An Atom-Economical Route to Substituted β-Arylethyl Ketones: Phosphomolybdic Acid-Catalyzed Carbohydroxylation of Terminal Alkynes in Organic Carbonate

Article abstract of DOI:10.1002/adsc.201601231

A highly efficient and atom-economical route for the synthesis of substituted β-arylethyl ketones was developed by using cheap phosphomolybdic acid (H₃PMo₁₂O₄₀) as catalyst and non-volatile propylene carbonate (PC) as green solvent via the carbohydroxylation of terminal alkynes with benzylic alcohols under mild conditions. Various functional groups on the benzylic alcohols and terminal alkynes were tolerated, giving the corresponding substituted β-arylethyl ketones as products in good to excellent yields (up to 95%). It is worth noting that a turnover number (TON) of up to 520 was achieved in the protocol. The mechanism investigation showed that PC might stabilize the heteropoly anion and the carbocation intermediate thus facilitating the carbohydroxylation reaction. (Figure presented.).

Full text of DOI:10.1002/adsc.201601231

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DOI: 10.1002/adsc.201601231
An Atom-Economical Route to Substituted b-Arylethyl Ketones:
Phosphomolybdic Acid-Catalyzed Carbohydroxylation of
Terminal Alkynes in Organic Carbonate
Guo-Ping Yang,a,b Nan Zhang,a Nuan-Nuan Ma,a Bing Yu,a,*
and Chang-Wen Hua,*
a
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/ Electrophotonic,
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, Peopleꢀs Republic of
China
Fax : (+86)-10-8138-1380; phone: (+86)-10-8138-1380; e-mail: bingyu@bit.edu.cn or cwhu@bit.edu.cn
China Academy of Engineering Physics, China
b
Received: November 4, 2016; Revised: December 27, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201601231.
Abstract: A highly efficient and atom-economical
route for the synthesis of substituted b-arylethyl ke-
tones was developed by using cheap phosphomolyb-
dic acid (H3PMo12O40) as catalyst and non-volatile
propylene carbonate (PC) as green solvent via the
carbohydroxylation of terminal alkynes with benzyl-
ic alcohols under mild conditions. Various function-
al groups on the benzylic alcohols and terminal al-
kynes were tolerated, giving the corresponding sub-
stituted b-arylethyl ketones as products in good to
excellent yields (up to 95%). It is worth noting that
a turnover number (TON) of up to 520 was ach-
ieved in the protocol. The mechanism investigation
showed that PC might stabilize the heteropoly
anion and the carbocation intermediate thus facili-
tating the carbohydroxylation reaction.
tention because these abundant, low toxic building
blocks can be regarded as an economical alternative
for organic halides and analogues.[7,8] In 2009, the Jiao
group reported the first example of C(sp3)–C(sp)
bond formation via dehydrative coupling of benzylic
alcohols with terminal alkynes catalyzed by inexpen-
sive Fe(OTf)3/TfOH in the absence of a base.[9] Subse-
quently, Cu(OTf)2,[10] In(OTf)3,[11] and Brønsted acidic
ionic liquids[12] were demonstrated as efficient systems
for this dehydrative coupling reaction (Scheme 1a).
Carbonyl groups are of great importance in natural
products, bioactive compounds and pharmaceutical
compounds, etc. Unlike many other syntheses of car-
bonyl compounds, the hydration of alkynes is an
atom-economical alternative for ketone synthesis.[13,14]
Consequently, various approaches have been devel-
oped for the hydration of alkynes. However, in these
protocols toxic or expensive catalysts such as mercu-
ry(II), gold(I), gold(III), platinum(II), and palladi-
Keywords: alcohols; alkynes; carbohydroxylation;
organic carbonates; polyoxometalates
AHCTUNGTREGuNNUN m(II) were generally required for highly efficient
transformations.[15–20]
Recently, the construction of b-arylethyl ketones
via a Friedel–Crafts-type reaction of benzylic alcohols
The construction of C–C bonds has emerged as one and aryl methyl ketones was disclosed using
of the most intriguing areas of organic chemistry as Fe(OTf)3/PhCl at 1308C,[21] AgSbF6/CH(OMe)3,[22]
[23]
proved by the award of the 2010 Nobel Prize in and
Amberlyst-15/
[Bmim][PF6]/CH(OMe)3
chemistry.[1–3] Apart from the traditional coupling re- (Scheme 1b). Notably, these dehydrative coupling
actions of organometallic reagents and corresponding procedures suffer from certain limitations with re-
coupling partners, reactions such as the Sonogashira spect to the use of elevated temperature or a stoichio-
coupling which directly uses C–H type substrates as metric amount of triethyl orthoformate as an activat-
reactant have drawn much attention in the recent de- ing reagent. Alternatively, Hashmi et al. developed
cades.[4–6] However, organic halides were required and the Au(III)-catalyzed addition reactions of electron-
waste was produced by using stoichiometric amounts rich arenes to methyl vinyl ketone for the synthesis of
of base in these methods. Particularly, the direct ap- b-arylethyl ketones.[24,25] However, in these ap-
plication of C–OH type substrates like aryl alcohols proaches, precious Au catalysts were needed.
and phenols as proelectrophiles is receiving broad at-
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economical and operationally simple Ritter-type addi-
tion of benzylic alcohols and terminal alkynes towards
substituted b-arylethyl ketones by using the unique
system
of
H3PMo12O40/propylene
carbonate
(Scheme 1c). It was found that the combination of
H3PMo12O40/propylene carbonate is critical for this
carbohydroxylation reaction.
Initially, diphenylmethanol 1a and phenylacetylene
2a were chosen as model compounds for the reaction
using
Keggin-type
POMs,
e.g.,
H4SiW12O40,
H3PW12O40, and H3PMo12O40, as catalysts in dichloro-
ethane at 808C for 3 h. The desired product 3a was
obtained in yields of 18%, 26% and 57%, respectively
(Table 1, entries 1–3). Among those Keggin-type
POMs, H3PMo12O40 possesses the weakest acidity but
is the softest heteropoly anion.[37] It was assumed that
a soft heteropoly anion may stabilize the reaction in-
termediate and thus facilitate the carbohydroxylation
reaction.[38] Subsequently, H3PMo12O40 was applied as
catalyst for solvent screening. Poor yields were detect-
Table 1. Effects of various solvents on the carbohydroxyla-
tion reaction.[a]
Scheme 1. C–C bond formation from benzylic alcohol.
Ideally, b-arylethyl ketones can be directly achieved
from benzylic alcohols and terminal alkynes with
100% atom economy (Scheme 1c). Although this car-
bohydroxylation strategy was recently realized by
using FeCl3·6H2O/MeNO2,[26] FeCl3/AgSbF6,[27] Am-
berlyst-15/[Bmim][PF6],[28] a large amount of catalyst
or promoter (10–300 mol%) was required to obtain
moderate yields. In this context, it is highly desirable
to exploit an efficient and practical catalytic system
for this reaction from readily available starting mate-
rials in an atom- and step-economical manner.
On the other hand, the inexpensive polyoxometa-
lates (POMs) have exhibited broad activities in organ-
ic synthesis by avoiding conventional organic and in-
organic acids.[29–32] Particularly, a Keggin-type POM,
such as phosphotungstic acid (H3PW12O40), exhibited
potential for dehydrative reactions of benzylic alco-
hols and different nucleophiles for the construction of
C–C bonds[33] and C–N bonds.[34] In these protocols, it
is believed that the benzylic alcohol is protonated by
POM to generate a stable benzyl cation for further
transformation. Therefore, we envisioned that the
coupling reaction between benzylic alcohol and termi-
nal alkynes catalyzed by a POM-based system would
be feasible.
Entry
Solvent
Conv. of 1a [%]
Yield[b] [%]
1[c]
2[d]
3
4
5
6
7
8
9
10
11
12
13
14
15
ClCH2CH2Cl
ClCH2CH2Cl
ClCH2CH2Cl
EtOH
i-PrOH
H2O
DMF
n-octane
PhCl
toluene
EtOAc
BrCH2CH2Br
DMC
EC
PC
>99
>99
>99
96
2
85
18
26
57
<1
<1
2
56
98
1
21
46
53
62
64
59
76
99
>99
>99
>99
95
>99
>99
>99
[a]
Reaction conditions: diphenylmethanol (0.2 mmol), phe-
nylacetylene (0.22 mmol), H3PMo12O40 (3 mol%), solvent
(1 mL). 808C, 3 h. DMC =dimethyl carbonate, PC=pro-
pylene carbonate, EC=ethylene carbonate.
The yields were determined by GC with biphenyl as the
internal standard. The main by-product is benzhydrol
ether.
[b]
[c]
[d]
As part of our interest in the field of POM catalysis
H4SiW12O40 (3 mol%) as catalyst.
H3PW12O40 (3 mol%) as catalyst.
and green chemistry,[35,36] we herein disclose an atom-
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ed when the reactions were conducted in solvents like
EtOH, i-PrOH, H2O, DMF and n-octane (entries 4–
8). Reactions in other solvents, including PhCl, tolu-
ene, EtOAc, BrCH2CH2Br gave the product 3a in
higher yields, but the selectivities were not satisfacto-
ry (entries 9–12). Based on these results, it seems that
the presence of aprotic polar solvents is beneficial to
give a better yield of 3a. Considering the high polarity
of the aprotic organic carbonates, commercially avail-
able organic carbonates like DMC, EC and PC were
surveyed in the further investigation (entries 13–15).
To our delight, the reaction selectivity was significant-
ly increased providing 3a in a yield of 99% when PC
was applied as solvent.
These results encouraged us to evaluate different
catalysts based on [PMo12O40]3À using PC as a unique
solvent. As shown in Table 2, the control experiment
without catalyst in PC did not lead to any 3a but
a trace amount of benzhydrol ether was detected,
demonstrating the importance of the catalyst
(entry 1). Cs0.5H2.5PMo12O40 showed a good catalytic
activity but lower selectivity (entry 3). However,
other salts of [PMo12O40]3À such as Cs1.5H1.5PMo12O40,
Cs2.5H0.5PMo12O40,
[DBUH]3PMo12O40,
and
[NMPH]3PMo12O40 gave inferior results (entries 4–7).
These results revealed that the protons of
H3PMo12O40 are significantly essential for the reac-
tion, which might promote protonation of the alcohol
and further generation of the carbocation intermedi-
ate after dehydration.[33,34]
Figure 1. (A) Effect of temperature for the reaction at 3 h
and (B) effect of reaction time at 808C.
Table 2. Examination of various catalysts.[a]
Based on these results, the reaction temperature
was further optimized by using the system of
H3PMo12O40/propylene carbonate. As shown in Fig-
ure 1A, poor yields were observed when the reactions
were performed at lower temperature (<808C) for
3 h. Therefore, 808C was chosen for subsequent stud-
ies. We further optimized the reaction time (Fig-
ure 1B) and found that an almost quantitative yield of
3a could be obtained after reaction at 808C for 2 h.
Having established the optimal conditions, we sur-
veyed the scope of this carbohydroxylation reaction
by using the system of H3PMo12O40/propylene carbon-
ate. As can be seen in Table 3, aromatic alkynes with
electron-withdrawing group or electron-donating
groups (2a–d) could be converted into the corre-
sponding products (3a–d) in excellent yields (84–
95%) via the reaction with 1a for 2–3 h (entries 1–4).
However, an aliphatic alkyne, such as 1-octyne 2e ex-
hibited diminished activity even at elevated tempera-
ture and extended time (1008C, 5 h). Unfortunately,
attempts to isolate the corresponding product 3e
failed, possibly due to its chemical lability (entry 5).
On the other hand, diphenylmethanols 1b–e substitut-
ed with electron-withdrawing or electron-donating
Entry Catalyst
Conv. of 1a [%] Yield[b] [%]
1
2
3
4
5
6
7
–
22
>99
>99
0
<1
99
88
0
H3PMo12O40
Cs0.5H2.5PMo12O40
Cs1.5H1.5PMo12O40
Cs2.5H0.5PMo12O40
[DBUH]3PMo12O40
0
0
9
<1
22
[NMPH]3PMo12O40 88
[a]
Reaction conditions: diphenylmethanol (0.2 mmol), phe-
nylacetylene (0.22 mmol), catalyst (3 mol%), PC (1 mL),
808C, 3 h. DBU=1, 8-diazabicyclo[5.4.0]undec-7-ene,
NMP=N-methyl-2-pyrrolidinone.
The yields were determined by GC with biphenyl as the
internal standard. The main by-product is benzhydrol
ether.
[b]
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Table 3. Substrate scope of H3PMo12O40-catalyzed carbohydroxylation reaction in propylene carbonate.[a]
Entry
Alcohol
Alkyne
Conditions
808C, 2 h
808C, 2.5 h
808C, 3 h
808C, 3 h
1008C, 5 h
Product
3a
Yield[b] [%]
1
2
3
4
5
91
95
86
84
35c
3b
3c
3d
3e
6
7
8
9
808C, 2 h
808C, 3 h
808C, 3 h
808C, 2.5 h
3f
3g
3h
3i
93
87
94
91
10
11
808C, 3 h
808C, 3 h
3j
56
3k
14,[c] 77[d]
12
13
1008C, 4 h
1008C, 4 h
1008C, 4 h
3l
88
77
64
3m
3n
14
[a]
Reaction conditions: alcohol (0.6 mmol), alkyne (1.1 equiv) or nitrile (2.0 equiv), H3PMo12O40 (3 mol%), and PC (3 mL)
as solvent.
Isolated yield.
[b]
[c]
[d]
Yield was estimated by GC-MS.
Direct dehydrative coupling product detected by GC-MS.
groups (Cl, Me, OMe) can smoothly react with alkyne product 1,3,3,3-tetraphenylpropyne was observed by
2a to give the desired products 3f–i in 87–94% yield GC-MS as the main product in a yield of 77%
(entries 6–9). When 2-methylbenzyl alcohol 1f was (entry 11). Unfortunately, only a trace amount of the
employed as substrate to react with 2a, only a 56% corresponding products were detected by GC-MS
yield of product 3j was observed (entry 10). In the when benzylic alcohol and cyclohexanol were em-
case of tertiary alcohol 1g, the dehydrative coupling ployed as substrates even at 1008C for 5 h (results not
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shown). These results indicate that primary alcohols alkyne hydration” pathway. More importantly, the ex-
and aliphatic alcohols are probably not suitable for periment using deuterium labelled phenylacetylene
this protocol.
The Ritter reaction is widely used for the prepara- [D]-3a in 90% yield, demonstrating that cleavage of
tion of acyclic amides as well as heterocycles.[39–41]
the terminal C–D bond was impossible under the re-
[D]-2a as reactant afforded the corresponding product
A
Brønsted acid was found to be critical for the gold- action conditions (Scheme 2c). On the other hand,
catalyzed system used in this reaction.[42–45] In this benzhydrol ether was detected during the time-course
H3PMo12O40/PC system, reactions of diphenylmetha- investigation. Then the gradual formation of the de-
nol 1a with nitriles 2f–h, i.e., Ritter reactions, gave sired products accompanied by the decrease of ether
the corresponding amide products in good yields (en- was observed, suggesting that benzhydrol ether prob-
tries 12–14).
ably is one of the intermediates in this reaction.
Further studies showed that the H3PMo12O40 cata-
To further understand the reaction, we investigated
the reaction mechanism by a series of control experi- lyst does not completely dissolve in propylene carbon-
ments. As shown in Scheme 2, the dehydrative cou- ate under the reaction conditions. However, the reac-
pling of diphenylmethanol 1a with acetophenone tion also proceeded well when we removed the in-
(Scheme 2a) and hydration of 1,3,3-triphenylpropyne soluble portion; the insoluble solid did not show any
3a’ (Scheme 2b) under standard conditions did not activity under identical conditions. These results indi-
generate the desired products, therefore ruling out of cated that this reaction runs via homogeneous cataly-
the tandem “alkyne hydration/dehydration coupling” sis. To explore the unique effect of propylene carbon-
pathway and the tandem “dehydration coupling/ ate in this reaction, the model reaction of 1a and 2a
catalyzed by H3PMo12O40 in PC was monitored with
ESI-MS. Interestingly, a species of m/z=1034 was ob-
served when PC and H3PMo12O40 were mixed for
5 min in MeOH, which is probably attributed to
[(HPMo12O40)+2PC+H2O]2À (Figure 2). However,
the interaction between PC and other reactants was
not observed. Based on these results and previous re-
ports,[48,49] we can presume that (i) PC might enhance
the catalytic activity of POM by stabilizing the corre-
sponding heteropoly anion and (ii) PC as polar sol-
vent could stabilize the carbocation intermediate and
increase the nucleophilicity of terminal alkyne.
On the basis of our observations and the relevant
reports,[23,28,49] a possible mechanism of the carbohy-
droxylation reaction was proposed as shown in
Scheme 3. Under the promotion of heteropoly acid
H3PMo12O40 and PC, carbocation species A would
generate via the ether 4 or directly by protonation/de-
hydration of the alcohol 1. Then nucleophilic addition
Scheme 2. Control experiments for exploring the reaction
mechanism.
Figure 2. Observation of the interaction between POM catalyst and PC by ESI-MS: (a) H3PMo12O40 in MeOH, (b)
H3PMo12O40 and PC mixture in MeOH.
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Experimental Section
Typical Procedure for the POM-Catalyzed
Carbohydroxylation Reaction
To a 4-mL reaction vial, diphenylmethanol (0.2 mmol), phe-
nylacetylene (0.22 mmol), H3PMo12O40 (3 mol%) and pro-
pylene carbonate (1 mL) were added. Then the reaction was
carried out in screw cap vials with a Teflon seal at 808C for
the desired time. After cooling to room temperature, the
mixture was diluted with H2O and extracted with ethyl
ether. The combined organic layers were washed with satu-
rated NaCl solution, then dried with anhydrous Na2SO4. The
residue was further purified by column chromatography (pe-
troleum ether/EtOAc) to afford the desired products.
Acknowledgements
We thank the Natural Science Foundation of China
(21501010, 21231002, 21276026) and 973 Program
(2014CB932103) for financial support. B. Y. is grateful for
the financial support from China Postdoctoral Science Foun-
dation (2015M570939) and BIT Fundamental Research
Foundation (20151942001).
Scheme 3. Plausible mechanism for addition of alcohol and
alkyne.
of A and alkyne 2 delivered the intermediate B. The
addition of water onto B gave the corresponding in-
termediate C, followed by tautomerization which pro-
vides the desired product 3.
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over number (TON) of 520.
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8 An Atom-Economical Route to Substituted b-Arylethyl
Ketones: Phosphomolybdic Acid-Catalyzed
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Guo-Ping Yang, Nan Zhang, Nuan-Nuan Ma, Bing Yu,*
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