Hypoiodite-catalyzed regioselective oxidation of alkenes: An expeditious access to aldehydes in aqueous micellar media

Article abstract of DOI:10.1002/adsc.201400986

A highly anti-Markovnikov selective oxidation of alkenes based on in situ generated hypoiodite catalysis in aqueous micellar media under mild conditions has been described. This novel catalytic system realizes an efficient synthesis of aldehydes from alkenes in an economically viable and environmentally safe fashion. The preliminary mechanistic studies suggest that the reaction proceeds via tandem iodofunctionalization/1,2-aryl or alkyl migration. The scope and limitations of this tandem process are demonstrated with various mono- and disubstituted (terminal and internal) olefins.

Full text of DOI:10.1002/adsc.201400986

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DOI: 10.1002/adsc.201400986
Very Important Publication
Hypoiodite-Catalyzed Regioselective Oxidation of Alkenes: An
Expeditious Access to Aldehydes in Aqueous Micellar Media
Peraka Swamy,a,b Marri Mahender Reddy,b Mameda Naresh,a,b
Macharla Arun Kumar,b Kodumuri Srujana,b Chevella Durgaiah,b
and Nama Narendera,b,*
a
Academy Scientific and Innovative Research, CSIR – Indian Institute of Chemical Technology, Hyderabad, Telangana –
500 007, India
b
I&PC Division, CSIR – Indian Institute of Chemical Technology, Hyderabad, Telangana – 500 007, India
E-mail: narendern33@yahoo.co.in or nama@iict.res.in
Received: October 16, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400986.
Abstract: A highly anti-Markovnikov selective oxi-
dation of alkenes based on in situ generated hypoio-
dite catalysis in aqueous micellar media under mild
conditions has been described. This novel catalytic
system realizes an efficient synthesis of aldehydes
from alkenes in an economically viable and envi-
ronmentally safe fashion. The preliminary mecha-
nistic studies suggest that the reaction proceeds via
tandem iodofunctionalization/1,2-aryl or alkyl mi-
gration. The scope and limitations of this tandem
process are demonstrated with various mono- and
disubstituted (terminal and internal) olefins.
Aldehydes are valuable precursors,[4] versatile inter-
mediates in target oriented organic synthesis[5] and es-
sential ingredients in the manufacture of flavours,
soaps and perfumes.[6] Traditional processes for alde-
hyde preparation rely on the oxidation of primary al-
cohols. Generally, these methods require prior synthe-
sis of alcohols from terminal olefins which is a critical
process.[7] The current approaches for aldehyde pro-
duction from C-C multiple bonds are hydroformyla-
tion of alkenes and hydration of alkynes. But, the hy-
droformylation provides homologous aldehydes and
the anti-Markovnikov hydration of alkynes frequently
utilizes metal-based catalysts.[8] As the terminal al-
kenes are attractive starting materials and key inter-
mediates for many reactions, their direct oxidative
transformation to methyl ketones on the basis of Mar-
kovnikovꢀs rule, known as Tsuji–Wacker oxidation,
has been broadly adapted in both academia and in-
dustry.[9] However, in contrast, the aldehyde selective
Keywords: aldehydes; hypoiodite catalysis; mi-
celles; oxidation; regioselectivity
With the increased environmental consciousness, oxidation (without the cleavage of C=C double bond)
achieving organic transformations in aqueous media of terminal olefins has represented a formidable syn-
under mild conditions is of great importance in thetic challenge for many decades.[10] Recently, signifi-
modern synthetic chemistry and paves the way to cant efforts have been made to address the historical
design green, safe and economically viable processes. challenge of selective anti-Markovnikov functionaliza-
Despite the inherent advantages of water, such as tion of terminal olefins to aldehydes, that led to di-
readily availability, non-toxicity, non-flammability, verse metal-based catalytic systems (Scheme 1a).[11]
cheapness and safe handling, over organic solvents,[1] However, most of them require relatively costly
its use as reaction medium has constraints due to the metals with some degree of toxicity, complex ligands,
poor solubility of most organic substances. This solu- hazardous solvents and harsh reaction conditions. Al-
bility issue can be overcome by using surfactants ternatively, a few metal-free protocols have appeared
which form nanometer micelles (nanoreactors) by in the literature which utilize hypervalent iodine com-
self-aggregation in water.[2] Over the past few years, pounds in stoichiometric amounts and strong acids as
the use of surfactants in aqueous reactions has re- additives (Scheme 1b).[12] But, the use of stoichiomet-
ceived considerable attention from synthetic chemists ric hypervalent iodine compounds generates equimo-
owing to their ability to not only increase the solubili- lar amounts of organic waste. Thus, the development
ty of organic substrates but also the selectivity and re- of simple, safer and sustainable strategies for the anti-
activity of a reaction.[3]
Markovnikov selective oxidation of alkenes under
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Peraka Swamy et al.
Table 1. Optimization study for the regioselective oxidation
of styrene (1a) to phenylacetaldehyde (3a).[a,b]
Entry NH4I
Oxidant
Surfactant
(mol%)
Time Yield
(mol%) (equiv.)
[h]
[%]
1
20
oxone (1)
N/A[c]
N/A[c]
2.5
5
24
43
00
trace
2
20
N/A[c]
3[d]
4
N/A[c]
20
oxone (1)
oxone (1)
oxone (1)
oxone (1)
oxone (1)
N/A[c]
SDS (20)
CTAB (20)
3PP[e] (20)
TWEENꢂ 80
(20)
0.25 83
Scheme 1. Different strategies for the anti-Markovnikov se-
lective oxidation of vinylarenes.
5
6
7
20
20
20
1
1
2
48
58
51
8
9
20
20
K2S2O8 (1) SDS (20)
24
24
00
18
mild conditions is highly desirable and presents a sig-
nificant challenge to research.
m-CPBA
(1)
aq. H2O2
(1)
aq. TBHP
(1)
SDS (20)
SDS (20)
SDS (20)
10
11
20
20
24
24
00
00
In recent years, hypoiodite-catalyzed oxidative
transformations have emerged as an attractive area of
research.[13] However, to the best of our knowledge,
there are no reports on hypoiodite-mediated catalytic
oxidation of alkenes in an anti-Markovnikov fashion.
Herein, we describe a novel and efficient method for
the highly regioselective oxidative functionalization of
olefins using stable, inexpensive and easy-to-handle
reagents, such as NH4I as iodine containing precata-
lyst and oxone as terminal oxidant, in presence of
aqueous SDS self-organized nanoreactors at room
temperature.
Initially, we anticipated the regioselective oxidation
of vinylarenes through the activation of C=C double
bond with in situ generated electrophilic iodine spe-
cies in aqueous media. To test our hypothesis, we
have chosen styrene as a model substrate and investi-
gated its reaction with NH4I (as precatalyst) and
oxone (as terminal oxidant) in water. The reaction of
styrene (1a) with 20 mol% of NH4I and 1 equiv. of
12
13
14
15
16
17
20
20
10
30
20
20
oxone (1)
oxone (1)
oxone (1)
oxone (1)
SDS (30)
SDS (40)
SDS (30)
SDS (30)
0.13 93
0.1 93
0.25 81
0.11 93
0.08 66
0.58 88
oxone (1.5) SDS (30)
oxone
SDS (30)
(0.75)
18[f]
20
oxone (1)
SDS (30)
0.13 68
[a]
Reaction conditions: styrene (1 mmol), NH4I, oxidant,
surfactant, water (10 mL), room temperature.
Isolated yields (as 2,4-DNP derivative 4a).
N/A refers to not applicable.
1-Phenylethane-1,2-diol was observed.
3PP=3-(1-pyridinio)-1-propanesulfonate.
5 mL of water were used as solvent.
[b]
[c]
[d]
[e]
[f]
oxone in water gave the corresponding product 3a in investigation and encouraged us to further study the
moderate yield (Table 1, entry 1). When the reaction reaction for optimal conditions.
was performed in the absence of NH4I, an extremely
In an attempt to improve the yield of 3a, various
low yield of the desired product 3a was observed reaction parameters have been considered and exam-
along with unwanted 1-phenylethane-1,2-diol in quan- ined sequentially. In this context, various other surfac-
titative yield, which is consistent with the report of tants including cetyltrimethylammonium bromide
Zhu and Ford,[14] and the reaction did not proceed in (CTAB) (cationic), 3-(1-pyridino)-1-propanesulfonate
the absence of oxone (Table 1, entries 2 and 3). These (zwitterionic) and Tweenꢂ 80 (non-ionic) were inves-
reactions highlight the role of the iodine precursor tigated and we found that not one of the surfactants
and oxone in the present catalytic system for the syn- was appropriate to increase the yield of desired prod-
thesis of aldehydes from olefins. Surprisingly, the se- uct above that obtained for SDS (Table 1, entries 5–
lectivity and reactivity of a reaction was greatly en- 7). Next, several oxidants were tested in the reaction
hanced when the reaction was carried out in the pres- and the replacement of oxone with K2S2O8, m-CPBA,
ence of an amphiphilic surfactant, i.e., sodium dode- aq.H2O2 or aqueous TBHP furnished the product 3a
cyl sulfate (SDS) (anionic) in water at room tempera- albeit in low or zero yield (Table 1, entries 8–11). Fi-
ture (Table 1, entry 4). These preliminary findings nally, the effects of solvent quantity and different
suggest that the in situ generated hypoiodite species, mole ratios of reagents (NH4I, oxone and SDS) on
i.e., [OI]À or (HOI) from NH4I and oxone[15] in aque- the reaction yield were established (Table 1, en-
ous micellar media, could be suitable for our current tries 12–18). After this extensive screening, we have
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Hypoiodite-Catalyzed Regioselective Oxidation of Alkenes
ent catalytic system and afforded the desired products
3a–3k in good to excellent yields (Table 2, entries 1–
11). The methyl-substituted styrenes 1b, 1c and 1d re-
acted smoothly to give the corresponding aldehydes
3b, 3c and 3d in 79–93% yields (Table 2, entries 2–4).
The bulky alkyl group-substituted styrene 1e exhibit-
ed slightly lower reactivity to generate the desired
product 3e in a synthetically useful yield of 55% after
6.33 h at room temperature, whereas the rate and
yield of the reaction were enhanced when the temper-
ature was raised to 558C (Table 2, entry 5). Notably,
the fluorine-substituted styrenes were efficiently oxi-
dized, irrespective of the position of substituent, to
the respective aldehydes 3f and 3g in excellent yields
Figure 1. (a) A schematic representation of the nanometer
micelle formed from SDS in water. (b) Illustration of differ-
ent regions in aqueous micellar media: (i) interior of micelle
(hydrophobic core); (ii) interfacial region (water-micelle in-
terface); (iii) bulk aqueous media.
observed that the 20 mol%, 1 equiv. and 30 mol% of (Table 2, entries 6 and 7). Meanwhile the chlorine and
NH4I, oxone and SDS, respectively, were optimum bromine substituents at the para position led to slight-
with respect to styrene to obtain the maximum yield ly higher yields than they do at a meta position of the
of the desired product in water at room temperature phenyl ring of styrene (Table 2, entries 8–11). Un-
(Table 1, entry 12).
fortunately, the substrates 2-vinylnaphthalene and 4-
The higher reactivity and selectivity of a reaction in vinylbiphenyl did not react under the present reaction
the presence of SDS molecules above their critical mi- conditions. This is possibly due to the poor solubility
celle concentration (CMC) in aqueous media might of these solid substrates in the present reaction
be attributed to the formation of nanometer micelles medium.
(Figure 1a). The in situ self-aggregation of SDS mono-
To extend the scope of this reaction further, we in-
mers in water was confirmed by DLS analysis and op- vestigated some 1,1-disubstituted, internal and ali-
tical microscope studies, which indicated the forma- phatic olefins and the results are summarized in
tion of sphere-like shapes of the nanoreactors (see Table 3. To our delight, the substrates 1l–1o were well
the Supporting Information).
tolerated under the present reaction conditions and
Having the optimized conditions in hand, we inves- resulted in the formation of anti-Markovnikov prod-
tigated the versatility of this methodology with a wide ucts 3l–3o in 83–95% yields (Table 3, entries 1–4).
variety of vinylarenes and the results are summarized The a- and b-substituted styrene derivatives were oxi-
in Table 2. Various electron-donating and electron- dized to the corresponding products 3l, 3m and 3n in
withdrawing groups were well tolerated with the pres- 93%, 86% and 83% yields, respectively (Table 3, en-
Table 2. Synthesis of aldehydes from vinyl arenes.[a,b]
Entry
Olefin 1
Time [h]
Yield [%] of 3
1[c]
2[c]
3
R1 =R2 =R3 =H; 1a
0.13
0.45
0.25
93
93
90
R1 =R2 =H, R3 =Me; 1b
R1 =R3 =H, R2 =Me; 1c
R1 =R3 =Me, R2 =H; 1d
R1 =R2 =H, R3 =t-Bu; 1e
4[c]
5
0.66
79
6.33 (0.75)[d]
55 (78)[d]
6[c]
X1 =H, X2 =F; 1f
X1 =F, X2 =H; 1g
X1 =H, X2 =Cl; 1h
X1 =Cl, X2 =H; 1i
X1 =H, X2 =Br; 1j
X1 =Br, X2 =H; 1k
0.15
0.58
0.58
1.83
2.91
2.96
94
92
93
77
92
77
7[c]
8[c,e]
9[e]
10[c,e]
11[c,e]
[a]
Reaction conditions: substrate (1 mmol), NH4I (20 mol%), SDS (30 mol%), oxone (1 mmol), H2O (10 mL), room temper-
ature.
Isolated yields.
[b]
[c]
[d]
[e]
Isolated as 2,4-DNP derivative 4.
Reaction at 558C.
<2% of Markovnikov product was observed by H NMR analysis of crude reaction mixture.
1
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Table 3. Hypoiodite-catalyzed oxidation of 1,1-disubstituted,
internal and aliphatic olefins.[a,b]
Entry Olefin
Time [h] Product
Yield [%]
1
1.16
7
93
2
86
3
4
1.25
0.13
83[c]
Scheme 3. Control experiments.
95[c]
–
5
1-dodecene 24
–
a radical mechanism. When 2-phenyloxirane (1p) was
subjected to the standard reaction conditions, the for-
mation of 3a was not observed [Scheme 3, Eq. (2)],
which indicates that 1p may not be the intermedi-
[a]
Reaction
conditions:
substrate
(1 mmol),
NH4I
(20 mol%), SDS (30 mol%), oxone (1 mmol), H2O
(10 mL), room temperature.
Isolated yields.
[b]
[c]
AHCTUNGTRENNUNG
ate[11a,b] in the aldehyde-selective oxidation process.
Isolated as 2,4-DNP derivative 4.
Likewise, we examined the reaction of 2a using the
same procedure and obtained the product 3a in 94%
tries 1–3). Interestingly, the oxidation of cyclic olefin yield [Scheme 3, Eq. (3)]. This reaction suggests the
1o leads to the ring contraction product 3o in 95% co-iodo product 2a as an intermediate in the regiose-
yield (Table 3, entry 4). However, the aliphatic acyclic lective oxidation of alkenes to aldehydes. To further
alkene, i.e., 1-dodecene, under standard conditions confirm the intermediate in the reaction, we studied
did not yield the desired oxidation product and only the styrene oxidation reaction under identical condi-
the starting material was recovered after 24 h tions at different time intervals and the yields[16] of
(Table 3, entry 5).
products and unreacted styrene were plotted against
As can be seen from Table 2 and Table 3, it is evi- time (see the Supporting Information). This reaction
dent that the vicinal migration of an aryl or alkyl profile unequivocally reveals the intermediacy of io-
moiety during the course of reaction leads to the de- dofunctionalized product 2 in the oxidation of alkene
sired anti-Markovnikov products. To confirm the mi- 1 to corresponding anti-Markovnikov product 3.
gration process, we have investigated the reaction of
Based on the observed results during the evolution
b,b-dideuterated styrene under standard reaction con- of the scope of the reaction and control experiments,
ditions and obtained the corresponding aldehyde 3a a plausible reaction mechanism for the formation of
(d2), with two deuterium atoms at the benzylic posi- aldehydes from alkenes is depicted in Scheme 4. It is
tion, in 91% yield (Scheme 2). This isotope labelling assumed that the oxone oxidizes IÀ to HOI or [IO]À
study unambiguously confirms the aryl or alkyl group (A) in the aqueous phase and most of these oxidized
migration in the oxidation of alkenes to the corre- iodine species reside in the immediate vicinity of an
sponding anti-Markovnikov products.
anionic micelle surface (Figure 1b).[17] The in situ gen-
To explore the possible pathway for this novel cata- erated hypoiodite species (A) reacts with the elec-
lytic reaction, several control experiments have been
carried out and are illustrated in Scheme 3. When the
styrene was subjected to our optimal conditions in the
presence of TEMPO, the desired product 3a was ob-
tained without any change in the yield [Scheme 3, Eq.
(1) and Table 2, entry 1]. This result clearly indicates
that the styrene oxidation did not proceed through
Scheme 4. Plausible mechanism for the hypoiodite-catalyzed
oxidation of alkenes to aldehydes.
Scheme 2. Isotope labelling experiment.
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Hypoiodite-Catalyzed Regioselective Oxidation of Alkenes
tored by TLC, eluent: n-hexane-ethyl acetate or as indicated
by the regeneration of iodine colour). The organic product
mixture was extracted with DCM (3ꢃ25 mL). The organic
layer was washed with 5% aqueous sodium thiosulfate solu-
tion (10 mL) and dried over anhydrous Na2SO4. The solvent
was removed under vacuum and the residue was purified by
column chromatography on silica gel using n-hexane-ethyl
acetate as eluent to give desired products. The products 3a,
3b, 3d, 3f–3h, 3j–3k, 3m and 3o were isolated as their corre-
sponding 2,4-DNP derivatives 4a, 4b, 4d, 4f–4h, 4j–4k, 4n
and 4o, respectively. Spectroscopic data of all products
(shown in Tables 2 and 3) and copies of their 1H and
13C NMR spectra are provided in the Supporting Informa-
tion.
tron-rich double bond of alkene 1 [located at the in-
terfacial region due to their equilibrium position be-
tween hydrophobic core and polar head group (Fig-
ure 1b)] to form a cyclic iodonium ion (B). Then, this
three-membered cyclic iodonium ring is opened by
the nucleophile (OHÀ) to form a co-iodo intermediate
2. De-iodination, in the presence of oxone, of inter-
mediate 2 and subsequent 1,2-aryl/alkyl migration
through a semipinacol rearrangement leads to the de-
sired product 3. Oxone converts the iodide ion gener-
ated in the first cycle into hypoiodite species (A) to
further continue the catalytic cycle until complete
consumption of the substrate.
In conclusion, we have developed a novel hypoio-
dite-catalyzed protocol for the anti-Markovnikov se-
lective oxidation of alkenes under mild conditions.
The present catalytic system utilizes stable, cheap and
easy-to-handle inorganic salts as reagents (NH4I as
iodine pre-catalyst and oxone as terminal oxidant)
and SDS as micelle forming surfactant in water. The
nanoreactors formed by SDS in aqueous media were
studied by optical microscopy and DLS. Moreover,
the possible reaction pathway is also proposed
through a tandem iodofunctionalization/1,2-aryl or
alkyl migration based on preliminary mechanistic in-
vestigations.
Acknowledgements
We thank the CSIR Network project CSC-0125 for financial
support. P.S. and K.S. acknowledge the UGC, India and
M.M.R., M.N., M.A.K., and C.H.D. acknowledge the CSIR,
India for financial support in the form of fellowships.
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Experimental Section
Materials and Methods
All chemicals (reagent grade) were purchased from Sigma–
Aldrich and used as received without further purification.
1H NMR spectra were recorded at 300 or 500 MHz and
13C NMR spectra at 75 or 125 MHz in CDCl3. The chemical
shifts (d) are reported in ppm units relative to TMS as an in-
1
ternal standard for H NMR and CDCl3 for 13C NMR spec-
tra. Coupling constants (J) are reported in hertz (Hz) and
multiplicities are indicated as follows: s (singlet), br s (broad
singlet), d (doublet), dd (doublet of doublet), m (multiplet).
GC analysis were carried out using GC Shimadzu (GC-
2014) gas chromatograph equipped with FID detector and
capillary column (EB-5, length 30 m, inner diameter
0.25 mm, film 0.25 mm). Mass spectra were recorded on
a time of fight (TOF) mass spectrometer. Size and shape
measurement studies were carried out using dynamic light
scattering (DLS) and an optical microscope. TLC inspec-
tions were performed on Silica gel 60 F254 plates. Column
chromatography was performed on silica gel (100–200 mesh)
using n-hexane-EtOAc as eluent.
General Procedure
To a well stirred (for about 10 min) solution of SDS
(30 mol%) in distilled water (10 mL) were added NH4I
(20 mol%) and alkene (1 mmol). The mixture was stirred
for 30 min and then the oxoneꢂ (1 mmol) was slowly added.
The reaction mixture was allowed to stir at room tempera-
ture until the alkene had completely disappeared (moni-
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6
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