Transition-Metal-Free Oxidative Decarboxylative Cross Coupling of α,β-Unsaturated Carboxylic Acids with Cyclic Ethers under Air Conditions: Mild Synthesis of α-Oxyalkyl Ketones

Article abstract of DOI:10.1021/acs.joc.6b02993

A novel K₂S₂O₈-promoted decarboxylative cross coupling of α,β-unsaturated carboxylic acids with cyclic ethers was developed under aerobic conditions. The present protocol, which includes C-C and C=O bond formation in one s

Full text of DOI:10.1021/acs.joc.6b02993

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Article
Transition-Metal-Free Oxidative Decarboxylative Cross Coupling
of alpha, beta-Unsaturated Carboxylic Acids with Cyclic Ethers
under Air Conditions: Mild Synthesis of alpha-Oxyalkyl Ketones
Peng-Yi Ji, Yu-Feng Liu, Jing-Wen Xu, Wei-Ping Luo, Qiang Liu, and Can-Cheng Guo
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02993 • Publication Date (Web): 22 Feb 2017
Downloaded from http://pubs.acs.org on February 23, 2017
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TransitionꢀMetalꢀFree Oxidative Decarboxylative Cross Coupling of α, βꢀ
Unsaturated Carboxylic Acids with Cyclic Ethers under Air Conditions: Mild
Synthesis of αꢀOxyalkyl Ketones
9
PengꢀYi Ji, YuꢀFeng Liu, JingꢀWen Xu, WeiꢀPing Luo, Qiang Liu, CanꢀCheng Guo*
College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering
Research Center of the Ministry of Education, Hunan University, Changsha 410082,
China
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Eꢀmail: ccguo@hnu.edu.cn
ABSTRACT
O
X
O
X
K2S2O8 (2 equiv)
100 oC, 12h
Air
H
+
R
OH
CO2
+
O
O
R
(solvent)
X = CH2, CH2CH2, CH2O, O
transition metal free decarboxylation
18 exmples, up to 92% yields
under air condition
A novel K2S2O8 promoted decarboxylative cross coupling of α, βꢀunsaturated
carboxylic acids with cyclic ethers was developed under aerobic conditions. The
present protocol, which included CꢀC and C=O bond formation in one step through
addition, oxidation and decarboxylation processes, leading to the desired ketone
products in moderate to excellent yields. In addition, mechanism researches showed
that the transformation process undergone a radical pathway via a direct activation of
αꢀsp3 CꢀH bond of oxygen of cyclic ether.
INTRODUCTION
The construction of CꢀC, CꢀO and C=O bond have resulted in main characters in
synthetic purpose and chemistry industrial through numerous synthetic approaches.1
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Among these brilliant avenues, decarboxylative coupling reactions, in which contain
CO2 releasing from metal carboxylates to afford classic organometallic species which
can efficiently conduct coupling reactions with other organic reagents under
transitionꢀmetalꢀcatalyzed conditions, show a great application potentiality in area of
CꢀC bond formation.2 Therefore, during the last few decades, a large number of
researchers laid their eyes on the research of transition metal catalytic CꢀC bond
formation from carboxylic acid derivatives and other counterparts.3 Specially, indeed,
In 2014, zhang et al. disclosed a nickelꢀ and manganeseꢀcatalyzed selective
decarboxylative cross coupling reactions with TBHP as additive oxidant and DBU as
base.4 However, most actualities indicated that the use of transitionꢀmetal catalysts
might not be considered the most ideal ones in pharmaceutical industry, since most of
them are limited by its toxic traits, sensitive characters under aerobic atmosphere, and
its essential connections with some special additives or cocatalysts.5 In these cases,
making more significant efforts on exploiting transitionꢀmetalꢀfree coupling reactions
to construct sustainable developing model in CꢀC bond formation becomes an
inevitable trend.
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As a result, along with the continuously breakthrough in science and technology,
numerous practices and coupling reactions which are tagged to transitionꢀmetalꢀfree
conditions have been sought out,6 such as DDQꢀpromoted oxidative coupling
reactions,7 organocatalytic or organophotoredox catalytic reactions,8 Hypervalent
Iodine Reagents (HIR) promoted coupling reactions9 etc. However, transitonꢀmetalꢀ
free decarboxylative reactions especially oxidative decarboxylative coupling reactions
of α, βꢀunsaturated carboxylic acids to form industrial useful ketones are still rarely
reported at present.4,10 Therein, as well as the steadfast endeavors of our laboratory
about decarboxylative coupling reactions,11 we now wish to report the first highly
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efficient and K2S2O8 facilitated one step CꢀC and C=O bond formation from α, βꢀ
unsaturated carboxylic acid with cyclic ether via oxidative coupling and
decarboxylative reactions under air atmosphere.
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RESULTS AND DISCUSSION
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Inspired by this comforting reactivity pattern, the coupling of the cinnamic acid (1a)
with tetrahydrofuran (THF, 2a) was chosen as a model reaction for the optimization
of reaction conditions (Table 1). Initially, the efficiency of different anions and
cations which constituted the external oxidant was tested under thermal conditions
(entries 1ꢀ4, Table 1). And then treatment of the substrates with organic dioxide
compound DTBP gave only 23% yields of the desired products 3aa (entry 5, Table 1),
however, it was worthy to note that 34% yields of alkene product were obtained at the
same time which was partly consisted with the results of Sun’s work.10a The yields of
desired ketones improved onto 88% with trace amount of aldehyde byproduct when
o
the temperature was raised up to 100 C (entry 6, Table 1). Predictably, trying to
decrease the amounts of peroxide had no good for the reaction activities (entry 7,
Table 1). In order to understood whether other solvent such as water could influence
this reaction system under aerobic conditions, we mixed THF with water in different
proportions, and found that the reaction activities had been deactivated to different
extent, which might imply that the solvent effect of water was not conducive to the
transformation of model substrates (entries 8ꢀ9, Table 1). For a further study, the
reaction was carried out under O2 for 12h, but the yields of desired product decreased
to 83%, and the TLC results showed that the reaction was more complicatedly than it
was carried out under air conditions (entry 10, Table 1). Notably, only 15% yields
were obtained without the presence of peroxides indicated that the appropriate amount
of oxidant was necessary for a better reaction activity (entry 11, Table 1).
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Table 1. Optimization of the Reaction Conditions for 3aaa
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Entry oxidant
temperature/oC solvent
yield/%
70
1
K2S2O8
Na2S2O8
(NH4)2S2O8
KHSO5
DTBP
80
80
80
80
80
100
THF
2
THF
35
3
THF
30
4
THF
65
5
THF
23
6
K2S2O8
THF
88
7
K2S2O8 (1 equiv) 100
THF
68
8
K2S2O8
K2S2O8
K2S2O8
ꢀ
100
100
100
100
THF/H2O (100:1)
THF/H2O (1:1)
THF
49
9
trace
83
10b
11b
THF
15
aGeneral reaction conditions unless otherwise pointed: 1 (0.2 mmol), 2a (1.5 ml),
K2S2O8 (0.4 mmol, 2 equiv) at 100 oC under air for 12 h. b under O2 for 12 h.
With the optimized conditions in hand, the generality and scope of substrates were
examined (Table 2). Both halogen and electronꢀrich or ꢀdeficient arylꢀsubstituented
cinnamic acids could be smoothly transformed in a range of 34ꢀ92% yields (3aaꢀ3ga).
A series of functional groups at metaꢀposition of the aryl ring were also toleranted
well in these oxidative decarboxylative cross coupling reactions (3haꢀ3ja). Then,
several orthoꢀsubtituented cinnamic acids except OH group still showed moderate to
good efficiency in these CꢀC and C=O bond formations (3kaꢀ3na). Part of the reason
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for various compatibility and reactivity might be that the electronic effects of different
substitutents on phenyl ring could influence the reaction activities of α, βꢀunsaturated
carboxylic acids. Furthermore, notably, the position of the substituents at aryl ring
could influence the efficiency of this transformation. For instance, methoxyꢀgroup at
metaꢀposition gave a better transformation efficiency than it at orthoꢀ/paraꢀposition,
probably because of the electronic effect of methoxyꢀgroup impacted the reaction
activities(3ea, 3ha, 3ka). For the heterocyclic derivatives, only (E)ꢀ3ꢀ(thiophenꢀ2ꢀ
yl)acrylic acid successfully transformed into corresponding products, and obtained in
45% yields (3oaꢀ3ra), which indicated that the influence of the heteroatoms in
aromatic ring was not negligible. Moreover, it was found that both (2E,4E)ꢀhexaꢀ2,4ꢀ
dienoic acid 3sa and (E)ꢀhexꢀ2ꢀenoic acid 3ta were not amenable to the present
transformation even under O2 for 15h.
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Table 2. Scope of α, βꢀUnsaturated Carboxylic Acidsa
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aGeneral reaction conditions unless otherwise pointed: 1 (0.2 mmol), 2a (1.5 ml),
o
b
K2S2O8 (0.4 mmol, 2 equiv) at 100 C under air for 12 h, yield of isolated product.
under O2 for 15 h.
Subsequently, we tested the scope of heterocyclic compounds (Table 3). When
pentabasic cyclic compounds such as tetrahydrofuran, tetrahydrothiophene and 1ꢀ
methylpyrrolidine were employed as substrates, it was found that only when the
C(sp3)ꢀH bond adjacent to oxygen atom, the heterocyclic compounds could be
activated successfully under the standard conditions, which might also implied that
heteroatoms in heterocyclic compounds played a leadership role in this activation
process (3aaꢀ3ac). Then, other cyclic ether like 1,3ꢀdioxolane and benzo[d]ꢀ
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[1,3]dioxole were investigated, and the desired product 3ad were obtained in 52%,
but benzo[d]ꢀ[1,3]dioxole was failed yet to give the product 3ae. Fortunately,
hexatomic cyclic ethers coupled well with cinnamic acids to give the corresponding
products in 71ꢀ63% yields (3afꢀ3ag). Linear ethers, such as dibutyl ether 3ah, are
failed to take part into this kind of transformation.
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Table 3. Scope of Cyclic or Linear Coupling Componenta
aGeneral reaction conditions unless otherwise pointed: 1a (0.2 mmol), 2 (1.5 ml),
o
K2S2O8 (0.4 mmol, 2 equiv) at 100 C under air for 12 h, yield of isolated product. b
reacted at 110 oC under air for 15 h.
For the possible reaction mechanism of the decarboxylative coupling process,
several control experiments were carried out at the beginning (Scheme 1). Initially, 2
equiv of the radical scavenger, such as 2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy (TEMPO)
or butylated hydroxytoluene (BHT), were added into the reaction mixture respectively,
the model reaction was not transformed successfully according to the results of TLC
and GCꢀMS (Scheme 1aꢀb), which made clear a radical process was included in this
decarboxylative coupling reaction. Delightfully, trace amount of the free radical
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intermediate species 4 was detected by GCꢀMS, which impelled us to interpret the
reaction was able to conduct via a direct activation of αꢀsp3 CꢀH bond of oxygen
under nitrogen conditions (Scheme 1c, for details, see Supporting Information). No
reaction products occurred and no styrene was obtained when cinnamic acid was
employed as the substrate only (Scheme 1d), furthermore, we employed styrene and
tetrahydrofuran as the substrates under standard conditions, and no desired products
3aa were detected (Scheme 1e). The results thus obtained showed that styrene might
not take a part in this decarboxylative cross coupling process of the model
transformation. While the model reaction was conducted under N2 for 12h, no desired
ketone products 3aa were obtained, and the recovery rate of material was about 90%.
It should be pointed out that trace amount of the alkenylation product was formed
under the standard reaction conditions, which might indicate that the dioxygen was
indispensable for the model transformation and was likely to act as an important role
for the origin of ketone oxygen (Scheme 1f, for more details see Scheme S2.1 in
Supporting Information). Subsequently, the model reaction was conducted under O2
without the existence of the K2S2O8 for 24h, to our surprise, about 16% yields of 3aa
and 8% yields of the alkylation product 3aa’ were formed, and we wondered whether
the alkylation compound 3aa’ was one of the intermediates to form the final ketone
product, then the alkylation compound was employed as the reaction agent under air
or N2 with 1 equiv of the oxidant, but no ketone products were obtained, according to
these, we believed that the alkylation compound might not act as an intermediate
compound for the formation of 3aa under the standard conditions (for more details,
see Scheme S2.2 in Supporting Information).
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Scheme 1. Experiments for Mechanism
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On the basis of the experiments mentioned above and preterit literatures,12 and in
contrast to the work which selectively formed ketones via the ineluctable produce of
Ni(II) carboxylate salt intermidiates,4 a possible inequable radical pathway of the
decarboxylative coupling reactions under transitonꢀmetalꢀfree conditions is proposed
(scheme 2). At the beginning, hydrogen abstraction of 2a generates αꢀoxyalkyl radical
A with the existence of K2S2O8 under thermal conditions.13 After a radical addition of
A to cinnamic acid 1a and direct O2 trapping process, then produces peroxide radical
B which could potentially undergo a decomposition process to form radical
intermediate C.12a,d Thereafter, a subsequent oxidation of C might adopt to form D.
Finally, compound D via a cyclizationꢀdecarboxylationꢀaromatization process14 under
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the standard conditions, produces E (for details, see Scheme S2.1 in Supporting
Information), which isomerizes and forms product 3aa. In addition, further researches
are still on the way for clarifying detailed mechanisms and underway by our group.
Scheme 2. Possible Mechanism
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CONCLUSIONS
From above all,
a
novel K2S2O8ꢀmediated oxidative decarboxylative
oxyalkylation of α, βꢀunsaturated carboxylic acids and cyclic ethers via selective
activation of αꢀsp3 CꢀH bonds of oxygen to construct new CꢀC bonds and C=O bonds
has been systematic researched. Prudently, it also invites us to utilize and improve
these particular protocols and potential synthetic utility in modern organic synthesis.
The vast field and mechanism of radical decarboxylative couplings with cyclic ethers
in the presence of 2 equiv of K2S2O8 under mild aerobic conditions has been
appropriately discussed as well. More oxidative decarboxylative coupling reactions
and a broader application of transitionꢀmetalꢀfree conditions thus mentioned above
will be continuously exploited by our group.
EXPERIMENTAL SECTION
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General Comments. All available compounds were purchased from commercial
suppliers, and the compounds were used without further purification unless otherwise
noted. All solvents were purified according to the method of Grubbs.15 1H NMR and
13C NMR spectra were recorded at 400 and 100 MHz in CDCl3 using TMS as the
internal standard. Multiplicities were indicated as s (singlet), d (doublet), t (triplet), q
(quartet), and m (multiplet). Coupling constants (J) were reported in hertz. Copies of
1H NMR and 13C NMR spectra were provided as Supporting Information. Column
chromatography was performed on 300−400 mesh silica gel. Thinlayer
chromatography (TLC) was performed on Silicycle 250 mm silica gel Fꢀ254 plates.
Highꢀresolution mass spectra (HRMS) were measured on a double focusing mass
spectrometer with EI source.
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General Procedure for the Decarboxylative Coupling reaction between various
α, βꢀUnsaturated Carboxylic Acids and THF: To a 20 mL Schlenk tube was added
α, βꢀunsaturated carboxylic acid (0.2 mmol), K2S2O8 (90.8 mg, 0.4 mmol),
o
tetrahydrofuran (1.5 ml). The reaction mixture was stirred at 100 C for 12 h in
sealed conditions. Upon completion of the reaction, the resulting mixture was dilute
by EtOAc and washed with equal amounts of saturated NaHCO3 solution, then the
organic phase was separated and washed with water, and the water phase was
extracted by EtOAc for three times. The combined organic extracts thus obtained
were dried over anhydrous Na2SO4 and filtered. Finally, after concentrated in vacuum,
the resulting mixture was purified by silica gel column chromatography (hexane/ethyl
acetate = 15:1) to afford the desired product.
General Procedure for the Decarboxylative Coupling reaction between various
Cyclic Coupling Components and Cinnamic Acid: To a 20 mL Schlenk tube was
added cinnamic acid (0.2 mmol), K2S2O8 (90.8 mg, 0.4 mmol), cyclic coupling
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o
component (1.5 ml). The reaction mixture was stirred at 100 C for 12 h in
sealed conditions. Upon completion of the reaction, the resulting mixture was dilute
by EtOAc and washed with equal amounts of saturated NaHCO3 solution, then the
organic phase was separated and washed with water, and the water phase was
extracted by EtOAc for three times. The combined organic extracts thus obtained
were dried over anhydrous Na2SO4 and filtered. Finally, after concentrated in vacuum,
the resulting mixture was purified by silica gel column chromatography (hexane/ethyl
acetate = 15:1) to afford the desired product.
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3ꢀoxoꢀ3ꢀphenylꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)propanoic acid (C). (new) Yellow oil:
1H NMR (400 MHz, CDCl3) δ 8.04 – 7.96 (m, 1H), 7.58 – 7.55 (m, 1H), 7.52 – 7.45
(m, 2H), 4.30 – 4.23 (m, 1H), 3.94 – 3.88 (dd, J = 14.7, 7.3 Hz, 1H), 3.82 – 3.76 (dd, J
= 14.7, 7.5 Hz, 1H), 2.63 – 2.56 (m, 1H), 2.16 – 2.08 (dt, J = 12.4, 6.5 Hz, 1H), 1.95 –
1.91 (m, 2H), 1.62 – 1.53 (dt, J = 19.8, 7.7 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
25.5, 31.2, 40.2, 68.1, 75.0, 128.1, 128.6, 133.1, 137.0, 175.7, 199.9. HRMS (EI)
Calcd for C13H14O4 (M+) 234.0892; Found, 234.0880.
1ꢀphenylꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3aa).16b Following the general
1
procedure, the product was isolated as yellow oil in 88% yields (33.4 mg). H NMR
(400 MHz, CDCl3) δ: 7.97 (d, J = 7.7 Hz, 2H), 7.56 (t, J = 7.3 Hz, 1H), 7.46 (t, J =
7.5 Hz, 2H), 4.44 – 4.38 (m, 1H), 3.91– 3.87 (dd, J = 14.6, 7.2 Hz, 1H), 3.76 – 3.75
(dd, J = 14.8, 7.4 Hz, 1H), 3.43 – 3.37 (dd, J = 16.3, 6.1 Hz, 1H), 3.09 – 3.03 (dd, J =
16.3, 6.7 Hz, 1H), 2.23 – 2.16 (dt, J = 13.0, 6.5 Hz, 1H), 1.98 – 1.88 (m, 2H), 1.61 –
1.52 (m, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.6, 31.6, 44.6, 67.8, 75.4, 128.2,
128.6, 133.1, 137.0, 198.4.
16b
1ꢀ(4ꢀfluorophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ba).
Following the
general procedure, the product was isolated as yellow oil in 90% yields (37.4 mg).
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1H NMR (400 MHz, CDCl3) δ: 8.01 – 7.98 (dd, J = 8.5, 5.5 Hz, 2H), 7.13 (t, J = 8.5
Hz, 2H), 4.44 – 4.35 (m, 1H), 3.90 – 3.86 (dd, J = 14.8, 7.0 Hz, 1H), 3.76 – 3.74 (dd,
J = 14.8, 7.4 Hz, 1H), 3.37 – 3.33 (dd, J = 16.1, 6.3 Hz, 1H), 3.05 – 3.00 (dd, J = 16.1,
6.4 Hz, 1H), 2.22 – 2.16 (td, J = 12.8, 6.5 Hz, 1H), 1.98 – 1.89 (m, 2H), 1.62 – 1.53
(ddd, J = 16.1, 12.5, 7.9 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.5, 31.6, 44.5,
67.8, 75.3, 115.6 (d, JCꢀF = 22.0 Hz), 130.8 (d, JCꢀF = 9.3 Hz), 133.5 (d, JCꢀF = 3.0 Hz),
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16b
1ꢀ(4ꢀchlorophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ca).
Following the
general procedure, the product was isolated as yellow oil in 92% yields (41.2 mg).
1H NMR (400 MHz, CDCl3) δ: 7.90 (d, J = 8.2 Hz, 2H), 7.43 (d, J = 8.2 Hz, 2H), 4.42
– 4.35 (m, 1H), 3.90 – 3.88 (dd, J = 14.6, 7.3 Hz, 1H), 3.78 –3.74 (dd, J = 14.9, 7.4
Hz, 1H), 3.37 – 3.31 (dd, J = 16.2, 6.3 Hz, 1H), 3.03 – 2.99 (dd, J = 16.2, 6.3 Hz, 1H),
2.22 – 2.15 (td, J = 12.8, 6.5 Hz, 1H), 1.98 – 1.88 (m, 2H), 1.61 – 1.52 (dq, J = 12.5,
8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.5 31.5, 44.5, 67.8, 75.3, 128.8, 129.6,
135.3, 139.5, 197.2.
16b
1ꢀ(4ꢀbromophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3da).
Following the
general procedure, the product was isolated as yellow oil in 80% yields (42.9 mg).
1H NMR (400 MHz, CDCl3) δ: 7.83 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 8.1 Hz, 2H), 4.42
– 4.36 (m, 1H), 3.90 – 3.88 (dd, J = 14.7, 7.2 Hz, 1H), 3.78 – 3.76 (dd, J = 14.8, 7.4
Hz, 1H), 3.36 – 3.31 (dd, J = 16.1, 6.3 Hz, 1H), 3.05 – 2.99 (dd, J = 16.2, 6.3 Hz, 1H),
2.22 – 2.15 (dt, J = 12.9, 6.4 Hz, 1H), 1.97 – 1.90 (dt, J = 13.4, 6.9 Hz, 2H), 1.57 –
1.52 (dd, J = 14.2, 6.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.6 31.6, 44.6, 67.9,
75.3, 128.3, 129.7, 131.9, 135.8, 197.5.
16b
1ꢀ(4ꢀmethoxyphenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ea).
Following the
general procedure, the product was isolated as yellow oil in 45% yields (19.8 mg).
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1H NMR (400 MHz, CDCl3) δ: 7.95 (d, J = 8.5 Hz, 2H), 6.93 (d, J = 8.5 Hz, 2H), 4.43
– 4.36 (m, 1H), 3.91 – 3.87 (m, 4H), 3.79 – 3.77 (m, 1H), 3.38 – 3.33 (dd, J = 15.9,
6.0 Hz, 1H), 3.03 – 2.98 (dd, J = 16.0, 6.8 Hz, 1H), 2.21 – 2.15 (dt, J = 19.1, 6.6 Hz,
1H), 1.97 – 1.88 (m, 2H), 1.62 – 1.55 (dd, J = 12.3, 8.0 Hz, 1H). 13C NMR (100 MHz,
CDCl3) δ: 25.6, 31.6, 44.3, 55.7, 67.8, 75.6, 114.8, 130.2, 130.5, 163.5, 197.1.
1ꢀ(4ꢀnitrophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3fa).(new) Following the
general procedure, the product was isolated as yellow oil in 56% yields (26.3 mg).
1H NMR (400 MHz, CDCl3) δ: 8.31 (d, J = 8.6 Hz, 2H), 8.12 (d, J = 8.6 Hz, 2H), 4.43
– 4.37 (m, 1H), 3.90 – 3.87 (dd, J = 14.8, 7.1 Hz, 1H), 3.77 – 3.75 (dd, J = 14.9, 7.4
Hz, 1H), 3.42 – 3.36 (dd, J = 16.2, 6.7 Hz, 1H), 3.13 – 3.04 (dd, J = 16.2, 5.8 Hz, 1H),
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2.24 – 2.18 (td, J = 12.8, 6.5 Hz, 1H), 1.99 – 1.92 (m, 2H), 1.62 – 1.57 (m, 1H). C
NMR (100 MHz, CDCl3) δ: 25.6, 31.6, 45.1, 68.0, 75.1, 123.8, 129.3, 141.5, 150.3,
+
197.1. HRMS (EI) Calcd for C12H13NO4 (M ) 235.0845; Found, 235.0840.
16c
2ꢀ(tetrahydrofuranꢀ2ꢀyl)ꢀ1ꢀ(4ꢀ(trifluoromethyl)phenyl)ethanone
(3ga).
Following the general procedure, the product was isolated as white solid in 34%
yields (17.6 mg). 1H NMR (400 MHz, CDCl3) δ: 8.07 (d, J = 8.1 Hz, 2H), 7.73 (d, J =
8.2 Hz, 2H), 4.44 – 4.37 (m, 1H), 3.90 – 3.88 (m, 1H), 3.77 – 3.75 (dd, J = 14.9, 7.4
Hz, 1H), 3.42 – 3.36 (dd, J = 16.2, 6.4 Hz, 1H), 3.11 – 3.05 (dd, J = 16.2, 6.1 Hz, 1H),
2.23 – 2.17 (td, J = 12.8, 6.5 Hz, 1H), 1.98 – 1.91 (m, 2H), 1.63 – 1.54 (ddd, J = 16.0,
12.4, 8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.6, 31.6, 44.9, 67.9, 75.2, 122.2,
125.6 (q, JCꢀF = 3.6 Hz), 128.5, 134.5 (d, JCꢀF = 33 Hz) 139.7, 197.5.
(new)
1ꢀ(3ꢀmethoxyphenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ha).
Following the
general procedure, the product was isolated as yellow oil in 87% yields (38.3 mg).
1H NMR (400 MHz, CDCl3) δ: 7.54 (d, J = 7.6 Hz, 1H), 7.49 (s, 1H), 7.37 (t, J = 7.9
Hz, 1H), 7.12 – 7.09 (dd, J = 8.2, 2.4 Hz, 1H), 4.44 – 4.37 (m, 1H), 3.90 – 3.85 (m,
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4H), 3.76 – 3.74 (dd, J = 14.9, 7.4 Hz, 1H), 3.40 – 3.35 (dd, J = 16.2, 6.1 Hz, 1H),
3.07 – 3.02 (dd, J = 16.2, 6.7 Hz, 1H), 2.22 – 2.16 (td, J = 12.8, 6.5 Hz, 1H), 1.97 –
1.89 (m, 2H), 1.61 – 1.52 (ddd, J = 16.0, 12.4, 7.9 Hz, 1H). 13C NMR (100 MHz,
CDCl3) δ: 25.6, 31.6, 44.7, 55.3, 67.8, 75.4, 112.2, 119.6, 120.8, 129.5, 138.4, 159.8,
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198.2. HRMS (EI) Calcd for C13H16O3 (M ) 220.1099; Found, 220.1098.
16b
2ꢀ(tetrahydrofuranꢀ2ꢀyl)ꢀ1ꢀ(mꢀtolyl)ethanone (3ia).
Following the general
procedure, the product was isolated as brown oil in 79% yields (32.2 mg).
1H NMR (400 MHz, CDCl3) δ: 7.76 (d, J = 9.9 Hz, 2H), 7.38 – 7.32 (m, 2H), 4.44 –
4.37 (m, 1H), 3.90 – 3.88 (dd, J = 14.8, 7.1 Hz, 1H), 3.78 – 3.74 (dd, J = 14.9, 7.4 Hz,
1H), 3.41 – 3.36 (dd, J = 16.2, 6.0 Hz, 1H), 3.07 – 3.01 (dd, J = 16.2, 6.8 Hz, 1H),
2.41 (s, 3H), 2.22 – 2.17 (dt, J = 12.6, 6.4 Hz, 1H), 1.97 – 1.90 (m, 2H), 1.61 – 1.52
(ddd, J = 16.1, 12.4, 7.9 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 21.3, 25.6, 31.6,
44.7, 67.8, 75.4, 125.4, 128.4, 128.7, 133.8, 137.1, 138.3, 198.6.
(new)
1ꢀ(3ꢀbromophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ja).
Following the
general procedure, the product was isolated as yellow oil in 54% yields (28.9 mg).
1H NMR (400 MHz, CDCl3) δ: 7.87 (s, 1H), 7.77 (d, J = 7.7 Hz, 1H), 7.46 (d, J = 7.9
Hz, 1H), 7.36 – 7.32 (t, J = 7.9 Hz, 1H), 4.36 – 4.29 (m, 1H), 3.82 (dd, J = 14.6, 7.3
Hz, 1H), 3.83 – 3.68 (dd, J = 14.9, 7.4 Hz, 1H), 3.30 – 3.25 (dd, J = 16.2, 6.3 Hz, 1H),
2.99 – 2.93 (dd, J = 16.2, 6.3 Hz, 1H), 2.15 – 2.09 (td, J = 12.8, 6.5 Hz, 1H), 1.90 –
1.83 (m, 2H), 1.50 – 1.45 (m, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.6, 31.6, 44.7,
67.9, 75.2, 126.3, 128.3, 129.9, 133.0, 134.9, 138.6, 197.1. HRMS (EI) Calcd for
+
C12H13BrO2 (M ) 268.0099; Found, 268.0103.
16a
1ꢀ(2ꢀmethoxyphenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ka).
Following the
general procedure, the product was isolated as yellow oil in 46% yields (20.2 mg).
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1H NMR (400 MHz, CDCl3) δ 7.72 – 7.70 (dd, J = 7.6, 1.3 Hz, 1H), 7.45 – 7.43 (m,
1H), 7.02 – 6.95 (m, 2H), 4.40 – 4.29 (m, 1H), 3.90 – 3.86 (m, 4H), 3.74 – 3.72 (dd, J
= 14.9, 7.4 Hz, 1H), 3.42 – 3.36 (dd, J = 16.8, 6.1 Hz, 1H), 3.17 – 3.11 (dd, J = 16.8,
6.9 Hz, 1H), 2.18 – 2.14 (m, 1H), 1.94 – 1.86 (m, 2H), 1.58 – 1.49 (m, 1H). 13C NMR
(100 MHz, CDCl3) δ: 25.6, 31.5, 49.9, 55.4, 67.7, 75.4, 111.5, 120.7, 128.3, 130.4,
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133.5, 158.6, 200.3.
16b
1ꢀ(2ꢀfluorophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3ma).
Following the
general procedure, the product was isolated as yellow oil in 82% yields (34.1 mg).
1H NMR (400 MHz, CDCl3) δ: 7.87 (t, J = 7.4 Hz, 1H), 7.52 – 7.48 (dd, J = 13.3, 6.7
Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 7.15 – 7.10 (dd, J = 10.8, 8.8 Hz, 1H), 4.45 – 4.38
(m, 1H), 3.89 – 3.85 (dd, J = 14.6, 7.2 Hz, 1H), 3.77 – 3.74 (dd, J = 14.7, 7.4 Hz, 1H),
3.33 – 3.31 (ddd, J = 17.0, 6.6, 2.4 Hz, 1H), 3.16 – 3.14 (ddd, J = 17.0, 5.7, 2.9 Hz,
1H), 2.20 – 2.16 (m, 1H), 1.95 – 1.90 (dd, J = 14.3, 7.3 Hz, 2H), 1.61 – 1.52 (m, 1H).
13C NMR (100 MHz, CDCl3) δ: 25.6, 31.6, 49.5 (d, JCꢀF = 6.9 Hz), 67.8, 74.8 (d, JCꢀF
= 1.9 Hz), 116.6 (d, JCꢀF = 24 Hz), 124.4 (d, JCꢀF = 3.4 Hz), 125.7, 130.6 (d, JCꢀF = 2.5
Hz), 134.5 (d, JCꢀF = 9.0 Hz), 161.9 (d, JCꢀF = 253.0 Hz), 196.5 (d, JCꢀF = 3.8 Hz).
16a
1ꢀ(2ꢀchlorophenyl)ꢀ2ꢀ(tetrahydrofuranꢀ2ꢀyl)ethanone (3na).
Following the
general procedure, the product was isolated as yellow oil in 87% yields (39.0 mg).
1H NMR (400 MHz, CDCl3) δ: 7.51 – 7.50 (d, J = 7.5 Hz, 1H), 7.41 – 7.37 (t, J = 7.6
Hz, 2H), 7.35 – 7.30 (dd, J = 14.4, 7.2 Hz, 1H), 4.38 – 4.32 (p, J = 6.7 Hz, 1H), 3.87 –
3.84 (dd, J = 14.6, 7.3 Hz, 1H), 3.74 – 3.72 (dd, J = 14.8, 7.5 Hz, 1H), 3.31 – 3.25 (dd,
J = 16.3, 6.9 Hz, 1H), 3.14 – 3.09 (dd, J = 16.3, 6.0 Hz, 1H), 2.18 – 2.13 (td, J = 12.7,
6.5 Hz, 1H), 1.95 – 1.90 (m, 2H), 1.62 – 1.53 (m, 1H). 13C NMR (100 MHz, CDCl3) δ:
25.6, 31.4, 48.9, 67.8, 75.1, 126.9, 129.1, 130.4, 130.8, 131.7, 139.4, 201.4.
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2ꢀ(tetrahydrofuranꢀ2ꢀyl)ꢀ1ꢀ(thiophenꢀ2ꢀyl)ethanone (3pa).
Following the
general procedure, the product was isolated as yellow oil in 45% yields (17.6 mg). 1H
NMR (400 MHz, CDCl3) δ: 7.74 – 7.71 (dd, J = 7.2, 3.8 Hz, 1H), 7.64 (d, J = 4.9 Hz,
1H), 7.13 (t, J = 4.3 Hz, 1H), 4.42 – 4.35 (m, 1H), 3.90 – 3.87 (dd, J = 14.5, 7.2 Hz,
1H), 3.76 – 3.74 (dd, J = 14.8, 7.5 Hz, 1H), 3.33 – 3.27 (dd, J = 15.4, 6.3 Hz, 1H),
3.01 – 2.96 (dd, J = 15.2, 6.5 Hz, 1H), 2.17 (dt, J = 12.5, 6.5 Hz, 1H), 1.93 (dt, J =
10.3, 8.5 Hz, 2H), 1.84 – 1.75 (m, 1H). 13C NMR (100 MHz, CDCl3) δ: 25.6, 31.5,
45.4, 67.9, 75.5, 128.1, 132.3, 133.8, 144.6, 191.1. HRMS (EI) Calcd for C10H12O2S
(M+) 196.0558; Found, 196.0563.
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2ꢀ(1,3ꢀdioxolanꢀ2ꢀyl)ꢀ1ꢀphenylethanone (3ad). 16b Following the general procedure,
the product was isolated as yellow oil in 52% yields (20.0 mg).
1H NMR (400 MHz, CDCl3) δ: 7.90 (d, J = 7.9 Hz, 2H), 7.50 (t, J = 7.2 Hz, 1H), 7.40
(t, J = 7.4 Hz, 2H), 5.38 (t, J = 4.8 Hz, 1H), 3.96 – 3.88 (m, 2H), 3.85 – 3.82 (m, 2H),
3.28 (d, J = 4.9 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ: 43.4, 65.0, 101.4, 128.3,
128.6, 133.3, 136.9, 196.5.
16b
1ꢀphenylꢀ2ꢀ(tetrahydroꢀ2Hꢀpyranꢀ2ꢀyl)ethanone (3af).
Following the general
procedure, the product was isolated as yellow oil in 71% yields (29.0 mg).
1H NMR (400 MHz, CDCl3) δ: 7.96 (d, J = 7.9 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.45
(t, J = 7.6 Hz, 2H), 3.98 – 3.93 (m, 2H), 3.48 (t, J = 11.2 Hz, 1H), 3.32 – 3.26 (dd, J =
16.0, 6.7 Hz, 1H), 2.95 – 2.90 (dd, J = 16.0, 5.7 Hz, 1H), 1.86 – 1.84 (m, 1H), 1.75 (d,
J = 12.9 Hz, 1H), 1.60 – 1.50 (m, 3H), 1.41 – 1.33 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ: 23.4, 25.8, 32.0, 45.4, 68.6, 74.3, 128.2, 128.5, 133.0, 137.3, 198.4.
16b
2ꢀ(1,4ꢀdioxanꢀ2ꢀyl)ꢀ1ꢀphenylethanone (3ag).
Following the general procedure,
the product was isolated as yellow oil in 63% yields (26.0 mg).
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1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.9 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.47
(t, J = 7.6 Hz, 2H), 4.28 – 4.22 (m, 1H), 3.93 – 3.89 (m, 1H), 3.80 – 3.71 (m, 3H),
3.66 – 3.60 (m, 1H), 3.39 (t, J = 10.6 Hz, 1H), 3.23 – 3.22 (dd, J = 16.5, 6.5 Hz, 1H),
2.92 – 2.86 (dd, J = 16.5, 6.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 40.7, 66.4,
66.8, 70.9, 71.8, 128.2, 128.6, 133.3, 136.8, 197.1.
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ASSOCIATED CONTENTS
Supporting Information
Copies of 1H and 13C spectra for all products and the mechanismꢀrelated experiments
are available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: ccguo@hnu.edu.cn.
Notes
The authors declare no competing financial interest.
Acknowledgements
Financial supports from the National Science Foundations of China (No.21372068,
21572049) are gratefully acknowledged.
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S.; Chem. Rev. 2007, 107, 5318. (c) Cao, H.; Liu, X.; Liao, J.; Huang, J.; Qiu, H,;
Chen, Q.; Chen, Y.; J. Org. Chem., 2014, 79, 11209. (d) Liu, Y.; Zhu, J.; Qian, J.; Xu,
Z.; J. Org. Chem., 2012, 77, 5411.
(2) For some selected examples, see: Rodriguez, N.; (a) Goossen, L. J.; Chem. Soc.
Rev. 2011, 40, 5030. (b) Arun, J. B.; Yan, G.; Org. Biomol. Chem. 2015, 13, 8094.
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(3) For some selected examples, see: (a) Rui, S. Lei, L.; Sci China Chem. 2011, 54, 11.
(b) Shen, C.; Zhang, P.; Sun, Q.; Bai, S.; Andy Hor, T.S.; Liu, X. G.; Chem. Soc. Rev.
2015, 44, 291. (c) Neely, J. M., Rovis, T.; J. Am. Chem. Soc. 2014, 136, 2735. (d)
Rong, G.; Liu, D.; Lu, L.; Yan, H.; Zheng, Y.; Chen, J.; Mao, J.; Tetrahedron. 2014,
70, 5033. (e) Zhang, L.; Hang, Z.; Liu, Z.; Angew. Chem. Int. Ed. 2016, 55, 236.
(4) Zhang, J. X.; Wang, Y. J.; Zhang, W.; Wang, N. X.; Bai, C. B.; Xing, Y. L.; Li, Y.
He.; Wen, J. L.; Sci. Rep. 2014, 4, 7446.
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