 (t, J=7.8 Hz, 1H), 7.55 (t,
2-Naphthaldehyde (4k) and 2-naphthonitrile (5k): Oil; IR
(4k and 5k, film): n=3059, 2823, 2719, 2226, 1695, 1628,
1463, 1350, 1264, 1214, 1165, 1119, 963, 904, 864, 819, 750,
J=7.8 Hz, 2H); known compound.[22]
3-Methylbenzaldehyde (4b): Oil; IR (film): n=3044, 3026,
2726, 1703, 1603, 1477, 1330, 1215, 996, 781, 688, 589 cmÀ1
;
628, 475 cmÀ1 1H NMR (4k, 400 MHz, CDCl3, TMS): d=
;
1H NMR (600 MHz, CDCl3, TMS): d=9.98 (s, 1H), 7.68 (d,
J=8.4 Hz, 2H), 7.44–7.40 (m, 2H), 2.42 (s, 3H); known
compound.[22]
10.14(s, 1H), 8.31 (s, 1H), 7.99–7.85 (m, 4H), 7.65–7.55 (m,
2H); 1H NMR (5k, 400 MHz, CDCl3, TMS): d=8.20 (s,
1H), 7.99–7.85(m, 3H), 7.65–7.55(m, 3H); known com-
pound.[22]
4-(tert-Butyl)benzaldehyde (4c) and 4-(tert-butyl)benzoni-
trile (5c): Oil; IR (4c and 5c, film): n=2966, 1697, 1608,
Thiophene-2-carbaldehyde (4l) and thiophene-2-carboni-
trile (5l): Oil; IR (4l and 5l, film): n=2924, 2863, 2209, 1641,
1
1413, 1269, 1157, 1075, 854, 785, 674, 544 cmÀ1; H NMR (4c,
600 MHz, CDCl3, TMS): d=9.98 (s, 1H), 7.83 (d, J=8.4 Hz,
2H), 7.56 (d, J=8.4 Hz, 2H), 1.35 (s, 9H); 1H NMR (5c,
600 MHz, CDCl3, TMS): d=7.59 (d, J=8.4 Hz, 2H), 7.50–
7.47 (m, 2H), 1.33 (s, 9H); known compounds.[6b,22]
1510, 1342, 1219, 985, 726, 668, 592 cmÀ1 1H NMR (4l,
;
400 MHz, CDCl3, TMS): d=9.96 (d, J=1.2 Hz, 1H), 7.80–
7.77 (m, 2H), 7.24–7.22 (m, 1H); 1H NMR (5l, 400 MHz,
CDCl3, TMS): d7.65–7.61 (m, 2H), 7.15–7.13 (m,1H);
known compound.[22]
2,4,6-Trimethylbenzaldehyde (4d) and 2,4,6-trimethylben-
zonitrile (5d): Oil; IR (4d and 5d, film): n=2925, 2863,
2218, 1685, 1610, 1459, 1370, 1215, 1029, 854, 779, 710, 660,
1
581 cmÀ1; H NMR (4d, 600 MHz, CDCl3, TMS): d=10.53(s,
1
1H), 6.87 (s, 2H), 2.56 (s, 6H), 2.31(s, 3H); H NMR (5d,
Acknowledgements
600 MHz, CDCl3, TMS): d=6.91 (s, 2H), 2.45 (s, 6H),
2.31(s, 3H); known compounds.[22]
This work was financially supported by NNSFC (21202141),
Priority Academic Program Development (PAPD) of Jiang-
su Higher Education Institutions, the Open Project Program
of Jiangsu Key Laboratory of Zoonosis (R1509), the Innova-
tion Foundation of Yangzhou University (2015CXJ009) and
the High Level Talent Support Project of Yangzhou Universi-
ty. We thank the testing centre of Yangzhou University for as-
sistance.
4-Methoxybenzaldehyde (4e) and 4-methoxybenzonitrile
(5e): Oil; IR (4e and 5e, film): n=3022, 2977, 2938, 2842,
1689, 1603, 1509, 1459,1306, 1260, 1170, 1025,835, 683, 600,
1
550 cmÀ1; H NMR (4e, 600 MHz, CDCl3, TMS): d=9.88 (s,
1H), 7.84 (d, J=8.4 Hz, 2H), 7.01 (d, J=8.4 Hz, 2H),
1
3.89(s, 3H); H NMR (5e, 600 MHz, CDCl3, TMS): d=7.59
(d, J=9.0 Hz, 2H), 6.96(d, J=8.4 Hz, 2H), 3.86 (s, 3H);
known compounds.[6b,22]
4-Chlorobenzaldehyde (4f): Solid, mp 45.8–47.38C (lit.
468C); IR (KBr): n=3060, 2926, 2843, 2735, 1704, 1589,
1485, 1374, 1291, 1207, 1165, 1090, 1011, 826, 694, 541,
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Green and Practical Oxidative Deoximation of Oximes to
Ketones or Aldehydes with Hydrogen Peroxide/Air by
Organoselenium Catalysis
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Adv. Synth. Catal. 2017, 359, 1 – 9
Xiaobi Jing, Dandan Yuan, Lei Yu*
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