Synthesis of α-Acyloxy-α′-hydroxy Ketones via Cyclic Carbonate Intermediates Generated from Tertiary Bromopropargylic Alcohols and Cs2CO3

Article abstract of DOI:10.1002/ejoc.201901226

A facile approach towards α-acyloxy-α′-hydroxy ketones by reaction of readily available tertiary bromopropargylic alcohols and carboxylic acids in system Cs₂CO₃/H₂O/DMF (50–55 °C, 4 h) was developed. Key intermediates of this synthesis are cyclic carbonates generated in situ from bromopropargylic alcohols and Cs₂CO₃ which have been utilized as both reagent and base promoter.

Full text of DOI:10.1002/ejoc.201901226

A Journal of
Accepted Article
Title: α-Acyloxy-α'-hydroxy Ketones via Cyclic Carbonate Intermediates
Generated in Situ From Tertiary Bromopropargylic Alcohols and
Cs2CO3
Authors: Olesya Shemyakina, Ol'ga G. Volostnykh, Anton V. Stepanov,
and Igor' A. Ushakov
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901226
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10.1002/ejoc.201901226
European Journal of Organic Chemistry
COMMUNICATION
α-Acyloxy-α'-hydroxy Ketones via Cyclic Carbonate Intermediates
Generated in Situ From Tertiary Bromopropargylic Alcohols and
Cs2CO3
Olesya A. Shemyakina,* Ol'ga G. Volostnykh, Anton V. Stepanov, Igor' A. Ushakov
Abstract: A facile approach to α-acyloxy-α'-hydroxy ketones by
reaction of readily available tertiary bromopropargylic alcohols and
carboxylic acids in system Cs2CO3/H2O/DMF (50-55 oC, 4 h) was
developed. Key intermediates of this synthesis are cyclic carbonates
generated in situ from bromopropargylic alcohols and Cs2CO3 which
have been utilized as both reagent and base promoter.
acyloxylation of functionalized carbonyl compounds (α-
haloketones, α-diazoketones) with an alkaline carboxylates or
carboxylic acids,[7] the direct oxidative coupling of ketones with
carboxylic acids,[7c,8] oxo-acyloxylation of the alkenes,[7c,9] Ru-
catalyzed addition of carboxylic acids to propargylic alcohol.[7c,10]
Also, there have been developed alternative methods: NBS/DBU
mediated α-acyloxylation of benzylic secondary alcohols with
carboxylic acids,[11] the transformation of enamides through an
intramolecular oxidative acetyl migration process mediated by
hydrogen peroxide and acetic anhydride,[12] PhI(OAc)2-promoted
umpolung acetoxylation of enamides,[13] Yb(OTf)3-catalyzed
oxidative decarboxylation of β‐keto acids mediated by
Introduction
The α-acyloxy carbonyl motifs are the key structural units, which
are met in natural products and pharmaceuticals such as
cortisone acetate,[1] valrubicin,[1a,2] cortivazol,[1a,3] bendacort,[1a,4]
aranidipine,[1a,5] and others that exhibit anti-inflammatory,
anticancer, antiallergic, hypotensive properties, etc. (Figure 1).
Also, α-acyloxy ketones are used as versatile synthons for
further transformations, in particular as precursors of α-hydroxy
ketones.[6]
(diacetoxyiodo)benzene
and
carboxylic
acids,[14]
self-
intermolecular oxidative coupling of aryl ketones using
I2/TBHP[15] and I2/TBHP-mediated α-benzoyloxylation of
ketones,[16] a HI-promoted di‐deidoination of α′‐acetoxy‐α,α‐
dihaloketones.[17]
Results and Discussion
O
OH
O
O
O
O
O
OH
O
OH
O
H
Herein, we present a new method for the preparation of α-
acyloxy-α'-hydroxy ketones by the reaction of tertiary
bromopropargylic alcohols 1 with carboxylic acids 2 in system alkali
metal carbonate/H2O/DMF. It is found that α-acyloxy-α'-hydroxy
ketones 3 are produced in up to 81% yield along with α,α'-
dihydroxy ketones 4 as by-products. Completion of the reaction
was monitored by IR and 1H NMR spectroscopy by the
disappearance of the bands at 2196–2212 cm–1 (–C≡C–Br) and
signals of the bromopropargylic alcohols 1, correspondingly.
To optimize the process conditions we have chosen the
reaction of bromopropargylic alcohol 1a with benzoic acid 2a as
model substrates (Table 1). When the reaction was monitored
by 1H NMR, at the initial stages of the reaction two signals were
detected at 5.42 and 1.63 ppm. These signals decreased with
simultaneous arise and increase of the product signals. This
intermediate was isolated and identified as α-bromoethylidene
carbonate 5. In our case, the carbonate 5 was obtained by the
reaction of bromopropargylic alcohol 1a and inorganic carbonate.
It was previously reported that Na2CO3 can serve as a CO2
source for the Pd-catalyzed synthesis of cyclic carbonates.[18]
Various alkali metal carbonates (Li2CO3, Na2CO3, K2CO3,
Cs2CO3) were studied. Cs2CO3 proved to be the most efficient
(Table 1, entry 4) ensuring the highest yields (61%) presumably
due to a better solubility and dissociation of cesium salts in DMF
as compared to the lithium, sodium or potassium salts.[19]
O
O
OH
HN
O
H
H
O
Valrubicin
CF3
Cortisone acetate
O
HO
O
O
O
OH
HO
NO2
O
O
H
O
OMe
N
H
H
O
N
N
H
Aranidipine
Cortivazol
HO
O
O
O
OH
O
N
N
H
H
H
O
Bendacort
Figure 1. Biologically active compounds incorporating the α-acyloxy carbonyl
unit.
The methods for α-acyloxy ketone synthesis are α-
[*]
Dr. O. A. Shemyakina, O. G. Volostnykh, A. V. Stepanov, I. A.
Ushakov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences 1 Favorsky Str., 664033, Irkutsk,
Russian Federation
Optimal loading of Cs2CO3 was
1 equivalent relative to
carboxylic acid. Utilizing 1.5 equivalent of the catalyst gave a
lower yield of product 3 (Table 1, entry 5), conversion of the
bromopropargylic alcohol 1a with 0.5 equivalent of Cs2CO3 after
E-mail: shemyakina@irioch.irk.ru
Supporting information for this article is given via a link at the end of
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10.1002/ejoc.201901226
European Journal of Organic Chemistry
COMMUNICATION
9 h was ~10%. In the presence of other alkali metal carbonates
(Li2CO3, Na2CO3, K2CO3), the yields decreased dramatically
(Table 1, entries 1-3). With K2CO3, the yield raised twice, when
1a:2a molar ratio was increased from 1:1 to 1.5:1, however the
reaction time prolonged to 14 h (Table 1, entry 10).
lead to α-acyloxy-α'-hydroxy ketone 3a (Table 1, entries 8, 9).
The sole product in these cases was α,α'-dihydroxy ketone 4 (up
to 38% isolated yields). In DMF (without additional water), after 4
h the crude reaction mixture contained cyclic carbonate 5 as a
major product (46% isolated yield, Table 1, entry 11). In this
case, complete hydration/acylation of the carbonate 5 occurred
for 9 h (Table 1, entry 12).
Finally, 1:2:Cs2CO3 molar ratio 1.2:1:1, H2O-DMF (1:5) as
a solvent and 50-55 oC were found to be the optimized
conditions and used to study the effect of the substituents at the
α-position of the hydroxyl group in bromopropargylic alcohols
1a–f (Table 2). In going from 1a (R1 = R2 = Me) to 1b (R1 = Et,
R2 = Me) and 1c [R1 - R2 = (CH2)5], there was not influence of
the substituents on the process (Table 2, entries 1-3), products
3a-c were formed in satisfactory yields. In contrast, rate of the
reaction of alcohols 1d–f bearing sterically hindered substituents
significantly reduced. The reaction time to full conversion for 1e
(R1 = Ph, R2 = Me) was 10 h. Increasing temperature up to 75 oC
led to a shorter reaction time (3 h) and the yield of the product
3e arisen from 31 to 57% (Table 2, entries 5, 6). For alcohols 1d
(R1 = tBu, R2 = Me) and 1f (R1 = R2 = Ph), the conversions were
incomplete after 11 h (Table 2, entry 4, 7). The yield of 3f was
Table 1. Optimization of reaction conditions[a]
Entry
Solvent
Inorganic
carbonate
Time,
h
Ratio of
Isolated
yield of
3a, %
3a:4a:5,[b]
%
1
H2O-DMF,
1:5
Li2CO3
Na2CO3
K2CO3
4
50/-/50
33/-/67
100/-/-
88/12/-
73/-/23
100/-/-
18/82/-
-/100/-
10
14
26
61
33
52
9
2
H2O-DMF,
1:5
4
o
poor even with temperature boost (to 75 C) and prolonging the
3
H2O-DMF,
1:5
4
process duration to 25 h (Table 2, entry 8). Based on these
results, substituents at the hydroxyl moiety generating steric
hindrance had a negative impact on the reaction. We tried to
involve secondary and primary bromopropargylic alkohols (4-
bromobut-3-yn-2-ol and 3-bromoprop-2-yn-1-ol) in the reaction
with benzoic acid 2a. The corresponding α-acyloxy-α’-hydroxy
ketones were detectable in the reaction solutions after 3 h by 1H
NMR (along with starting compounds), however, the attempts to
isolate the products failed. Hence, these reactions require
further optimization.
The synthesis was proved to be efficiently extendable over
to various carboxylic acids (Scheme 1). Carboxylic acids with
alkyl, aryl and hetaryl substituents were successfully involved
into the reaction to afford the corresponding products 3g-n in up
to 81% isolated yields under the optimized conditions.
4
H2O-DMF,
1:5
Cs2CO3
4
[c]
5
H2O-DMF,
1:5
Cs2CO3
3
6[d]
H2O-DMF,
1:5
Cs2CO3
Cs2CO3
Cs2CO3
20
7
7
H2O-DMF,
1:1
8
H2O-DMF,
5:1
8
-
9
H2O
Cs2CO3
K2CO3
13
14
-/100/-
91/-/9
-
10[e]
H2O-DMF,
1:5
55
O
Me
O
Cs2CO3, H2O/DMF
50-55 oC, 4 h
Me
Me
O
R3
R3
Me
Br
+
OH
OH
OH
3g-n
O
11
12
13
DMF
Cs2CO3
Cs2CO3
Cs2CO3
3
17/-/83
85/15/-
trace/-/-
11
55
-
1a
2b-i
DMF
9
O
O
Me
Me
Me
O
Me
O
O
nPr
Me
Me
MeCN
10
Me
O
OH
O
OH
O
OH
O
3g, 53%
3h, 81%
3i, 80%
[a] Conditions: bromopropargylic alcohol 1a (1.0 mmol), acid 2a (1.0
mmol), inorganic carbonate (1.0 mmol). [b] According to 1H NMR
spectra of crude mixture. [c] 1.5 mmol. [d] At rt. [e] 1.5 mmol of alcohol
1a.
O
O
O
O
Me
Me
Me
Me
Me
Me
O
O
S
O
N
H
OH
OH
3k, 77%
OH
O
O
O
The reaction at room temperature [Cs2CO3, H2O-DMF
3l, 64%
3j, 59%
(1:5)] slowed down and took 20 h (Table 1, entry 6).
Cl
O
O
Me
The H2O-DMF (1:5) mixture is an efficient solvent for the
hydration/acylation of bromopropargylic alcohols 1 (Table 1,
entry 4). Only trace of α-acyloxy-α'-hydroxy ketone 3a was
observed when DMF was replaced by MeCN probably due to
the limited solubility of inorganic carbonates in this solvent
(Table 1, entry 13). Using water as a solvent or increasing the
amount of water in the system H2O-DMF up to 5:1 ratio did not
Me
Me
O
Me
Me
O
O
S
OH
O
Me
OH
O
3n, 33%
3m, 52%
Scheme 1. Scope with respect to carboxylic acids 2b-i.
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10.1002/ejoc.201901226
European Journal of Organic Chemistry
COMMUNICATION
opening of the carbonate. α,α'-Dihydroxy ketones 4 are
obviously resulted from hydrolysis of products 3.
Table 2. Scope with respect to bromopropargylic alcohols 1a-f [a]
Me
OH
KOH or DBU
H2O-DMF
O
Me
Me
Br
Br
+
no products
OH
50-55 o
C
1a
1a
2a
Cs2CO3
En
try
Propar
gylic
alcohol
1
Time,
h
Product, 3
Isolat
ed
yield,
%
Product,
4
Isolated
yield, %
Me
Me
Me
OH
DMF
O
50-55 oC, 3 h
Br
O
O
5, 44%
1
2
3
4
4
70
78
76
56
7
Me
Me
O
O
Cs2CO3
O
Me
Me
Me
O
+
O
OH
+
1a
1b
4a
4b
4c
4d
H2O-DMF
50-55 oC, 3 h
O
Me
OH
3a
3b
3c
OH
Br
Br
O
O
OH
O
2a
5
4a, 3%
3a, 62%
4
14
Me
Me
O
O
BzOCs
Me
Me
Me
O
O
OH
+
H2O-DMF
conversion ~45%
Me
OH
O
OH
O
50-55 oC, 3 h
3a
4a
5
4
18
4:1 (1H NMR data)
conversion ~10%
Me
O
Me
Cs2CO3
Me
1c
OH
O
Me
OH
H2O-DMF
O
Br
O
O
50-55 oC, 3 h
4a, trace
Me
19
trace
5
O
tBu
OH
O
1d[b]
O
O
1.3 equiv KOH
aq EtOH, 50 oC, 4 h
Me
Me
Me
Me
O
OH
3d
OH
O
OH
3a
4a, 44%
5
10
31
15
Scheme 2. Control experiments.
4e
4e
3e
3e
1e
1e
6[c]
7
3
57
34
26
A plausible mechanism has been proposed (Scheme 3).
Initially, the formation of cyclic carbonate from
5
11
trace
bromopropargylic alcohol 1 and Cs2CO3 proceeds. Then, the
hydration of 5 promoted by cesium carboxylate and the
release of CO2 give the bromoketone A, followed by the
substitution of bromine with carboxylic acid to deliver the α-
acyloxy-α'-hydroxy ketone 3.
1f[d]
1f[e]
3f
3f
4f
4f
8[c]
25
13
trace
[a] Conditions: bromopropargylic alcohol 1 (1.2 mmol), benzoic
acid 2a (1.0 mmol), Cs2CO3 (1.0 mmol), H2O (1 ml), DMF (5
ml). [b] Conversion was 60%. [c] At 75 °C. [d] Conversion
was 30%. [e] Conversion was 75%.
Several control experiments were carried out (Scheme 2).
We tested KOH or DBU as base promoter (H2O-DMF, 1:5, 50-55
oC, 20 h) in the reaction of bromopropargylic alcohol 1a with
benzoic acid 2a, which failed to provide the desired product.
Next, cyclic carbonate 5 was formed from bromopropargylic
alcohol 1a and Cs2CO3 in DMF and underwent
hydration/acylation to afford the product 3a. These findings
suggest that the carbonate 5 is the key intermediate in the
formation of α-acyloxy-α'-hydroxy ketones and Cs2CO3 acts as
both reagent and base promoter. We evaluated the reaction of 5
with BzOCs and Cs2CO3 in DMF/H2O. When BzOCs was
applied, crude product contained α-acyloxy-α'-hydroxy ketone 3a
and α,α'-dihydroxy ketone 4a along with unreacted carbonate
(5:3a:4a ratio is 4:4:1, 1H NMR data). At the same time, Cs2CO3
hardly catalyzed hydration of carbonate 5. These results
indicated the participation of the carboxylic acid in the ring
Scheme 3. Proposed mechanism.
We made an experiment using CO2 gas instead of Cs2CO3
(Scheme 4). Reaction of bromopropargylic alcohol 1a with free
CO2 gas in the presence of 100 mol% of CsOH and benzoic acid
in H2O-DMF after 3 h afforded acyloxy ketone 3a in 48% yield.
However, these results do not clarify the mechanism clearly
since Cs2CO3 is likely to form in reaction mixture from CO2 gas
and CsOH.
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COMMUNICATION
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Scheme 4. Control experiment.
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The formation of cyclic carbonates from propargylic alcohols
are known to proceed with CO2 in the presence of transition
metal catalysts[20] or phosphines,[21] guanidine,[22] K2CO3-crown
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unique example of transition-metal-free synthesis of cyclic
carbonates from propargylic alcohols without using CO2 gas. Taking
into account that the starting bromopropargylic alcohols are
readily prepared from commercially available propargylic
alcohols and hypobromite[27] or N-bromosuccinimide [28] (Scheme
5), the method presented here may be considered as one of the
most expedient approaches to so far known to α-acyloxy-α'-
hydroxy ketones.
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In conclusion, we have developed a new approach to
synthesis of α-acyloxy-α'-hydroxy ketones by hydration/acylation
of tertiary bromopropargylic alcohols with carboxylic acids in
system Cs2CO3/H2O/DMF. The reaction proceeds via transition-
metal-free formation of cyclic carbonate intermediates from
bromopropargylic alcohols and Cs2CO3. This step-economical
process takes place under mild reaction conditions with simple
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Acknowledgements
The main results were obtained using the equipment of Baikal
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Keywords: α-acyloxy ketone • cyclic carbonate • propargylic
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COMMUNICATION
COMMUNICATION
Key Topic: bromopropargylic
alcohols hydration/acylation
Olesya A. Shemyakina,* Ol'ga G.
Volostnykh, Anton V. Stepanov, Igor' A.
Ushakov
Page No. – Page No.
The Cs2CO3-catalyzed synthesis of α-acyloxy-α'-hydroxy ketones is reported, in
which tertiary bromopropargylic alcohols undergo hydration/acylation with
carboxylic acids via in situ formation of cyclic carbonates.
α-Acyloxy-α'-hydroxy Ketones via
Cyclic Carbonate Intermediates
Generated in Situ From Tertiary
Bromopropargylic Alcohols and
Cs2CO3
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