Iodide reagent controlled reaction pathway of iodoperoxidation of alkenes: A high regioselectivity synthesis of α- And β-iodoperoxidates under solvent-free conditions

Article abstract of DOI:10.1039/c8gc00209f

A highly atom economical, efficient and environmentally friendly iodoperoxidation of alkenes with tert-butyl hydroperoxide (TBHP) and iodide/iodine is reported in this paper. This method afforded a convenient path to obtain two different configurations of iodoperoxidates from the same starting materials. Notably, the regiodivergent iodoperoxidation reaction was achieved by using different iodide reagents. A series of control experiments were performed, which suggested the involvement of a radical pathway for the anti-Markovnikov type iodoperoxidates (α) in the combination of ammonium iodide (NH₄I)/TBHP, and an active cationic iodine pathway for the Markovnikov type adduct (β) with iodine (I₂) and TBHP.

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Iodide Reagents Controlled the Reaction Pathway of
Iodoperoxidation of alkenes: A High
Cite this: DOI: 10.1039/x0xx00000x
Regioselectivity Synthesis of αꢀ and βꢀ
iodoperoxidates under Solventꢀfree Conditions†
Received 00th January 2012,
Accepted 00th January 2012
Xiaofang Gao*, Hongling Yang, Chen Cheng, Qi Jia, Fang Gao, Hongxiang Chen,
Qun Cai and Chuangjian Wang *
DOI: 10.1039/x0xx00000x
www.rsc.org/
A highly atomꢀeconomical, efficient and environmentꢀfriendly reactions, including oxidation, KornblumꢀDeLaMare reactions,
iodoperoxidation of alkenes with TBHP and iodide/iodine is and epoxidation, but also can play important roles in the injury of
reported herein. This method afforded a convenient path to cells, food safety, or medicinal chemistry as therapeutic drugs.6
obtain two different configurations of iodoperoxidates from On the other hand, iodinated compounds have been recognised as
7
the same starting materials. Notably, the regiodivergent important and versatile building blocks in organic synthesis,
iodoperoxidation reaction was achieved by using of different which are valuable reagents in preparative nucleophilic
iodide reagents.
A series of control experiments were substitution reactions occurring with retention of the peroxide
performed, which suggested the involvement of a radical
pathway for the antiꢀMarkovnikov type iodoperoxidates (α)
in the combination of NH4I/TBHP, and an active cationic
iodine pathway for the Markovnikov type adduct (β) with I2
and TBHP.
The simultaneous introduction of two different functional groups
into the carbonꢀcarbon double bonds of alkenes is an important
fundamental process in organic synthesis.1 Particularly, the
regiodivergent difunctionalization reaction of alkenes is urgently
desirable, since various molecular structures achieved.2
Conventionally, the coupling reaction of alkene with an
electrophile and a nucleophile is an efficient way to obtain the
sole Markovnikov type adduct, due to the stabilization of
carbocations.3 Another observed regioselective reaction of alkene
is the radical coupling reaction, and high regioselectivity of this
type of reaction depends on the persistent radical effect.4
Although steric hindrance of alkene structure could alter the
regioselectivity type completely in the former reaction,3b it was
still limited to some special substrates. In addition, only one
type of adducts was formed in most of the reported
difunctionalization reactions of alkenes. Therefore, controlling
the regioselectivity in the difunctionalization reaction of alkenes
remains a challenge.
Scheme 1 Approaches to iodoperoxidation of alkenes
fragment. Therefore, the simultaneous generation of iodide and
peroxide moieties in the same molecule, may provide an easy
access to compounds with pharmaceutical potential.
The method for the synthesis of iodoperoxidates was first
reported in the 1970s, which was achieved through the
peroxymercuration of alkenes followed by iodination (Scheme
1a).8 Since then, the chemistry of iodoperoxidates compounds
has developed rapidly, as its great potential for the design of new
antimalarial drugs. Then the reaction of alkenes with 1,3ꢀdiiodoꢀ
5,5ꢀdimethylhydantoin and hydrogen peroxide was reported.9
The synthesis of iodoperoxidates has earned much attention in
recent years, as the unique chemical and biological properties of
peroxy and iodide groups.5 The organic peroxides not only can
serve as key reactive intermediates in diverse organic synthesis
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Table 2 Scope of styrenes for the synthesis of αꢀiodoperoxidatesa,b
Recently, an iodine and hydroperoxides system were developed
by Terent’ev and coꢀworkers in the synthesis of vicinal
iodoperoxidates (Scheme 1b).5a, 10a More recently, Zhu and coꢀ
workers reported the synthesis of 2ꢀiodoꢀ1ꢀperoxidates from
styrenes and other olefins by using I2 and TBHP at room
tempereture in toluene.10b In contrast, these methods made
progress in the used reagents. However, all the reported
iodoperoxidates before were the Markovnikovꢀtype iodoꢀ
containing adducts, to the best of our knowledge. No reports
have been demonstrated for the synthesis of antiꢀMarkovnikov
type iodoperoxidates. Continued to our research interest in
difunctionalization of alkenes,11 herein we report a high atom
economical and metalꢀfree method for regioselectivity sythesis
of αꢀ and βꢀ iodoperoxyalkanes under solventꢀfree reaction
conditions (Scheme 1c).
At first, the iodoperoxidation of styrene 1a and TBHP (in 70%
aqueous) using 1.0 equiv of NIS as iodide source and MeCN as
o
solvent at 80 C for 10 h was performed. Fortunately , the target
product 2a was obtained in 10% yield under this reaction
condition (Table 1, entry 1). Switching the iodide to KI did not
raise the reaction efficiency. Interestingly, we found that
decreasing the temperature resulted in a significant improvement
of the yield of 2a (Table 1, entries 2ꢀ3). When substituted Bu4NI
or NH4I for KI, a further improvement of the yield to 93% (Table
Table 1 Optimization of reaction conditionsa
Iodide source Solvent Oxidant
Temp ( °C ) Yield(%)b
Entry
(equiv.)
(equiv.)
TBHPc
TBHPc
TBHPc
TBHPc
TBHPc
TBHPc
TBHPc
TBHP c
TBHPc
TBHP c
TBHPc
TBHPc
/time ( h )
80/10
80/10
60/10
40/10
25/10
25/4
2a
10
16
21
49
93
90
92
94
88
96
ꢀ
3a
1
NIS (1.0)
KI (1.0)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
EtOAc
DCM
ꢀ
2
ꢀ
3
KI (1.0)
ꢀ
4
Bu4NI(1.5)
NH4I (1.5)
NH4I (1.1)
NH4I (1.1)
NH4I (1.1)
NH4I (1.1)
NH4I (1.1)
I2 (1.0)
ꢀ
5
6 c
ꢀ
a
Reaction conditions: styrene (1.0 mmol), NH4I (1.1 mmol), and TBHP (5.8
ꢀ
b
c
7
25/4
ꢀ
mmol, 70% aqueous solution) were stirred at 25 °C for 4 h. Isolated yield.
8
25/4
ꢀ
transꢀβꢀMethylstyrene was used as substrate.
9
DMF
25/4
ꢀ
1, entries 4ꢀ5). Lower amounts of NH4I and shorten reaction time
led to a slightly lower yield (90%; Table 1, entry 6). Different
solvents such as EtOAc, DCM and DMF afforded the similar
yields of 2a (Table 1, entries 7ꢀ9). This indicated that the
solvents had no effect on the product formation. Thus, we
suspected that under solventꢀfree condition the iodoperoxidation
of styrene with TBHP and NH4I could also perform well. And it
was confirmed by the 96% yield of 2a under solventꢀfree.
condition (Table 1, entry 10). To explore the role of iodide in
this transformation, we replaced NH4I with I2. To our surprise,
the 2a product was not obtained but a regioisomer 3a product
generated (Table 1, entry 11). Decreasing the amount of iodine
from 1 to 0.6 equiv, resulted in slightly lower yield (78%; Table
1, entry 12). Further swithching the solvents did not improve the
10
11
12
13
14
15
16
17
18
19 e
ꢀꢀꢀꢀꢀꢀꢀꢀ
DCM
25/4
ꢀ
25/4
80
78
75
73
75
95
89
ꢀ
I2 (0.6)
Et2O
25/4
ꢀ
I2 (0.6)
DMF
TBHP c 25/4
ꢀ
I2 (0.6)
MeCN
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
MeCN
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
TBHPc
TBHP c
TBHPd
TBHPd
TBHP d
TBHPd
25/4
25/4
25/4
25/4
80/2
25/2
ꢀ
I2 (0.6)
ꢀ
I2 (0.6)
ꢀ
I2 (0.6)
ꢀ
I2 (0.6)
ꢀ
I2 (0.6)
ꢀ
98
a
Reaction conditions: Styrene (1 mmol), TBHP (5.8 mmol), Solvent (2 mL).
b
c
Yield determined by NMR analysis using an internal standard. TBHP (70%
d
aqueous solution, 5.8 mmol). TBHP (6.7 M TBHP in decane, 3.6 mmol ).
2 | J. Name., 2012, 00, 1-3
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Table 3 Scope of alkenes for the synthesis of βꢀiodoperoxidatesa,b
yield of 3a, since the byproduct 2ꢀiodoꢀ1ꢀphenylethanol was
always produced. When changing the aqueos TBHP (in 70%
aqueous) to nonaqueous TBHP (6.7 M TBHP in decane), the yield
of 3a dramatically increased to 95%. However, when reaction
temperature further increased and reaction time shortened, the
amount of 3a decreased, due to the transformation of 3a into 2ꢀ
iodoꢀ1ꢀ phenylethanone. Therefore, the optimal conditions for 2a
and 3a were those described in entry 10 and 19.
Under the optimal conditions, a wide range of styrenes 1
were investigated to evaluate the efficiency and substrates scope
of this novel protocol for the synthesis of αꢀiodoperoxidates
(Table 2). In general, the reaction tolerated a wide range of
substituted aryl alkenes to give the corresponding αꢀ
iodoperoxidates in excellent yields (Table 2, entries 2aꢀ2n). It is
noted that styrenes bearing electroꢀwithdrawing groups (4ꢀNO2,
3ꢀF and 1ꢀFꢀ2ꢀCF3) gave the disired products in higher yields
than those bearing electroꢀdonating groups (2ꢀMe or 2,5ꢀ
dimethyl) on the phenyl ring (Table 2, entries 2bꢀ2d, 2f, 2l and
2s). Styrenes with diverse functions were well tolerated, granting
entry for further functionalization. Styrene with halogen
substituents provided the products in good yields of 90ꢀ92% (2fꢀ
2m). Other functional motifs such as trifluoromethyl, cyano and
nitro group on the styrene remained intact and the corresponding
αꢀiodoperoxidates were isolated in 93%, 90% and 92% (2d, 2k,
2l) respectively. However, neither did the reaction with 4ꢀ
hydroxystyrene 1e nor 4ꢀmethoxystyrene 1p worked, but a large
amount of black precipitation formed after the reaction.
Moreover, vinyl substituted aromatic compounds such as
pyridine, thiophene and thiazole were also suitable for the αꢀ
iodoperoxidation reaction, thus providing good yields of the
corresponding products (2j, 2t and 2u). Furthermore, the
optimized reaction conditions was also successful for internal
styrene transꢀβꢀmethylstyrene 1n, forming the desired product 2n
in high yield with a diastereoselective ratio 1:1.16. However,
transꢀβꢀbromostyrene 1o, failed to give the corresponding
product. Similarly, aliphatic olefin such as cyclohexene 1q or
enven the nonconjugated olefin allylbenzene 1r were completely
unreactive, these results show that a resonance stabilizing group
on the olefin is beneficial. It was noteworthy that
a
Reaction conditions: styrene (1.0 mmol), I2 (0.6 mmol) and TBHP (3.6
c
mmol, 6.7 M TBHP in decane) were stirred at 25 °C for 2 h. bIsolated yield.
transꢀβꢀMethylstyrene was used as substrate.
Scheme 2 Control experiments for the reaction mechanism
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when αꢀMethylstyrene 1v, vinylnaphthalene 1w and 2ꢀchloroꢀ5ꢀ radical mechanism for the formation of βꢀiodoperoxidates in
vinylfuran 1x were used as substratea, diperoxidate products their work10b, based on our reaction results, an active cationic
rather than the αꢀiodoperoxidate were obtained.
iodine mechanism is presented in Scheme 3b for the formation of
Subsequently, the olefin scope for the synthesis of βꢀ βꢀiodoperoxidates with I2 and TBHP.14 Initially, iodine reacts
iodoperoxidates was explored using nonaqueous TBHP and I2 as with TBHP and generates the reactive hypoiodite acid and
the standard coupling partner (Table 3). In general, all styrenes tBuOI,14a,b which coordinates with styrene at the βꢀC position and
with either electroꢀdonating or electronꢀwithdrawing substituents
(a)
afforded products in good yields (Table 3, entries 3aꢀ3o).
However, 4ꢀvinylbenzoic acid and 4ꢀvinylphenol did not form
the desired products. This reaction gave good yields for αꢀ and βꢀ
substituted styrenes (Table 3, entries 3pꢀ3r). Notably, the method
was also proved to be applicable to aliphatic olefins. When
cyclohexene and octꢀ1ꢀene were used as substrate, the desired
iodoperoxide 3t and 3r were obtained in 88% and 86% yields,
respectively, under solventꢀfree reaction condition.
To gain insight into the reaction mechanism, several control
experiments were performed. When 1.0 equiv of TEMPO
(2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy),
a wellꢀknown radical
inhibitor, was added to the reaction mixture of syrene, NH4I, and
TBHP, the yield of 2a decreased from 96% to 16% (Scheme 2,
eqn(1)). When 2.0 equiv of TEMPO was added, the reaction was
completely halted (Scheme 2, eqn(2)). While in the standard
condition, no 3a product was obtained, after 1.0 equiv of
TEMPO was added (Scheme 2, eqn(3)). Notably, a high amount
of 1,2ꢀbis (tertꢀbutylperoxy) ethyl) benzene 4a and 2ꢀ(tertꢀ
butylperoxy)ꢀ1ꢀphenylethanol 4b were isolated, when etheneꢀ1,1ꢀ
diyldibenzene was employed under the standard reaction
conditions (Scheme 2, eqn (4)). These findings offered
(b)
Scheme 3 Suggested mechnisms of products formation
t
convincing evidence for the addition of BuOO• radical to the
polarizes the carbonꢀcarbon double bond. This is followed by
nucleophilic attack of BuOOH on αꢀCꢀatom to generate the βꢀ
double bond of styrene. The tBuOO• radical was generated from
the redox reaction between NH4I and TBHP. However, in the
t
t
t
iodoperoxidate and elimination of H2O or BuOH. BuOOH plays
dual roles in these transformation, acting as an oxidant to
increase the electrophilicity of the elemental iodine in the first
step and as a nucleophile in the second step. Conversion of both
iodine atoms of I2 into the final product resulted in 100% iodine
atom economy for iodoperoxidation of alkenes reaction.
One could argue that why the formation of βꢀiodoperoxidates
were totally halted in the combination of NH4I/TBHP reaction
system, since the formation of I2 during the redox reaction
same condition, the βꢀiodoperoxidate 3q and
βꢀiodoꢀ1,1ꢀ
diphenylethanol were formed especially, when replacing NH4I
with I2 (Scheme 2, eqn (5)). In addition, the experimental results
of the olefin scope for the synthesis of αꢀ and βꢀiodoperoxidates
indicated that different reaction mechanisms existed between
NH4I/TBHP and I2/TBHP reaction systems with following
reasons: (i) different reactivities of aliphatic olefins (Table 2,
entries 2q, 2r & Table 3, entries 3sꢀ3u); (ii) different products of
αꢀsubstituted alkenes (Table 2, entry 2p & Table 3, entry 3p;
Scheme 2, eqn (4) & (5)); (iii) different configurations of product
with βꢀsubstituted alkenes in the two different reaction condition
(Table 2, entry 2n & Table 3, entry 3r); (iv) only the trans
product was formed from cyclohexene (Table 3, entry 3t).
On the basis of the above results and reports in literatures, 12
two plausible mechanisms for the formation of αꢀ and βꢀ
iodoperoxidates are proposed (Scheme 3). In the reaction
condition of NH4I and TBHP for the synthese of αꢀ
iodoperoxidate ( Sheme 3a ), first, the tertꢀbutoxyl radical and
iodine radical formed.13 Then, the tertꢀbutoxyl radical abstracts a
hydrogen from TBHP to generate tertꢀbutylperoxyl radical. The
persistent radical tBuOO· is then immediately trapped by styrene,
leading to the formation of the benzylic radical intermediate I.
Finally, the rapid combination of I· and intermediate I results in
the αꢀiodoperoxidate product. Although Zhu et al. proposed a
between NH4I and TBHP. This may be attributed to the fact that,
I3 exists rather than I2 in abundance of iodide ion,15 thus exclude
ꢀ
continued oxidation by TBHP to form the
the reactive
hypoiodite acid or tBuOI. Therefore, the combination of
NH4I/TBHP provides the sole antiꢀMarkovnikov type
iodoperoxidate.
Conclusions
In conclusion, we have successfully developed a highly atomꢀ
economical, environmentꢀfriendly, and efficient method for
synthesis of αꢀ and βꢀiodoperoxidates with TBHP and
iodide/iodine under solventꢀfree reaction conditions. By varying
the iodide reagents, the reaction conditions can be fineꢀtuned to
regioselective synthesis of αꢀiodoperoxidates and βꢀ
iodoperoxidates. The excellent regioselectivity for the antiꢀ
Markovnikov type iodoperoxidates (αꢀiodoperoxidates) depended
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on the persistent radical effect while the exclusive formation of
Markovnikov type iodoperoxidates (βꢀiodoperoxidates) was
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attributed to the formation of
a more stable carbocation
intermediate. The reactions have broad substrate scope, mild
reaction conditions, and high functional group tolerance.
Investigation of the detailed reaction mechanism and potential
medicinal activities is underway in our laboratory.
We thank the Postdoctor Funding of Wuhan University of
Science and Technology (04026301) for financial support.
6
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Notes and references
School of Chemistry and Chemical Engineering, Wuhan University of
Science and Technology, Wuhan 430081, P. R. China. Eꢀmail:
gaoxf@wust.edu.cn.
†
Electronic Supplementary Information (ESI) available: Detailed
experimental procedures, characterization of products, and NMR spectral
charts. See DOI: 10.1039/b000000x/
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J. Name., 2012, 00, 1-3 | 5

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COMMUNICATION
Journal Name
DOI: 10.1039/C8GC00209F
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Green Chemistry
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DOI: 10.1039/C8GC00209F
Graphical Abstract
A highly atom-economical, efficiency and environment-friendly iodoperoxidation of alkenes with
TBHP and iodide/iodine is reported.