Hypervalent iodine catalysis for selective oxidation of Baylis-Hillman adducts via in situ generation of o-iodoxybenzoic acid (IBX) from 2-iodosobenzoic acid (IBA) in the presence of oxone

Article abstract of DOI:10.1039/c6nj02628a

An efficient, environmentally benign, eco-friendly protocol for selective oxidation of primary and secondary Baylis-Hillman alcohols to the corresponding carbonyl compounds has been developed. We have demonstrated the catalytic use of o-iodoxybenzoic acid

Full text of DOI:10.1039/c6nj02628a

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Hypervalent Iodine Catalysis for Selective Oxidation of Baylis–
Hillman adducts via In Situ Generation of o-Iodoxybenzoic Acid
(IBX) from 2-Iodosobenzoic acid (IBA) in Presence of Oxone
Received 00th January 20xx,
Accepted 00th January 20xx
Raktani Bikshapathi,a Sai Prathima Parvathaneni,a* and Vaidya Jayathirtha Raoa,b
*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient, environmentally benign, eco-friendly protocol for selective oxidation of primary and secondary Baylis–Hillman
alcohols to the corresponding carbonyl compounds has been developed. We have demonstrated the catalytic use of o-
iodoxybenzoic acid (IBX) generated in situ from 2-Iodosobenzoic acid (IBA) in presence of oxone (2KHSO5·KHSO4·K2SO4) as a
co-oxidant. This efficient method notably enables better to high yields without the use of any toxic heavy metals and
direct use of tricky IBX. Furthermore, the synthesized catalyst could be recovered conveniently using a reductive work-up.
OAc
OH
O
OH
O
AcO
OAc
I
Introduction
I
I
O
O
Selective oxidation of primary and secondary alcohols to aldehydes,
ketones are important fundamental transformations in synthetic
organic chemistry. To date, many excellent catalytic methods have
been developed for oxidations of alcohols.1 However there is a
strong impetus to develop efficient, greener methods with greater
selectivity without the use of transition metals. Such methods are
highly desirable, and very important for both chemical and
pharmaceutical industry.2
O
O
O
IBX
B
DMP (12-I-5) C
IBA (10-I-3)
A
In order to solve this problem catalytic systems with in situ
generation of iodine (V) species from the corresponding iodine
reagents have also been developed to minimize the hazardness of
highly reactive iodine (V) species during the reaction.9 We have thus
planned in situ formation of active I (V) state of IBX from catalytic
amounts of iodosobenzoic acid (IBA) (Scheme 1), by employing
During the past decade hypervalent iodine compounds have
attracted a significant interest as mild, selective, easily available and
environmentally benign reagents with high oxidizing capabilities in
synthetic organic chemistry.3 The most important representatives
of this class of compounds are 2-iodosylbenzoic acid (IBA),
iodoxybenzoic acid (IBX) and Dess-Martin periodinane (DMP) which
have found wide applications as oxidizing reagents in the synthesis
of biologically important complex organic molecules.4 Recently 2-
Iodoxybenzenesulfonic Acid was proved to be an extremely active
catalyst for the selective oxidations in the presence of catalytic
iodine(V)/Oxone oxidation system.5 In particular, hypervalent
iodine heterocycles derived from benziodoxoles with pentavalent
iodine are Dess–Martin periodinane (DMP, C)6 and 1-hydroxy-1, 2-
benziodoxol-3-(1H)-one-1-oxide (IBX, B)7 have emerged as the
reagents of choice for selective oxidative transformations. Despite
the polymeric structure of IBX, its low solubility and potentially
explosive nature restrict the practical application of IBX.8
oxone as
a co-oxidant. The application of oxone (2KHSO5·
KHSO4·K2SO4) has increased rapidly as it offers several advantages,
such as stability, nontoxic, simple handling, controllable addition
etc.10
OH
HO
O
I
I
KHSO5
O
O
O
O
IBA
A
IBX
B
Scheme 1. Insitu generation of iodoxybenzoic acid (IBX)
The Morita–Baylis–Hillman (MBH) reaction is an organocatalyzed
chemical transformation used for the preparation of natural
products, heterocycles and drugs.11 MBH adducts are highly
functionalized small molecules with high synthetic versatility.12
Recently our group has reported the successful synthesis of new
epalrestat analogues from Morita–Baylis–Hillman adducts,
especially for those derived from aromatic aldehydes with nitrile
functionality.13 It is worth noting that the oxidation reaction can be
troublesome for MBH adducts derived from acrylic esters to form
aldehydes, since they are prone to extensive oxidative degradation.
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The biological and chemical relevance of these adducts justify the Table 1: Screening of Hypervalent iodine induced oxidation
reactionsa
development of alternative methods for their oxidations as they
have conjugated, highly reactive functionalisations. The synthesis of
this potential 1,1-dicarbonyl-substituted alkene
3 has been
reported from the corresponding saturated 1-phenylsulfinyl
derivatives, either by oxidation of β-hydroxy-α-phenylsulfenyl
carbonyl compounds or direct acylation of α-phenylsulfenyl enolate
anions with acid chloride in the literature.14 Herein we employ MBH
derived alcohols as synthetic equivalents for selective production of
1,1-dicarbonyl-substituted alkenes making this approach a valuable
alternative for their synthesis.
In recent years IBX has been used for oxidative transformations
involving MBH adducts.15 In all the cases they have employed IBX
1.5-3.0 equivalents for oxidation of Morita–Baylis–Hillman
adducts.16 However, there have been no reports on the catalytic use
of IBA for in situ generation of IBX for oxidation of MBH adducts.
Thus, we sought to develop highly efficient benziodoxole derived
iodine(III)-analogs as catalysts for the oxidation of alcohols with
oxone allowing high selectivity under mild conditions.
Scheme 2. Oxidation of MBH derived alcohols to carbonyl
compounds using a catalytic amount of IBA.
In continuation to our interest to develop metal free oxidative
protocols with hypervalent iodine reagents,17 we envisaged that in
situ generated IBX could function as efficient system for selective
formation of carbonyls from MBH derived alcohols. Till date very
few reports are available in literature for isolating the MBH derived
aldehydes with ester functionality.18 We have successfully
circumvented the over oxidation issues associated with the
oxidation of MBH adducts and their derived alcohols, as they have
conjugated system with competiting groups. By employing this in
situ iodine (V) strategy as a key step for the oxidations of variety of
MBH adducts with excellent yields and high selectivity. A wide
variety of Morita-Baylis–Hillman adducts and their derived alcohols
could be selectively oxidized directly leading to carbonyl
compounds in simple manner (Scheme 2).
a All reactions were carried out at 1mmol scale at 80 °C for 6h in
2mL of solvent.b Isolated Yield. cTemperature at 100 °C for 24h,
d40 °C, e60 °C.
Reactions were carried with 2-iodo benzoic acid (2IBAcid), Phenyl
iodine(III) diacetate (PIDA), 1-(tert-Butylperoxy)-1,2-benziodoxol-
3(1H)-one (IBP) by employing 2 equiv without using any external
oxidant (entries 1 to 3). Although PIDA gave 20% yield (entry 2),
2IBAcid and IBP could not furnish the desired product (entries 1 and
3). In pursuit we have chosen oxone as an environmentally safe co-
oxidant for a catalytic hypervalent iodine oxidation with 2IBAcid
and PIDA as they are commercially available. The 2IBAcid was found
to be ineffective even in presence of co-oxidant (entry 4), however
PIDA gave the corresponding oxidized product in 40% yield (entry
5). Then we have synthesized IBA from 2-iodo benzoic acid and
Results and Discussion
Our initial attempts were directed towards identifying suitable
hypervalent iodine based catalytic system for selective oxidation of
MBH derived alcohols. Methyl 2-benzoylacrylate was selected as a
model substrate to identify the suitable catalytic system (Table 1).
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DMSO as a solvent system, only trace amount of oxidized product To explore the generality of the in situ generated B catalyzed
was observed (entry 6). Then TBHP, oxygen and oxone were oxidation of alcohols with oxone, various structurally diverse
employed as oxidants with IBA system (entries 7 to 9). To our secondary alcohols were examined as substrates under optimized
surprise the corresponding carbonyl compound was formed in 95% conditions. First, MBH adducts were prepared from acrylates and
yield with in-situ generated IBX oxidation (entry 9). The molar ratios were tested for IBA oxidations. All the MBH adducts (2a-2s) gave
of IBA and oxone required to achieve quantitative conversion of corresponding keto derivatives (3a-3s) with good to excellent yields
primary alcohols was closely monitored. Among them 0.6, 0.5 and Table 2. The reactions with different electron-donating and
0.2 equiv gave 95%, 95% and 94% yields respectively. Remarkable electron-withdrawing substituents on the phenyl ring of BH adducts
solvent effects were observed with catalytic hypervalent iodine were tolerated leading to the high yields of oxidized products.
oxidation system (entries 12-16). However the reaction was sluggish There is not much change in the yields for para and meta
with other solvents and the yield of 3a was only 60% with EtOAC, substituted MBH alcohol derivatives. The unsubstituted phenyl ring
and 50% with DCM and DMSO. It gave only 30 % with THF and 90 % with methyl (3a) and ethyl (3j) ester functionality proceeded to give
yield with toluene only after 24h. The reaction did not proceed with the desired products in good to excellent yields 94% and 95%
oxone and TBHP in the absence of IBA (entry 17 and 18). Thus with respectively. The bromo substitution at meta position containing
only 0.2 equiv of B and 1 equiv of oxone, the reaction was finished products delivered in low yields (3g and 3k) 84%, 85% when
within 4 h to give the desired product 3a in 94% yield in CH3CN compared to chloro substituted meta isomer (3i) with 89%. The
system (entry 11).
meta (CH3, OMe) substituted MBH adducts with ethyl ester
functionality gave (3n) 94%, (3o) 92%, whereas with methyl acrylate
derived BH alcohols resulted in (3h) 91%, (3b) 92% yields of the
desired products. However electron-donating group substituted
MBH adducts (OMe, CH3) gave better yields, (3d) 94%, (3f) 95% and
(3m) 96% than electron withdrawing substituents. In case of para
fluoro substituted the desired product was achieved in (3c) 88%,
and chloro substituted with (3e) 89%, (3l) 92% yields respectively.
Table 2: Oxidation of MBH adduct with IBA/Oxonea
Table 3: Oxidation of MBH allylic Alcohol with IBA/Oxonea
a All reactions were carried out at 1mmol scale, IBA (0.2 equiv),
Oxone (1 equiv) in 2mL of CH3CN, reflux. bIsolated Yield.
a All reactions were carried out at 1mmol scale, IBA (0.2 equiv),
Oxone (1 equiv) in 2mL of CH3CN, reflux.bIsolated Yield.
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Table 4: Oxidation of MBH allylic Alcohol with IBA/Oxone:
Journal Name
O
IBX, KHSO5
CH3CN
OH
H
R4
R4
CN
CN
7a-7g
6a-6g
Yield (%)b
Keto Product
Entry
MBH
Time (h)
Fig 1: Reusability of IBA
A
7a, R4 = Phenyl
95
96
6a, R4 = Phenyl
1
2
4
4
6b, R4= 4-Me Phenyl
7b, R4 = 4-Me Phenyl
7c, R4 = 4-Et Phenyl
7d, R4 = 4-OMe Phenyl
In order to show the scale-up potential of this efficient selective
transformation, we have conducted a gram-scale synthesis of 3a
and 5a using respective MBH adduct (40 mmol), IBA (8 equiv),
Oxone (40 equiv) in 80 mL of CH3CN for about 6h under reflux
conditions. This gave excellent yield of the desired products,
demonstrating the industrial viability for selective synthesis of MBH
oxidized products.
6c, R4 = 4-Et Phenyl
95
95
3
4
4
5
6
7
6d, R4 = 4-OMe Phenyl
4
5
6e, R4= 3-OMe Phenyl
6f, R4 = 2-OMe Phenyl
7e, R4 = 3-OMe Phenyl
7f, R4 = 3-OMe Phenyl
7g, R4 = 2-OMe Phenyl
92
91
We have proposed a possible reaction pathway for oxidation of
alcohols with IBX B is represented in Scheme 3.5a,21 The catalytic
cycle of B, which was prepared in situ from A, could be
accomplished by regenerating A through the oxidation of 3a with
oxone. It was experimentally confirmed that IBX is the true active
species with oxidation state of “I(V)” which is essential in the
catalytic cycle of IBA-catalyzed oxidation with oxone.5a Initially IBA
gets oxidized by oxone to generate IBX, which will activate the
Baylis Hillman alcohol 2a with elimination of water molecule and
generate the intermediate X.5a This will undergo elimination of
alpha hydrogen and further rearrange to form the oxidized product
3a with regeneration of the IBA A as demonstrated in X of Scheme
3. At the end of reaction the reduced form of IBX B is easily
separated by simple filtration and can be regenerated by oxidation
with oxone9 and can be reused for four cycles without any
appreciable loss in its activity as shown in Figure 1.
5
6
6g, R4 = 4-Br Phenyl
88
a All reactions were carried out at 1mmol scale, IBX (0.2 equiv),
oxone (1 equiv) in 2mL of CH3CN, reflux. bIsolated Yield.
In addition, we also tested the reaction with more challenging MBH
derived allylic alcohols with ester functionality for selective
oxidation to aldehydes, and the results are represented in Table 3.
To extend this methodology we have synthesised (2E)-3-phenyl-2-
hydroxymethylprop-2-enoate (4a) directly from methyl 3-phenyl-3-
hydroxy-2-methylenepropanoate (2a) under reported reaction
conditions.19 It is interesting to note that BH derived allylic alcohols
(4a) proceeded reaction well with 100% conversion, selectively (5a)
with 98% yield of the aldehyde as desired product. It is noteworthy
to observe only aldehyde as oxidised product for primary allylic
alcohols (Table 3) when compared to reported oxidation of primary
alcohols to corresponding carboxylic acids.9a Notably para, meta,
ortho substituted Me gave (5d) 95%, (5c) 92%, (5b) 90% and
meta substituted OMe resulted in (5e) 85%, yield of the
corresponding aldehydes. In case of fluoro substitution at
phenyl the product (5f) was formed with 85% yield (Table 3,
OXONE
KHSO4
HO
O
I
OH
O
I
O
O
O
IBX B
OH
IBA A
R
entries 1 to 6)
.
2a
-H2O
Further, we extended scope of the reaction with various BH
alcohols with ester functionality for selective oxidation to aldehydes
under the optimized reaction conditions (Table 4, entry 1 to 7).
R
H
O
O
O
I
R
Then we have carried out the synthesis of [E]-α cyano cinnamyl
alcohols from Baylis-Hillman adducts,20 and their subsequent
O
3a
O
X
oxidation to aldehydes. All cyano cinnamyl alcohols (6a-6g) were
Scheme 3: Plausible Reaction Mechanism
oxidized selectively with major [E]- α-cyanocinnamic aldehydes (7a-
7g) in excellent yields.
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in
Current
Chemistry,
Vol.
224,
Springer-Verlag,
Stang,
Conclusion
Berlin Heidelberg, 2003; c) V. V. Zhdankin, P.
J. Chem. Rev. 2002, 102, 2523; d) M.Uyanik and K. Ishihara
Chem. Commun., 2009, 45, 2086; e) A. Duschek and S. F. Kirsch
Angew. Chem. Int. Ed. 2011, 50, 1524; f) V.V. Zhdankin Chem.
Rev. 2008, 108, 5299; g) A.Yoshimura and V. V. Zhdankin Chem.
Rev. 2016, 116, 3328; h) F. Chen and A. S. K. Hashmi Org.
Lett. 2016, 18, 2880.
In summary, we report a facile oxidation system for one-step
conversion of the Baylis-Hillman adducts to potential synthons i.e.,
secondary alcohols to ketones and primary alcohols to aldehydes in
the presence of IBA. Several significant features of this protocol are
the catalytic use of 2-iodosobenzoic acid (IBA) A that tolerates the
presence of a wide range of substituents on substrates under mild
conditions with high selectivity. We anticipate that the simplicity,
catalytic nature of this system, regeneration by simple filtration,
with no byproducts, high selectivity meet the desirable goals of eco-
friendly chemical transformations.
4
a) T. Wirth, Angew. Chem., Int. Ed. 2001, 40, 2812; c)
V. V. Zhdankin, Reviews on Heteroatom Chemistry, 1997, 17,
133; c) Wirth, T. Organic Synthesis Highlights V; Wiley-VCH:
Weinheim, 2003; p 144.
5. a) M. Uyanik, M. Akakura, K. Ishihara J. Am. Chem. Soc. 2009,
131, 251; b) M. Uyanik, R. Fukatsu, K. Ishihara Org. Lett., 2009,
11, 3470; c) M. Uyanik, T. Mutsuga, K. Ishihara Molecules 2012,
17, 8604-8616; d) M. Uyanik, K. Ishihara Org. Synth. 2012, 89,
105-114
ExperimentalSection
General Procedure for IBA A-Catalyzed Oxidation: An oven-dried
flask was charged with stir bar, BH derived alcohol 2(a-o), (1.0
mmol), IBA A (0.2 equiv), Oxone (1 equiv) in dry acetonitrile (2.0
mL) under reflux conditions. Then the reaction mixture was stirred
until complete conversion takes place as indicated by TLC analysis.
The crude reaction was cooled to room temperature, the 2-
iodosylbenzoic acid (IBA) was filtered off and the solvent was
removed under vacuum. The filtrate was concentrated in vacuo and
was purified by silica gel column chromatography to afford the
desired products 3(a–o). The IBA was reoxidized using oxone and
can be reused for consecutive cycles.
6
a) D. E. Dess, J. C. Martin, J. Org. Chem. 1983, 48,
4155; b) D. E. Dess, S. R. Wilson, J. C. Martin, J.
Am. Chem. Soc. 1993, 115, 2488; c) P. Wipf, J. K.
Jung, J. Org. Chem. 1998, 63, 3530; d) D. L. Clive, S.
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Tueckmantel, A. P. Kozikowski, L. Romanczyk, J. Am.
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Acknowledgements
PSP and VJR thank 12th Five-year plan ORIGIN Project (CSC-0108)
for funding. PSP and RB acknowledge CSIR-SRA, UGC, Govt of India
for the fellowship.
7
a) C. Hartman, V. Meyer, Chem. Ber. 1893, 26, 1727;
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New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ02628A
Graphical Abstract:
An efficient, eco-friendly protocol for selective oxidation of primary and secondary Baylis–
Hillman alcohols to the corresponding carbonyl compounds in high yields has been developed
with 2-Iodosobenzoic acid (IBA).