Indium(III)-Catalyzed Hydration and Hydroalkoxylation of α,β-Unsaturated Ketones in Aqueous Media

Article abstract of DOI:10.1002/adsc.201800301

The hydration of α,β-unsaturated ketones with water proceeded efficiently in the presence of In(OTf)₃ (20 mol%) in aqueous media to afford synthetically versatile β-hydroxyketones in moderate to good yields with good functional group compatibility. The method also can be extended to the hydroalkoxylation of α,β-unsaturated ketones with various alcohols for the efficient synthesis of β-alkoxyketones as well as tetrahydrofuran derivatives. (Figure presented.).

Full text of DOI:10.1002/adsc.201800301

Title: Indium(III)-Catalyzed Hydration and Hydroalkoxylation of α,β-
Unsaturated Ketones in Aqueous Media
Authors: Jin-Jin Yun, Man-Ling Zhi, Wen-Xiao Shi, Xue-Qiang Chu,
Zhi-Liang Shen, and Teck-Peng Loh
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800301
Link to VoR: http://dx.doi.org/10.1002/adsc.201800301

10.1002/adsc.201800301
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Indium(III)-Catalyzed Hydration and Hydroalkoxylation of
α,β-Unsaturated Ketones in Aqueous Media
Jin-Jin Yun,a Man-Ling Zhi,a Wen-Xiao Shi,a Xue-Qiang Chu,a Zhi-Liang Shen,a,* and
Teck-Peng Loha,b,*
a
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic
Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang
b
Technological University, Singapore 637371, Singapore
Phone: (+65) 6316 8899; Fax: (+65) 6791 1961; E-mail: teckpeng@ntu.edu.sg
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######. ((Please
delete if not appropriate))
Abstract. The hydration of α,β-unsaturated ketones with
water proceeded efficiently in the presence of In(OTf)3 (20
mol%) in aqueous media to afford synthetically versatile β-
hydroxyketones in moderate to good yields with good
functional group compatibility. The method also can be
extended to the hydroalkoxylation of α,β-unsaturated
ketones with various alcohols for the efficient synthesis of
β-alkoxyketones as well as tetrahydrofuran derivatives.
compounds remains a big challenge and has been
rarely explored.[4,7-8] In this regard, the development
of an efficient method for the direct addition of water
molecule to α,β-unsaturated carbonyl compounds still
remains highly desirable.
On the other hand, indium(III) salt has been widely
demonstrated to be an efficient Lewis acid for
catalyzing a broad range of organic transformations,
because of its powerful catalytic activity and water-
tolerant nature.[9] For instances, indium(III) salts were
found to effectively catalyze the addition reactions of
alkenes with various nucleophiles, including thiol,[10a-
Keywords: Indium; Hydroxylation; Hydroalkoxylation, β-
Hydroxyl ketone, Aqueous media
b]
phenol,[10c] amine,[10e] silyl enol ether,[10f] and
arenes,[10g] as demonstrated by Duñach and others. In
continuation of our efforts to develop indium
chemistry[11] in organic synthesis as well as water-
based[12-13] organic reactions which are in accordance
with the principle of Green Chemistry, herein we
report an efficient method for the synthesis of β-
hydroxyketones by means of In(OTf)3-catalyzed
direct addition of water molecule to α,β-unsaturated
ketones in aqueous media. The reactions involving
various α,β-unsaturated ketones proceeded efficiently
in water-containing solvent to produce β-
hydroxyketones in moderate to good yields. In
addition, the use of alcohol as Michael donor worked
equally well under the optimized reaction conditions
to afford the corresponding β-alkoxyketones in
moderate to good yields. The synthetic utility of the
method was further demonstrated by the synthesis of
tetrahydrofuran derivatives.
β-Hydroxyl carbonyl compounds are widely
featured in natural products and serve as pivotal
intermediates and building blocks in organic
synthesis.[1,2] Conventionally, β-hydroxyl carbonyl
compounds are prepared either by aldol-type
reaction[2] or by epoxidation of enones followed by
selective reduction.[3] In 2003, Bergman and Toste
have seminally developed an efficient method for the
synthesis of β-hydroxyl carbonyl compounds via the
direct Michael-type addition of water molecule to
α,β-unsaturated carbonyl compounds by using
phosphine as a catalyst.[4] Although the conjugate
additions of alcohols to α,β-unsaturated carbonyl
compounds have been widely exploited for the
synthesis of β-alkoxyl carbonyl compounds,[5] the use
of water molecule as Michael donor for the synthesis
of β-hydroxyl carbonyl compounds has been proven
to be difficult because of the following two main
reasons: 1) water as an uncharged nucleophile is a
relatively poor nucleophile as compared to carbon
and nitrogen nucleophiles; 2) the addition of water to
α,β-unsaturated carbonyl compound is an equilibrium
which lies substantially on the substrate side, even in
the presence of excess water.[6] Thus, the Michael-
type addition of water to α,β-unsaturated carbonyl
Initially, a variety of indium(III) salts (20 mol%)
were screened by employing 1-phenylprop-2-en-1-
one (1a) as model substrate in CH3CN/H2O (1:2) at
80 oC for 24 h to optimize the reaction conditions. As
shown in Table 1, among the various indium(III)
catalysts investigated (Table 1, entries 1-8), In(OTf)3
was found to be the catalyst of choice, affording the
1
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10.1002/adsc.201800301
Advanced Synthesis & Catalysis
desired product 2a in 80% NMR yield (75% isolated
yield; Table 1, entry 5). Subsequently, in the presence
of 20 mol% In(OTf)3, a range of water-containing
solvent systems were studied (Table 1, entries 9-14).
However, only poor to moderate yields of product 2a
was obtained when CH3CN/H2O was replaced by
DMSO/H2O, DMF/H2O, THF/H2O, or other solvent
systems. Furthermore, it was observed that
decreasing either the catalyst loading (Table 1, entries
15-16) or the reaction temperature (Table 1, entry 5,
footnote d) only led to erosion of product yields.
Thus, the optimized reaction conditions were
established as follows: 1a (1 mmol), In(OTf)3 (20
Table 2. Substrate scope study by using various
enones.[a]
Entry
1
Substrate
Product
Yield[b] [%]
60
2b
2
3
47
70
2c
o
mol%), CH3CN/H2O (1:2), 80 C, 24 h (Table 1,
entry 5).
2d
Table 1. Optimization of reaction conditions.[a]
4
5
69
76
2e
2f
Entry Catalyst
Solvent
Yield[b] [%]
1
2
3
4
InCl3 (20 mol%)
InBr3 (20 mol%)
InF3 (20 mol%)
CH3CN
CH3CN
CH3CN
CH3CN
26
38
31
6
7
8
48
50
44
2g
2h
2i
In(OAc)3 (20 mol%)
27
80 (75)[c]
5
In(OTf)3 (20 mol%)
CH3CN
(38)[d] (64)[e]
6
7
8
In(acac)3 (20 mol%)
In(OH)3 (20 mol%)
InPO4 (20 mol%)
CH3CN
CH3CN
CH3CN
DMSO
DMF
DMA
DME
THF
11
43
28
39
35
33
24
11
46
48
55
9
In(OTf)3 (20 mol%)
In(OTf)3 (20 mol%)
In(OTf)3 (20 mol%)
In(OTf)3 (20 mol%)
In(OTf)3 (20 mol%)
In(OTf)3 (20 mol%)
In(OTf)3 (5 mol%)
In(OTf)3 (10 mol%)
10
11
12
13
14
15
9
66
82
2j
acetone
CH3CN
CH3CN
10
2k
16
[a]
Unless otherwise noted, the reactions were performed
at 80 oC for 24 h by using 1-phenyl-prop-2-en-1-one (1a,
1 mmol) and indium(III) salt (0.20 mmol) in solvent/H2O
(1 mL/2 mL).
11
12
56
48
2l
[b]
Yield was determined by NMR analysis of the crude
2m
reaction mixture by using 1,4-dimethoxy-benzene as an
internal standard.
13
14
53
21
2n
2o
[c] Isolated yield.
[d] At 50 oC.
[e] TfOH (20 mol%) was used as reaction catalyst in place
of In(OTf)3.
15
NR
2p
[a]
o
The reactions were performed at 80 C for 24 h by
using enone 1 (1 mmol) and In(OTf)3 (0.20 mmol) in
CH3CN/H2O (1 mL/2 mL).
With the optimized reaction conditions in hand,
subsequently we explored substrate scope of the
reaction by utilizing a wide array of α,β-unsaturated
carbonyl compounds as substrates. As outlined in
Table 2, the reactions involving various α,β-
unsaturated ketones proceeded smoothly under well-
established conditions in aqueous media to generate
the expected β-hydroxyketones in moderate to good
yields (Table 2, entries 1-13). Various aryl, heteroaryl,
and alkyl substituted α,β-unsaturated ketones were
[b] Isolated yield.
proven to be suitable candidates for the present
organic transformations. In addition, the mild
reaction conditions also allowed the tolerance to
important functional groups, such as nitro, cyano, and
2
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10.1002/adsc.201800301
Advanced Synthesis & Catalysis
carbonyl groups (Table 2, entries 1-4). Moreover,
α,β-unsaturated ketones bearing thienyl, furyl and
benzofuryl substituents (Table 2, entries 9-11), which
were somewhat sensitive to acidic conditions, were
amenable to the mild reaction condition, leading to
the desired products 2j-l in moderate to good yields.
However, when β or α position of α,β-unsaturated
ketones was substituted by a methyl group (Table 2,
entries 14-15), either poor yield was obtained or no
reaction occurred.
alkoxyketones 4a-l in 43-90% yields.The mild
reaction conditions entailed the use of various
alcohols, including alkyl alcohols(Table 3,
entries 1-6, and 12), propargylic alcohol (Table 3,
entry 7), and benzyl alcohols (Table 3, entries 8-
11). In addition, sterically hindered secondary
alcohol (Table 3, entries 2 and 12) could be used
as substrates with equal ease, leading to the
anticipated products 4b and 4l in 77-88% yields.
As expected, substrates bearing functional
groups (Table 3, entries 5, 6, 9, and 10) were also
capable of efficiently participating in the
Table 3. Substrate scope study by using various
alcohols.[a]
transformations,
without
touching
these
important functionalities.
Table 4. Substrate scope study by using cyclic enones
Entry
ROH
Product
Yield[b] [%]
and alcohols.[a]
1
2
3
EtOH[c]
90
77
89
4a
4b
4c
i-PrOH[c]
n-BuOH[c]
4
49
4d
5
6
56
68
4e
4f
Yield[b]
[%]
31
Entry Substrate ROH
Product
1
2
EtOH[c]
EtOH[c]
7
8
46
86 (69)[d]
4g
4h
1q
1r
4m
4n
78
3
51
1r
4o
9
67
43
56
4i
4
64
1r
4p
[a] Unless otherwise noted, the reactions were performed
at room temperature for 24 h by using cyclic enones 1q-
r (1 mmol), alcohol 3 (6 mmol) and In(OTf)3 (0.20
mmol) in CH3CN (1 mL).
10
11
4j
4k
[b] Isolated yield.
[c] The reaction was directly performed in ethanol (3 mL)
instead of in CH3CN.
12
88
4l
[a]
In contrast to acyclic enones which reacted with
water in moderate to good yields, the reaction of
cyclic enone (e.g., 2-cyclohexen-1-one) with water
proceeded sluggishly under the optimized reaction
conditions to give the corresponding product in <10%
yield, which might be due to the ready competing
elimination and/or retro-aldol reaction of the in situ
formed product under the relatively acidic reaction
conditions. Similarly poor results (<30% yields) were
also observed by Hanefeld and co-workers[14] who
used amino acid or enzyme as reaction catalyst for
the addition of water to cyclic enones of 2-
cyclopenten-1-one, 2-cyclohexen-1-one, and 2-
cyclohepten-1-one.[15-16] In contrast to water addition,
the reaction of cyclic enones 1q-r with alcohols
proceeded with improved performance under optimal
reaction conditions to furnish the corresponding
products 4m-p in 31-78% yields (Table 4).
Unless otherwise noted, the reactions were performed
at 80 oC for 24 h by using 1-(4-nitrophenyl)-prop-2-en-1-
one (1b, 1 mmol), alcohol 3 (6 mmol) and In(OTf)3 (0.20
mmol) in CH3CN (1 mL).
[b] Isolated yield.
[c] The reaction was directly performed in alcohol (ROH,
3 mL) instead of in CH3CN.
[d]
TfOH (20 mol%) was used as reaction catalyst in
place of In(OTf)3.
Next, to further demonstrate the efficiency of
the method, we continued to study the reaction of
α,β-unsaturated ketones with a spectrum of
alcohols for the preparation of β-alkoxyketones.
As indicated in Table 3, the hydroalkoxylation of
1-(4-nitrophenyl)prop-2-en-1-one (1b) with a
wide variety of alcohols 3 worked equally well
o
when the reactions were performed at 80 C for
24 h in CH3CN in the presence of 20 mol%
In(OTf)3, furnishing the corresponding β-
Mechanistically, it is believed that In(OTf)3 might
help to coordinate with the carbonyl group of the α,β-
3
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10.1002/adsc.201800301
Advanced Synthesis & Catalysis
unsaturated ketone to enhance the electrophilicity of
the carbonyl group as well as the C-C double bond of
α,β-unsaturated ketones to facilitate the subsequent
Michael-type addition of water or alcohol. It was
reported that In(OTf)3 might partially hydrolyze in
aqueous media to generate TfOH, which might
catalyze organic transformations. To determine the real
catalyst in the present protocol, we examined the
reactions of enone 1a with water and enone 1b with
benzyl alcohol, respectively, in the presence of TfOH
(20 mol%) under optimized reaction conditions. It
was found that 64% yield of product 2a (Table 1,
entry 5, footnote e) and 69% yield of product 4h
(Table 3, entry 8, footnote d) were obtained, both of
which are lower than the same reactions conducted
by using In(OTf)3 (20 mol%) as catalyst (75% and
86% yields, respectively). Thus, we believed that
In(OTf)3 should play a major role in catalyzing the
present organic reactions, though we cannot
completely rule out some positive effect of the
generated TfOH for catalyzing the addition reactions.
It should be noted that the present method using
In(OTf)3 as an Lewis acid catalysis is in sharp
contrast with the method developed by Bergman and
Toste[4] where phosphine was employed as reaction
catalyst and the concomitant formation of a strong
base during the course of the reaction was proposed.
To further demonstrate the synthetic utility of the
present method, it was applied to the synthesis of
tetrahydrofuran derivative, an important skeleton
recurrently encountered in nature and biologically
active compounds.[17] As listed in Scheme 1, when
α,β-unsaturated ketones were subjected to In(OTf)3-
catalyzed reactions with 2-iodoethanol (3m) under
desired β-hydroxyketones in moderate to good yields.
In addition, the method could be extended to the use
of various alcohols as Michael donors to produce the
corresponding β-alkoxyketones with high efficiency.
The mild reaction conditions also allowed the use of
various substrates containing functional groups, such
as nitro, cyano, carbonyl, and other functionalities.
Moreover, the method was applied to the synthesis of
synthetically versatile tetrahydrofuran derivative via
In(OTf)3-catalyzed reactions of α,β-unsaturated
ketones with 2-iodoethanol followed by NaNH2-
promoted intramolecular cyclization of the in situ
generated enolate with alkyl iodide via an SN2-type
reaction pathway. Further application of the present
method in organic synthesis for the construction of
cyclic compounds is currently in progress in our
group.
Experimental Section
General procedure for the hydration of α,β-
unsaturated ketone with water
α,β-Unsaturated ketone 1 (1.0 mmol, 1.0 equiv.) and
In(OTf)3 (0.20 mmol, 20 mol%) were stirred in
CH3CN/H2O (1 mL/2 mL) at 80 oC for 24 h. Upon
completion of the reaction (as indicated by TLC), the
reaction mixture was extracted with ethyl acetate (3 x 20
mL). The combined organic phases were washed with
brine (20 mL), dried over anhydrous Na2SO4 and
concentrated in vacuo. The crude residue obtained was
purified by silica gel column chromatography using ethyl
acetate and petroleum ether as eluant to afford pure β-
hydroxyl carbonyl compound 2.
Acknowledgements
well-established
reaction
conditions,
the
corresponding β-alkoxyketones 5a-c bearing iodide
moiety were obtained in moderate yields. Upon
NaNH2-promoted intramolecular cyclization of the in
situ generated enolate with alkyl iodide via an SN2-
type reaction pathway, synthetically versatile
tetrahydrofuran derivatives were produced in 59-66%
yields.
We gratefully acknowledge the financial support from Nanjing
Tech University (Start-up Grant No. 39837118, 39837101, and
39837146), the SICAM Fellowship from Jiangsu National
Synergetic Innovation Center for Advanced Materials, and
Nanyang Technological University.
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5
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10.1002/adsc.201800301
Advanced Synthesis & Catalysis
COMMUNICATION
Indium(III)-Catalyzed
Hydration
and
Hydroalkoxylation of α,β-Unsaturated Ketones in
Aqueous Media
Adv. Synth. Catal. Year, Volume, Page – Page
Jin-Jin Yun, Man-Ling Zhi, Wen-Xiao Shi, Xue-
Qiang Chu, Zhi-Liang Shen,* and Teck-Peng Loh*
6
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