Iodobenzene-catalyzed oxidative cleavage of olefins to carbonyl compounds

Article abstract of DOI:10.1016/j.tetlet.2020.152204

A metal-free approach for the oxidative cleavage of carbon–carbon double bonds of olefins to carbonyl compounds was established by using oxidant m-CPBA and non-metallic organocatalyst PhI in toluene/H₂O. A broad scope of aromatic olefins was used. All the reactions proceeded smoothly at 35 °C in short reaction time to furnish the respective mono- and double carbonyl compounds selectively in moderate to good yields.

Full text of DOI:10.1016/j.tetlet.2020.152204

Journal Pre-proofs
Iodobenzene-Catalyzed Oxidative Cleavage of Olefins to Carbonyl Com‐
pounds
Lele Du, Zechao Wang, Junliang Wu
PII:
S0040-4039(20)30669-9
DOI:
Reference:
https://doi.org/10.1016/j.tetlet.2020.152204
TETL 152204
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
20 May 2020
28 June 2020
29 June 2020
Please cite this article as: Du, L., Wang, Z., Wu, J., Iodobenzene-Catalyzed Oxidative Cleavage of Olefins to
Carbonyl Compounds, Tetrahedron Letters (2020), doi: https://doi.org/10.1016/j.tetlet.2020.152204
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Graphical Abstract
Iodobenzene-Catalyzed Oxidative Cleavage of Olefins Leave this area blank for abstract info.
to Carbonyl Compounds
Lele Dua , Zechao Wangb and Junliang Wua 
O
O
PhI, m-CPBA, HBF4
Toluene/H2O, 35 oC, 1-7 h
Ar
Ar
Metal-free
31 examples, up to 88% yield
Oxidative cleavage of C=C bonds
Mono- and double carbonyl compounds

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Iodobenzene-Catalyzed Oxidative Cleavage of Olefins to Carbonyl Compounds
Lele Dua , Zechao Wangb and Junliang Wua 
aCollege of Chemistry, and Institute of Green Catalysis; Zhengzhou University, Zhengzhou 450001, P. R. China
bDivision of Molecular Catalysis & Synthesis, Henan Institute of Advanced Technology; Zhengzhou University, Zhengzhou 450001, P. R. China
———
ARTICLE INFO
ABSTRACT
a,b Corresponding author. Tel.: +86-371-6778-3126; fax: +86-371-6778-3126; e-mail: wujl@zzu.edu.cn
c Corresponding author. E-mail: zechao_wang@163.com
Article history:
Received
A metal-free approach for the oxidative cleavage of carbon-carbon double bonds of olefins to
carbonyl compounds was established by using oxidant m-CPBA and non-metallic organocatalyst
Received in revised form
Accepted
PhI in toluene/H2O. A broad scope of aromatic olefins was used. All the reactions proceeded
smoothly at 35 C in short reaction time to furnish the respective mono- and double carbonyl
o
Available online
compounds selectively in moderate to good yields.
Keywords:
Metal-free
Oxidation
2009 Elsevier Ltd. All rights reserved.
Aromatic olefins
C=C bond cleavage
Mono- and double carbonyl compounds
carbon-carbon double bonds of olefins to aldehydes or ketones in
Introduction
toluene/H2O selectively through using PhI as a catalyst and m-
o
CPBA (3-chloroperbenzoic acid) as an oxidant at 35 C in 1-7
hours.
The oxidative cleavage of carbon-carbon double bonds of
olefins into corresponding carbonyl compounds (e.g., aldehyde,
ketone, etc.), without over oxidation to carboxylic acid, is a
wildly practiced transformation in organic synthesis.1 These
carbonyl compounds are significant intermediates in fine
chemicals, such as pharmaceuticals, agrochemicals, fragrances,
and food additives.2 A variety of methodologies have been
demonstrated with great interest for oxidative cleavage reaction.3
Normally, the oxidative cleavage of carbon-carbon double bonds
is carried out by metal oxidants, such as KMnO4,4 NaIO4,5
oxone,6 and non-metal oxidants, such as TBHP,7 O3.8 However,
many of these oxidants undergo drawbacks, such as toxicity of
metals, low selectivity, difficult handling, and over oxidation of
aldehyde to carboxylic acid.9 To solve these problems, various
heterogeneous catalysts10 and homogeneous catalysts11 are
invented and attract great attention to cleave carbon-carbon
double bonds of olefins with clean oxidants (e.g., O2, H2O2,
etc.).12 Although heterogeneous catalysts can be separated and
reused, their activity and selectivity are inferior. Moreover,
preparation of heterogeneous catalysts increases cost and lead to
environmental pollution. Nevertheless, the use of homogeneous
catalysts suffers from the drawbacks regarding the toxic metal
contaminants left in products and non-recyclability. Therefore,
Results and discussion
Our initial investigation was started with p-bromostyrene (1d,
1 equiv.), HBF4 (2.2 equiv.), PhI (20 mol%), and m-CPBA in
CH3CN/H2O mixture. To our delight, 12% yield of p-
bromobenzaldehyde (2d) was formed after 6 hours at 35 oC
(Table 1, entry 1). According to previous reports, solvent had
extremely important influence on oxidative cleavage reaction.15
To investigate the solvent effect in our catalytic system, several
solvents were screened. As shown in Table 1, 10:1 volume ratio
of DCM (dichloromethane)/H2O, CH3OH/H2O, and toluene/H2O
were tested as solvent mixtures (Table 1, entries 2-4).
Toluene/H2O (10:1) was the best solvent mixture to afford
desired aldehyde in 52% yield. Subsequently, different volume
ratios of toluene/H2O were optimized (Table 1, entries 4-6),
which was observed that 3:1 volume ratio of toluene/H2O gave
the best result of 74% yield (Table 1, entry 5). Then we explored
the oxidative cleavage of C=C bonds in various oxidants, such as
Table 1. Optimization of reaction conditionsa
development of
a
metal-free condition combined with
inexpensive and environmentally benign oxidants for the
oxidative cleavage of olefins is of great importance.13 In recent
years, [bis(trifluoroacetoxy)iodo]benzene (PIFA), iodosyl-
benzene (PhIO), (diacetoxyiodo)benzene [PhI(OAc)2], and
iodylbenzene (PhIO2) have been reported in organic synthesis
owing to their ready availability, low toxicity, and easy
handling.14 In order to fix these problems above and lay a solid
foundation for large-scale industrial production, herein, we report
a metal-free, effective approach for the oxidative cleavage of

2
Tetrahedron Letters
Table 2. Oxidation of terminal olefins to aldehydesa
O
Catalyst, Oxidant
HBF4, Solvent
PhI (20 mol%), m-CPBA (2.2 equiv.)
O
R1
Br
Br
R1
HBF4 (2.2 equiv.), Toluene/H2O (3:1), 35oC, 1-6 h
1d
2d
1
2
Entry
1
Catalyst
PhI
Oxidant
Solvent
Yield
12
Substrate
Product and Yieldb
O
Substrate
Product and Yieldb
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
Oxone
CH3CN/H2O 10:1
DCM/H2O 10:1
CH3OH/H2O 10:1
Toluene/H2O 10:1
Toluene/H2O 3:1
Toluene/H2O 1:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
Toluene/H2O 3:1
F
F
O
2
3
PhI
PhI
35
7
1a
2a
2b
2c
1g
2g
, 65%
, 72%
, 74%
, 71%
Cl
O
O
O
O
O
O
4
PhI
52
F
F
Cl
1b
1c
1d
1e
1h
1i
2h
, 25%
5
PhI
74
6
PhI
36
Cl
Cl
7
PhI
10
2i
2j
, 55%
8
PhI
H2O2
n.r.
n.r.
n.r.
63c
56c
57c
12c
O
O
Br
Br
9
PhI
K2S2O8
c
2d
, 74%
1j
, 61%
10
11
12
13
14
PhI
TBPB
PhI
m-CPBA
m-CPBA
m-CPBA
m-CPBA
d
2e
, 66%
2k
2l
, 57%
1k
1l
p-MeC6H4I
p-MeOC6H4I
p-NO2C6H4I
O
O
MeO2C
1f
MeO2C
c
d
2f
, 51%
, 62%
aReaction condition: Substrate (0.2 mmol, 1 equiv.), PhI (0.04 mmol, 20
mol%), m-CPBA (0.44 mol, 2.2 equiv.), HBF4 (0.44 mol, 2.2 equiv.),
toluene/H2O (1.2 mL:0.4 mL), 35 oC, 1-6 h. bYield are determined by 1H
NMR using 1,1,2,2-tetrachloroethane as an internal standard. cHFIP (0.1 mL)
was added. dHFIP (0.2 mL) was added.
aReaction condition: 1d (0.2 mmol, 1 equiv.), catalyst (0.04 mmol, 20 mol%),
oxidant (0.44 mol, 2.2 equiv.), HBF4 (0.44 mmol, 2.2 equiv.), organic solvent
(1.2 mL), 35 oC, 6 h. bYield are determined by 1H NMR using 1,1,2,2-
tetrachloroethane as an internal standard. CUse p-methylstyrene as a substrate
for 2 h.
Table 3. Oxidation of olefins to ketonesa
oxone, H2O2, TBPB (tert-butyl peroxybenzoate) and K2S2O8
(Table 1, entries 7-10). However, none of them had better
performance than m-CPBA. Encouraged by these results, next we
turned our attention to study the effects of non-metallic
organocatalysts (Table 1, entries 11-14). p-Methylstyrene was
chosen as the substrate. p-Methyliodobenzene, p-methoxyliodo-
benzene, and p-nitroiodobenzene were performed in oxidative
cleavage reaction. Screening of these catalysts indicated that
iodobenzene had the best catalytic activity to the oxidative
cleavage of C=C bonds of olefins.
O
R2
R2
PhI (20 mol%), m-CPBA (2.2 equiv.), HFIP
R1
R1
HBF4 (2.2 equiv.), Toluene/H2O (3:1), 35oC, 4 h
3
4
Substrate
Product and Yieldb
O
Substrate
Product and Yieldb
O
S
S
3h
3i
3a
4a
, 65%
O
4h
, 36%
O
With the optimized conditions in hand (Table 1, entry 5), a
variety of terminal olefins were performed subsequently. As
shown in Table 2, different olefins proceeded well under our
reaction conditions. Olefins with either electron-donating or
electron-withdrawing groups led to the formation of the
corresponding aldehydes in moderate to good yields. Substrates
could tolerate various functional groups, such as Me, F, Cl, Br,
Ph, and CO2Me. Notably, halogen-substituted olefins were found
to be favored in this reaction, affording aldehydes 2b, 2c, and 2d
in 72%, 74%, and 74% NMR yields, respectively. The position of
substituent R1 had a critical effect on this oxidative reaction.
Olefins substituted with functional groups in the meta position
worked well. 2g was generated in 71% yield. However, olefins
substituted with functional groups in the ortho position gave
lower yields (2h and 2i). Based on results of GC-MS, the yield of
2h was low because side-products were generated, such as ο-
chlorobenzoic acid and styrene oxide. GC result showed that the
conversion of 1h was 90%. In addition, vinylnaphthalene (1j)
was employed under the reaction conditions with HFIP as an
additive and oxidized to naphthylacetaldehyde (2j) in 61% yield.
F
F
3b
4b
, 72%
O
4i
, 80%
O
Cl
F
Cl
Br
Cl
F
3c
3d
4c
, 74%
O
3j
4j
, 68%
O
Br
Br
NC
Cl
4d
, 66%
O
3k
4k
, 71%
O
NC
Br
3l
4l
3e
3f
4e
4f
, 88%
O
, 66%
O
Cl
F
Cl Cl
Cl
MeO
MeO
c
3m
, 51%
O
4m
, 71%
O
CN
F
CN
4n
, 68%
3g
4g
3n
, 55%
Inspired by the promising results above, we explored α-
substituted olefins to form ketones shown in Table 3. Methyl
substituent on α-position of styrene afforded 65% isolated yield
aReaction condition: Substrate (0.2 mmol, 1 equiv.), PhI (0.04 mmol, 20
mol%), m-CPBA (0.44 mol, 2.2 equiv.), HBF4 (0.44 mol, 2.2 equiv.), HFIP
(0.2 mL), toluene/H2O (1.2 mL:0.4 mL), 35 oC, 4 h. bIsolated yield. cReaction
for 7 h.
Table 4. Oxidation of olefins to double carbonyl compoundsa

3
OH
O
O
OH
Standard Conditions
Standard Conditions
O
PhI (20 mol%), m-CPBA (2.2 equiv.), HFIP
O
(a)
n
R1
R1
HBF4 (2.2 equiv.), Toluene/H2O (3:1), 35oC, 4 h
73%
63%
trace
13%
5
6
Substrate
Product and Yieldb
O
Substrate
Product and Yieldb
O
O
(b)
(c)
O
O
4
5
O
O
F
Standard Conditions
without PhI
6a
, 62%
F
6d
, 50%
5a
5d
Br
Br
Br
Br
O
O
O
5
O
5
Standard Conditions
PhIO instead of PhI
(d)
6b
, 55%
5b
5c
5e
6e
, 49%
O
O
6
Scheme 1. Control experiments
6c
, 47%
aReaction condition: Substrate (0.2 mmol, 1 equiv.), PhI (0.04 mmol, 20
mol%), m-CPBA (0.44 mol, 2.2 equiv.), HBF4 (0.44 mol, 2.2 equiv.), HFIP
(0.2 mL), toluene/H2O (1.2 mL:0.4 mL), 35 oC, 4 h. bIsolated yield.
R-CHO
of acetophenone (4a). Successfully, a series of functional groups,
such as F, Cl, Br, CN and OMe, were compatible under our
conditions, and gave the desired ketones in moderate to good
yields (4b-4f). Electron-donating group (OMe) decreased the
process of oxidative cleavage reaction slightly, and generated
corresponding ketone (4f) in 51% isolated yield. Remarkably,
isopropenylnaphthalene (3g) could produce acetonaphthone (4g)
in 55% isolated yield as well. Moreover, aromatic substituents on
α-position of styrenes converted to corresponding ketones in 36%
to 88% isolated yields (4h-4n), whereas thienyl group on α-
position of styrene only gave 4h in 36% isolated yield.
Unfortunately, aliphatic olefins could not be tolerated in this
work due to their lower activity than aromatic olefins.
Cyclohexene was used as substrate, however, only trace of
carbonyl product could be detected by GC-MS.
Ar
I
O
O
PhI
HBF4, H2O
R
C
m-CPBA
OH
I
Ar
OH2
OH
m-CBA
OH2
O
D
H+
ArI (III)
or
BF4
OH
R
R
R
H2O
D
m-CPBA
B
A
Scheme 2. Proposed mechanism
A possible mechanism of the catalytic cycle for the oxidative
cleavage of carbon-carbon double bonds was shown in Scheme 2
on the basis of control experiments and references.3a,3b Initially,
hydroxy-λ3-iodane D was generated in situ after non-metallic
organocatalyst PhI was oxidized by m-CPBA.3a,3b At the same
time, olefin was oxidized to generate intermediate A. Then
intermediate A was hydrolyzed to form 1,2-diol B rapidly.
Subsequently the iodane D underwent oxidative cleavage of 1,2-
diol B, and formed the cyclic dialkoxy-λ3-iodane C.16 Finally,
carbonyl compound was formed after decomposition of cyclic
dialkoxy-λ3-iodane C. Based on kinetic measurements of
previous reports, we suggested a rapid pre-equilibrium formation
of cyclic dialkoxy-λ3-iodane C, followed by its rate-limiting
decomposition to aldehyde.16 PhI was regenerated for the next
catalytic cycle.
To further evaluate the substrate scope of this process, plenty
of cyclic benzylic systems (5a-5e) were demonstrated under our
reaction conditions, since these compounds had a high tendency
to undergo oxidative cleavage of C=C double bonds to afford
moderate yields of double carbonyl compounds. As shown in
Table 4, cyclohexene, cycloheptene, and cyclooctene with phenyl
substituents on double bonds were catalytically cleaved favorably
in 62%, 55%, and 47% isolated yields, respectively (6a, 6b, 6c).
Cycloheptene with p-fluorophenyl substituent on double bond
generated corresponding double carbonyl compounds 6d in 50%
isolated yield. Besides, p-methylphenyl substituent on double
bond (5e) was subjected to the oxidative cleavage and provided
dialdehyde (6e) in 49% isolated yield.
In order to get some insight into the reaction mechanism,
several control experiments were carried out (Scheme 1). Details
referred to SI. Primarily, 1-phenylethane-1,2-diol was added to
standard conditions. Benzaldehyde was obtained in 73% yield.
Then, 2-phenyloxirane was transformed to benzaldehyde in 63%
yield under standard conditions. It suggested that 1-phenylethane
-1,2-diol and 2-phenyloxirane might be intermediates in the
system. When PhI was not added to the standard conditions, only
trace of ρ-bromobenzaldehyde was generated. However, styrene
oxide was detected by GC-MS. While PhIO was instead of PhI in
the absence of m-CPBA, 13% yield of ρ-bromobenzaldehyde was
formed. It indicated that m-CPBA or hypervalent iodine reagent
could oxidize olefin to styrene oxide.
Conclusion
In summary, we have successfully developed a simple,
convenient, metal-free procedure for the oxidative cleavage of
carbon-carbon double bonds of olefins to carbonyl compounds by
using oxidant m-CPBA and non-metallic organocatalyst PhI in
toluene/H2O. A broad scope of aromatic olefins could be
oxidized via direct carbon-carbon bonds cleavage to mono- and
o
double carbonyl compounds smoothly at 35 C in short reaction
time. High selectivity and good functional group tolerance could
be demonstrated. Mono- and double carbonyl compounds were
isolated in moderate to good yields.
Declaration of Competing Interest

4
Tetrahedron
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The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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Supplementary Material
Supplementary material that may be helpful in the review
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Declaration of interests
☑The authors declare that they have no known
competing financialinterestsor personal

5
relationships that could have appeared to influence
the work reported in this paper.
2. The reactions proceeded smoothly at mild
conditions.
3. Mono- and double carbonyl compounds
were formed.
☐The authors declare the following financial
interests/personal relationships which may be
considered as potential competing interests:
Graphic abstract
Iodobenzene-Catalyzed Oxidative
Cleavage of Olefins to Carbonyl
O
O
PhI, m-CPBA, HBF4
Toluene/H2O, 35 oC, 1-7 h
Ar
Ar
Metal-free
31 examples, up to 88% yield
Oxidative cleavage of C=C bonds
Mono- and double carbonyl compounds
Compounds
Highlight
1. A metal-free method for oxidative cleavage
of olefins to carbonyl compounds.