Functionalized Allyl Aryl Ether Synthesis from Benzoic Acids Using a Dearomatization and Decarboxylative Allylation Approach

Article abstract of DOI:10.1021/acs.joc.8b02487

A strategy toward the preparation of substituted allyl aryl ethers from benzoic acids via a dearomatization and decarboxylative allylation (DcA) reaction is presented. The benzoic acids undergo a dearomatization to give alkylated 2,5-cyclohexadienyl ketoesters which are subjected to a palladium-catalyzed DcA reaction, providing a variety of functionalized allyl aryl ethers. In addition, the combination of a resonance stabilized DcA reaction with a Claisen rearrangement for the synthesis of multisubstituted phenols and applying to dihydroplicatin B derivative synthesis is also presented.

Full text of DOI:10.1021/acs.joc.8b02487

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Article
Functionalized Allyl Aryl Ethers Synthesis from Benzoic Acids
Using Dearomatization and Decarboxylative Allylation Approach
Cheng-En Hsieh, Yu-Min Jiang, and Chih-Ming Chou
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02487 • Publication Date (Web): 31 Dec 2018
Downloaded from http://pubs.acs.org on January 1, 2019
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The Journal of Organic Chemistry
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Functionalized Allyl Aryl Ethers Synthesis from Benzoic Acids Using
Dearomatization and Decarboxylative Allylation Approach
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Cheng-En Hsieh, Yu-Min Jiang, and Chih-Ming Chou*
Department of Applied Chemistry, National University of Kaohsiung, 700, Kaohsiung University Road, Nanzih District,
81148 Kaohsiung, Taiwan.
Supporting Information Placeholder
R2
O
R2
CO2H
allyl
O
R1
dearomatization
Pd cat.
R1
R1
decarboxylative
O-allylation
O
O
allyl
21 examples, 58-
97%
via Resonance Stabilized Aryl Oxide
R2
O
R2
Pd(II)Ln
Pd(II)Ln
R1
R1
Rearomatization
O
ABSTRACT: A strategy towards the preparation of substituted allyl aryl ethers from benzoic acids via a dearomatization and
decarboxylative allylation (DcA) reaction is presented. The benzoic acids undergo a dearomatization to give alkylated 2,5-
cyclohexadienyl ketoesters which are subjected to a palladium-catalyzed DcA reaction providing a variety of functionalized allyl aryl
ethers. In addition, the combination of resonance stabilized DcA reaction with a Claisen rearrangement for the synthesis of multi-
substituted phenols and applying to dihydroplicatin B derivative synthesis is also presented.
chloroformates under basic conditions.7f Nevertheless, some
phenolic substrates bearing multi-substituents are not readily
■ INTRODUCTION
available. Hence, extending the substrate scope of highly
substituted allyl aryl ethers to improve the synthetic potentials
in bioactive molecules synthesis is of particular interests.
Functionalized arenes are important scaffolds for the
preparation of natural products, pharmaceuticals, and functional
materials. Among all of the functionalized arenes, allyl aryl
ethers particularly draw our attention because they are key
precursors used in natural product synthesis.1 For instance, allyl
aryl ethers can undergo aryl-Claisen [3,3]-sigmatropic
rearrangements2 providing ortho-allyl phenols followed by
cyclization to give dihydrobenzofurans,3 which are important
backbones in many biologically active molecules.4 Moreover,
isochroman and dioxabicyclooctane scaffolds can be prepared
through Friedel-Crafts type cyclizations of allyl aryl ethers.5
Scheme 1. Various Intermediates in DcA Reactions
enolate
-imino anion
-sulfonyl anion


Ph
H
O
O
O
Pd(II)Ln
Pd(II)Ln
Pd(II)Ln
S
N
Ph
R
-nitronate
anionic nitrogen
aryl oxide

Generally, the Williamson ether synthesis is a classical
method for the preparation of allyl aryl ethers.6 This protocol
involves the SN2 attack of a phenoxide with allyl halides or
tosylates. However, a stoichiometric amount of a base and an
unhindered alkylating reagent are often required under these
reaction conditions. Recently, the transition metal-catalyzed
decarboxylative allylation (DcA) of allyl aryl carbonates or
vinyl cyclic carbonates have been used to prepare allyl aryl
ethers with advantages over the Williamson ether synthesis.
These catalytic process are conducted under neutral conditions
with broad substrate scope of allyl moieties in a regioselective
and/or enantioselective manner.7 Typically, allyl aryl
carbonates are prepared by reaction of phenols with allyl
O
O2N
Pd(II)Ln
R1
Pd(II)Ln
Pd(II)Ln
N
R2
Earlier studies have shown that DcA reactions can be carried
out using a wide range of starting materials. During the DcA
process, it is thought that the reactants can form a stable carbon
or heteroatom nucleophiles via decarboxylation.8 For example,
enolates,9 -imino anions,10 -sulfonyl anions,11 -nitronates,12
anionic nitrogens,13 and aryl oxides7 can act as good
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rearrangement of compound 2a. Next, we replaced the
nucleophiles toward Pd--allyl-complexes in DcA reactions to
furnish carbon-carbon or carbon-heteroatom bond formations
(Scheme 1). We recently developed two protocols for the
preparation of ortho-alkylated vinylarenes or meta-alkylated
vinylarenes through the dearomatization of benzoic acids
affording alkylated 2,5-cyclohexadiene-1-carboxylic acids
followed by decarboxylative C-H olefination14 and
decarboxylative −olefination/rearomatization,15 respectively
(Scheme 2a).
1
2
3
4
5
6
7
8
Pd(PPh3)4 with Pd(dba)2. However, the yield dropped
dramatically and compound 1a was recovered, regardless of
which of the three solvents (toluene, tetrahydrofuran,
acetonitrile) that were used (entries 2-4). Pleasingly, we
obtained up to 95% yield by simply lowering the reaction
temperature to room temperature in the presence of Pd(PPh3)4
(entry 5). The effect of various solvents at room temperature
was also studied and the resulting product yields were nearly
the same. To study the effect of catalyst loading, 1 mol % of
Pd(PPh3)4 was tested, but resulted in poorer yield (entry 8).
Therefore, we used 5 mol % of Pd(PPh3)4 in acetonitrile at rt as
the standard conditions in the following experiments.
In light of the above, we investigated ways in which to
expand the reaction repertoire of alkylated 2,5-cyclohexadiene-
1-carboxylic acids.14-16 We envisioned that the cross-conjugated
ketoesters 1 or 3 derived from alkylated 2,5-cyclohexadiene-1-
carboxylic acids by sequential Birch reduction, esterification
and oxidation, (see Supporting Information (SI) for details), can
be utilized in Pd-catalyzed decarboxylative allylic etherification
reactions. During the DcA reaction, the aromaticity of the
products can be regained due to the formation of a resonance
stabilized aryl oxide intermediate (Scheme 2b). This reaction
will be referred to as the resonance stabilized DcA (RSDcA)
reaction. Upon reaction of an aryl oxide with a Pd--allyl
complex, highly substituted allyl aryl ethers 2 or 4 were formed
in high yield (58-97%) with good regioselectivity (Table 2 and
3). Herein, we reported a Pd-catalyzed decarboxylative allylic
etherification of cross-conjugated ketoesters via a resonance
stabilized intermediate for preparation of functionalized allyl
aryl ethers, and its potential application to dihydroplicatin B
synthesis.
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Table 1. Optimization of the Pd-Catalyzed RSDcA
Reactiona
O
O
Pd cat.
+
CO2
solvent, temp.
30 min
O
O
1a
2a
entry
Pd (mol %)
solvent
toluene
T (oC)
110
r.t.
yield (%)b
8c
1
2
3
4
5
6
7
8
Pd(PPh3)4 (5)
Pd(dba)2 (5)
Pd(dba)2 (5)
Pd(dba)2 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (1)
toluene
<5d
<5d
<5d
95
THF
r.t.
acetonitrile
toluene
r.t.
Scheme 2. Regioselective Functionalization of Arenes via
Decarboxylative Couplings Approach
r.t.
THF
r.t.
95
(a) Previous work:
R1
acetonitrile
acetonitrile
r.t.
95
<1d
decarboxylative
R2
C-H olefination
r.t.
rearomatization
R1 CO2H
CO2H
Birch
aReaction conditions: 1a, 0.1 mmol in 1.0 mL solvent under
reduction
b
c
argon atmosphere. Isolated yield. 2-Allyl-4-isopropylphenol
and 4-isopropylphenol were isolated as byproducts. dRecovering
of 1a.
R1
1. decarboxylative
-olefination
2. DDQ
R2
(b) This work:
With the optimized reaction conditions in hand, the substrate
scope of the RSDcA reaction shown in Scheme 2B was
investigated. As is shown in Table 2, a series of cross-
conjugated ketoesters 1 were prepared and applied under the
optimized conditions to give substituted allyl aryl ethers 2a−2k
in good to excellent yields. The reaction tolerates a wide range
of substituents at the 1-position of compound 1 including,
methyl, isopropyl, n-hexyl, benzyl, and methylene methyl ester
groups (2a, 2b, 2i, 2j, and 2k). An additional methyl or fluoro
substituent at the 2- or 3-position of the cross-conjugated
ketoester was well tolerated and the reaction furnished tri-
substituted aryl allyl ethers (2c, 2d, 2h, 2i, and 2j) in 70-90%
isolated yields. In addition, highly substituted substrates, 1e and
1g, were compatible with this procedure, providing
corresponding compounds 2e and 2g in good yield. Notably, the
sterically hindered substrate 1f, afforded the corresponding
2,4,6-substituted aryl allyl ether 2f in 92% yield under our
RSDcA reaction conditions.
R2
O
R2
CO2H
allyl
1. Birch
reduction
decarboxylative
O-allylation
O
R1
R1
R1
2. esterification
3. oxidation
O
O 1
3
or (substituted allyl)
allyl
or (substituted allyl)
2
4
Resonance Stabilized Aryl Oxide
R2
O
R2
Pd(II)Ln
Pd(II)Ln
R1
R1
Rearomatization
O
■ RESULTS AND DISCUSSION
We began our investigation of the RSDcA reaction using
starting material 1a in various solvents at elevated or room
temperature. By using 5 mol % of Pd(PPh3)4 in toluene at 110
°C for 1 h, the decarboxylative O-allylation product 2a was
obtained and isolated in 8% yield (Table 1, entry 1). We also
Next, the regioselectivity of the RSDcA reaction was
investigated by varying the allyl substituents of compounds 3,
and the resulting decarboxylative O-allylation products of 4 are
shown in Table 3. The non-fluorinated or fluorinated cross-
isolated
2-allyl-4-isopropylphenol
(48%)
and
4-
isopropylphenol (44%) as byproducts, produced from a Claisen
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conjugated ketone esters with prenyl substituent provided the kinetic product, regenerating the Pd(0) catalyst completing the
1
2
3
4
5
6
7
8
branched allylation products exclusively in good yields (entries
1 and 2). The 1-methylallyl substrate gave branched allylation
products with moderate regioselectivies and yields (entries 3
and 4). 3-alkyl-substituted allyl substrate was also compatible
with this procedure and resulted in 92% yield but with nearly
no regioselectivity (entry 5). The RSDcA reaction of 2-
methylallyl derivatives proceeded smoothly and provided
products in good yields (entries 6 and 7). Notably, cinnamyl
substrate 3h and 1-phenylallyl substrate 3j both gave linear
allylation product 4h exclusively in good yields. However, the
reaction of fluorinated cinnamyl substrate 3i showed poor
regioselectivity and resulted in linear product to branched
product in 1/0.57 ratio. These results suggest that the
regioselectivity of the RSDcA reaction is highly dependent on
the structures of the starting materials, strongly suggesting that
product formation is under kinetic control. This conclusion is
catalytic cycle.
Table 3. Substrate Scope of Allyl Electrophilesa
O
R3 R5
iPr
iPr
R2
O
R6
R2
Pd(PPh3)4 (5 mol %)
CH3CN, rt, 30 min
R4
CO2
+
R4
O
R6
O
3a j
-
4a h
-
R3 R5
9
Entry
1, 2
Substrate
Product
Yield (%)b
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O
iPr
iPr
O
c
4a
, R = H, 70%
c
4b
, R = F, 80%
O
O
3a
3b
, R = H
, R = F
R
R
R
O
O
O
iPr
consistent
with
the
iron-catalyzed
decarboxylative
c
iPr
4c
, R = H, 78%
(l:b = 0.31:1)d
etherification of carbonates reported by Tunge’s group in
3, 4
2009.7d
c
3c
3d
, R = H
, R = F
4d
, R = F, 73%
(l:b = 0.23:1)d
R
O
O
Table 2. Substrate Scope for the RSDcA Reactiona,b
iPr
iPr
O
C3H7
92%
5
R1
(l:b = 0.95:1)d
O
O
C3H7
R1
3e
O
4e
O
R2
Pd(PPh3)4 (5 mol %)
R2
O
CO2
+
CH3CN, rt, 30 min
iPr
iPr
O
O
O
4f
, R = H, 91%
6, 7
8, 9
10
4g
, R = F, 92%
O
O
1a k
-
2a k
-
R
3f
3g
, R = H
, R = F
R
R
O
iPr
iPr
iPr
O
Ph
Ph
iPr
iPr
iPr
O
Ph
4h
, R = H, 97%
, R = F, 95%
(l:b = 1:0.57)d
4i
3h
, R = H
, R = F
R
3i
O
O
O
O
O
2c
, 90%
2d
, 92%
2a
2b
, 89%
, 94%
O
Ph
iPr
O
iPr
iPr
iPr
iPr
90%
O
3j
4h
O
F
aReaction was performed with 3 (0.1-0.2 mmol), and 5 mol % of
Pd(PPh3)4 in 1 mL of acetonitrile. Isolated yields. 5 mol % of
Pd(dba)2 and 10 mol % of PPh3 was used. dRatio was determined
by 1H NMR, l: linear, b: branched.
O
O
O
O
b
c
2e
2f
2g
2h
, 86%
, 69%
, 92%
, 77%
O
Ph
n-Hex
Scheme 3. Proposed Mechanism for the RSDcA Reaction
O
R2
O
R2
O
O
R1
R3
O
R1
O
R3
O
Pd(0)Ln
2i
2j
2k
, 87%
, 93%
, 81%
4
3
O
aReaction was performed with 1 (0.2-0.5 mmol), and 5 mol % of
Coordination
& Ionization
O-allylation
Pd(PPh3)4 in 1 mL of acetonitrile. bIsolated yields.
Based on our experiment results, we propose a plausible
mechanism for the RSDcA (Scheme 3). The reaction substrate
3 is first ionized by the Pd(0) catalyst to afford a Pd−−allyl
species and carboxylate ion pair A. Next, the decarboxylation
of carboxylate occurs to give the cyclohexadienone anion and
Pd−−allyl species ion pair B. The cyclohexadienone anion
then rearomatizatizes generating a stable aryloxide intermediate
C. Finally, the O-allylation of aryloxide occurs with Pd−−allyl
species to afford a branched or linear allyl aryl ether 4 as a
R2
R2
O
R2
Pd(II)Ln
R3
Pd(II)Ln
R3
O
R1
R1
R1
Pd(II)Ln
R3
O
O
Rearomatization
O
C
B
A
Decarboxylation
CO2
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million (ppm) downfield from tetramethylsilane (TMS) and are
The Claisen rearrangement of allyl aryl ethers is a useful
method in natural product synthesis.2 Hence, we investigate the
O-allylation products of 1a, 1h, 1k, and 3f under microwave
assisted Claisen rearrangement (Scheme 4A). The product
yields of this reaction towards highly substituted phenols are
considerably high (5a−d, 66-82%). Furthermore, we utilized
this protocol for the synthesis of dihydroplicatin B derivative
(Scheme 4B, 5e), whereas its methyl ester analogues have
antimutagenic activity.17 Satisfyingly, this synthetic strategy
achieved dihydroplicatin B derivative in about 30% overall
yield in five steps starting from commercially available benzoic
acid (see details in the SI).
1
2
3
4
5
6
7
8
referenced to residual protium in the NMR solvent (CDCl3, δ 7.26).
Chemical shifts for 13C NMR spectrum are reported in ppm
downfield from TMS and were referenced to the carbon resonances
of the solvent (CDCl3, δ 77.0 ppm). Data are represented as
follows: chemical shift, multiplicity (s= singlet, d= doublet, t=
triplet, q= quartet, p= pentet, m = multiplet), coupling constants in
Hertz (Hz), integration. Spectrum were calibrated related to the
solvent residual proton and carbon, chemical shift: CDCl3 (δ = 7.26
for 1H NMR and δ = 77.0 for 13C NMR). Thin-layer
chromatography (TLC) was performed using Merck silica gel 60
F-254 plates, the detection of compounds was performed using
ultra violet (UV) light or immerse in a solution of potassium
permanganate (1.5 g of KMnO4, 5 g NaHCO3, and 400 mL H2O)
followed by heating the TLC plates. Flash column chromatography
was performed using Merck silica gel 60 (40-63 μm) with an
applied pressure of 0.5 bar. High Resolution Mass (HRMS)
Spectra were obtained on a Finnigan/Thermo Quest MAT 95XL
(EI), Thermo Scientific TSQ Quantum Triple Quadrupole (ESI and
APCI), JEOL JMS-700 (FAB). Melting points were obtained using
a Fargo MP-2D capillary melting point apparatus. The microwave
assisted reactions were performed using a CEM discover SP
microwave synthesis system with a sealed reaction vessels, the
reaction temperature was monitored through external surface
sensor.
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Scheme 4. (A) RSDcA and Microwave Assistance Claisen
Rearrangement. (B) Approach to Dihydroplicatin B
Derivative (5e)a
A.
O
R1
R1
O
1) Pd(PPh3)4 (5 mol %)
R2
R2
2) DMF, W, 230 °C
20 min
OH
O
1a 1h 1k 3f
5a 5d
-
,
,
,
O
O
General procedure of Birch reductive alkylation. To a 250
mL round bottle benzoic acid/benzoic acid derivatives (1 equiv.)
was added. The bottle was vacuumed and filled with Argon (Ar)
gas. Then started to condense liquid ammonia at -78 °C. Lithium
metal (Li) (2.5 equiv.) was added in to the solution, the color of
solution became dark blue after the addition of lithium was
finished. After 1 hour, the alkyl halide (3 equiv.) was added in to
the solution and reaction for 1 hour. The liquid ammonia was
evaporated overnight, and the residue was dissolved in 200 mL of
water. Concentrated hydrochloric acid (HCl) was added until pH 1-
2. After the addition of HCl, solution was extracted with diethyl
ether. The organic phase was washed with 10% NaHCO3(aq) and
saturated NaCl(aq). The organic phase was dried over MgSO4 and
concentrated by rotary evaporator. Compound 1aa-1ka,14 or 3ka
were purified by recrystallization or column chromatography (see
chemical structures in the SI).
General procedure of the allylation of cyclohexadiene
carboxylic acids. Allyl bromide (1.5 equiv.) was added into a
solution contain K2CO3 (1.2 equiv.) and compounds 1aa-1ka in dry
dimethylformamide (DMF) under Ar gas at room temperature. The
solution was then heated up to 75 °C for 30 minutes. After 30
minutes, the reaction mixture was cool to room temperature by ice-
water bath. Water was added into the reaction solution, then
extracted with diethyl ether. Organic phase was washed with 10%
F
OH
OH
5b
OH
5c
OH
b
b
b
b
5a
5d
, 68%
, 72%
, 66%
, 82%
B.
O
O
O
O
1) Pd(dba)2 (5 mol %)
PPh3 (10 mol %)
O
O
2) DMF, W, 230 °C
20 min
O
OH
5e
b
3k
, 58%
Dihydroplicatin B derivative
aStep 2 were performed on 0.23-0.63 mmol reaction scale in 1 mL
of DMF. bCombined yields of two steps.
■ CONCLUSIONS
In conclusion, we have developed a protocol for the synthesis
of versatile allyl aryl ethers from readily available benzoic
acids. This reaction protocol consists of a dearomatization of
benzoic acids by Birch reductive alkylation, and
rearomatization of the alkylated 2,5-cyclohexadienyl ketoesters
by a Pd-catalyzed decarboxylative allylic etherification. The
yields of the RSDcA reaction are generally high and provided
diverse allyl aryl ethers with good regioselectivity. Moreover,
we utilized the RSDcA reaction with a Claisen rearrangement
for the synthesis of dihydroplicatin B derivative. We anticipate
the concept of RSDcA reaction can be further applied on
carbon−carbon or other carbon−heteroaton bond forming
reactions. Indeed, the study of these aforementioned reactions
is currently being investigated in our laboratory.
NaHCO3(aq)
,
saturated NaCl(aq)
,
and dried over MgSO4.
Concentrated by rotary evaporator to give compounds 1ab-1kb
without further purification. Compounds 1ab-1kb were
synthesized from a modified literature procedure.18
General procedure of the allylation of cyclohexadiene
carboxylic acids to give substituted allyl esters. Oxalyl chloride
(2 equiv.) was added to a solution of compound 1aa or 1ha (1
equiv.) in dry DCM under Ar gas. The solution was put into ice-
water bath, then added few drops of DMF. The reaction mixture
then started to bubble. After 1 hour, the solvent was removed under
vacuum. Yellow-white solid was obtained. Dry DCM was added
into the reaction container under Ar gas. A solution contained
substituted allyl alcohol (1.1 equiv.), pyridine (1.2 equiv.), DMAP
(catalytic amount) in DCM was added and the reaction was carried
out overnight under Ar gas. 10% HCl was added to the reaction
mixture and extracted with diethyl ether. The organic phase was
washed by 10% NaHCO3(aq), saturated NaCl(aq), and dried over
MgSO4. Concentrated by rotary evaporator to give compounds
■ EXPERIMENTAL SECTION
General information. All solvents and reagents were purified
according to standard procedures or were used as received from
Aldrich, Fluka, Acros, or Lancaster. 1H NMR (300 MHz) spectrum,
13C{1H} NMR (75 MHz) spectrum, and 19F NMR (282 MHz)
spectrum were obtained on a Varian-Mercury-300 spectrometer.
1
Chemical shifts for H NMR spectrum are reported in parts per
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3ab-3jb with further purification by column chromatography.
25.8. HRMS (ESI) calculated for C11H14NaO2 ([M+Na]+):
201.0891. Found: 201.0886.
1
Compounds 3ab-3jb were synthesized from a modified literature
procedure.19
Allyl
1-isopropyl-2-methylcyclohexa-2,5-dienecarboxylate
2
3
4
5
6
7
8
9
General procedure of the allylic oxidation of cyclohexadiene
esters. Method A, cooper iodide (0.03 equiv.) was added into the
solution contain compound 1ab-1kb or 3ab-3gb or 3kb (1 equiv.)
in acetonitrile. tert-Butyl hydroperoxide (TBHP) (7 equiv.) was
added into the solution. The reaction mixture was reflux overnight.
10% of Na2S2O3 was added to the solution after cooling down to
room temperature. The solution was extracted with diethyl ether.
Organic phase was washed by 10% NaHCO3(aq) and saturated
NaCl(aq), then dried over MgSO4. The solvent was removed by
rotary evaporator to give compounds 1a-1k or 3a-3g or 3k with
further purification by column chromatography. Compounds 1a-1k
or 3a-3g or 3k were synthesized from a modified literature
procedure.20
General procedure of the allylic oxidation of cyclohexadiene
esters. Method B, 3,5-dimethylpyrazole (3,5-DMP) (1 equiv.) and
chromium trioxide (CrO3) (1 equiv.) was added into dry DCM at
−20 °C and stirred at −20 °C for 10 minutes. Compound 3eb or
3hb-3jb was added into the solution and stir overnight at room
temperature. The solution was cooled to 0 °C and NaOH(aq) (5 M)
was added. The solution was extracted with diethyl ether. Organic
phase was washed by 10% NaHCO3(aq) and saturated NaCl(aq), then
dried over MgSO4. The solvent was removed by rotary evaporator
to give compounds 3e or 3h-3j with further purification by column
chromatography. Compounds 3e or 3h-3j were synthesized from a
modified literature procedure.21
General procedure of the Pd-catalyzed RSDcA reaction for
allyl aryl ethers synthesis. Compounds 1a-1k or 3a-3k and
Pd(PPh3)4 (5 mol%) or Pd(dba)2 (5 mol%) were added into the
reaction container. Acetonitrile was added into the container under
Ar gas. The reaction was traced by TLC, after 1 hour at room
temperature showed full conversion of the reactant. The mixture
was filtered with celite to give the crude reaction mixture, then
purified by silicagel column chromatography to afford the allyl aryl
ether products2a-2k or 4a-4j.
General procedure of the microwave-assisted Claisen
rearrangement for allyl aryl ethers. Compound 2a, 2h, 2k, 4f,
or 4k was added to reaction vessel contain DMF and magnetic
stirring bar. Followed by microwave-assisted Claisen
rearrangement in a sealed reaction vessel, the solution undergoes
microwave irradiation at 230 °C for 20 minutes. Saturated
NaHCO3(aq) was added to the reaction mixture, then extracted with
diethyl ether. The combined organic phase was washed by
saturated NaCl(aq) and dried over MgSO4. The solvent was removed
through rotary evaporator to give compounds 5a-5e with further
purification by column chromatography. Compounds 5a-5e were
synthesized from a modified literature procedure.22
(1cb). According to general procedure, compound 1ca (500 mg, 2.8
mmol), allyl bromide (0.36 mL, 4.2 mmol), and K2CO3 (459 mg,
3.3 mmol) in dry DMF (10 mL). Compound 1cb was achieved as
1
colorless liquid without further purification (591 mg, 97%). H
NMR (300 MHz, CDCl3): δ 6.01-5.84 (m, 2H), 5.66-5.63 (m, 2H),
5.33-5.26 (m, 1H), 5.22-5.18 (m, 1H) , 4.61-4.58 (m, 2H), 2.68-
2.64 (m, 2H), 2.60-2.46 (m, 1H), 1.70 (s, 3H), 0.91 (d, J = 6.7 Hz,
3H), 0.72 (d, J = 6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 173.4,
132.3, 131.5, 126.3, 124.0, 123.4, 117.7, 65.1, 55.4, 31.4, 26.9,
19.5, 17.8, 17.1. HRMS (EI) calculated for C14H20O2 ([M]+):
220.1463. Found: 220.1461.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Allyl
1-isopropyl-3-methylcyclohexa-2,5-dienecarboxylate
(1db).According to general procedure, compound 1da (500 mg, 2.8
mmol), allyl bromide (0.36 mL, 4.2 mmol), and K2CO3 (459 mg,
3.3 mmol) in dry DMF (10 mL). Compound 1db was achieved as
colorless liquid with further purification by flash column
chromatography (EA/Hexane) (397 mg, 65%).1H NMR (300 MHz,
CDCl3): δ 5.99-5.86 (m, 2H), 5.78-5.73 (m, 1H), 5.46-5.45(m, 1H),
5.35-5.28 (m, 1H), 5.24-5.19 (m, 1H), 4.57-4.60 (m, 2H), 2.52 (s,
2H), 2.16-2.07 (m, 1H), 1.7 (s, 3H), 0.82 (d, J = 3.7 Hz, 3H), 0.79
(d, J = 3.6 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 174.8, 133.7,
132.3, 126.3, 125.2, 120.5, 117.8, 65.1, 53.2, 36.0, 31.3, 23.2, 17.3.
HRMS (EI) calculated for C14H20O2 ([M]+): 220.1463. Found:
220.1470.
Allyl 1-isopropyl-2,3-dimethylcyclohexa-2,5-dienecarboxylate
(1eb). According to general procedure, compound 1ea (500 mg, 2.6
mmol), allyl bromide (0.33 mL, 3.9 mmol), and K2CO3 (426 mg,
3.1 mmol) in dry DMF (10 mL). Compound 1eb was achieved as
colorless liquid with further purification by flash column
chromatography (EA/Hexane) (429 mg, 71%). 1H NMR (300 MHz,
CDCl3): δ 6.02-5.80 (m, 2H), 5.66-5.55 (m, 1H), 5.32-5.13 (m, 2H),
4.58 (d, J = 5.5 Hz, 2H), 2.67-2.43 (m, 3H), 1.68 (s, 3H), 1.62 (s,
3H), 0.91 (d, J = 6.7 Hz, 3H), 0.66 (d, J = 6.9 Hz,3H). 13C NMR
(75 MHz, CDCl3): δ 173.9, 132.4, 128.1, 126.3, 124.1, 123.8,
117.6, 65.0, 56.4, 33.1, 31.9, 19.4, 18.1, 17.3, 13.5. HRMS (EI)
calculated for C15H22O2 ([M]+): 234.1620. Found: 234.1623.
Allyl 1-isopropyl-3,5-dimethylcyclohexa-2,5-dienecarboxylate
(1fb). According to general procedure, compound 1fa (500.0 mg,
2.6 mmol), allyl bromide (0.33 mL, 3.9 mmol), and K2CO3 (426
mg, 3.1 mmol) in dry DMF (10 mL). Compound 1fb was achieved
as colorless liquid without further purification (596 mg, 99%). 1H
NMR (300 MHz, CDCl3): δ 5.99-5.86 (m, 1H), 5.45 (s, 2H), 5.34-
5.19 (m, 2H), 4.58 (d, J = 5.5 Hz, 2H), 2.43 (s, 2H), 2.17-2.03 (m,
1H), 1.76 (s, 6H), 0.78 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz,
CDCl3): δ 175.2, 133.6, 132.4, 120.0, 117.7, 65.0, 54.4, 36.2, 23.0,
17.4. HRMS (EI) calculated for C15H22O2 ([M]+): 234.1620. Found:
234.1627.
Allyl
1-isopropylcyclohexa-2,5-dienecarboxylate
(1ab).
Allyl 1-isopropyl-1,4-dihydronaphthalene-1-carboxylate (1gb).
According to general procedure, compound 1ga (500 mg, 2.3
mmol), allyl bromide (0.30 mL, 3.5 mmol), and K2CO3 (382 mg,
2.8 mmol) in dry DMF (10 mL). Compound 1gb was achieved as
According to general procedure, compound 1aa (670 mg, 4 mmol),
allyl bromide (0.52 mL, 6.0 mmol), and K2CO3 (663 mg, 4.8 mmol)
in dry DMF (10 mL). Compound 1ab was achieved as colorless
1
liquid without further purification (817 mg, 99%). H NMR (300
1
colorless liquid without further purification (565 mg, 95%). H
MHz, CDCl3): δ 6.11-5.87 (m, 3H), 5.85-5.66 (m, 2H), 5.41-5.14
(m, 2H), 4.60 (d, J= 5.6 Hz, 2H), 2.62 (s, 2H), 2.12 (m, 1H), 0.83
(d, J= 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 174.5, 132.2,
126.4, 125.7, 118.0, 65.1, 52.0, 35.8, 26.5, 17.3. HRMS (EI)
calculated for C13H18O2 ([M]+): 206.1307. Found: 206.1305.
Allyl 1-methylcyclohexa-2,5-dienecarboxylate (1bb). According
to general procedure, compound 1ba (600 mg, 4.3 mmol), allyl
bromide (0.56 mL, 6.5 mmol), and K2CO3 (709 mg, 5.2 mmol) in
dry DMF (10 mL). Compound 1bb was achieved as colorless liquid
NMR (300 MHz, CDCl3): δ 7.54-7.51 (m, 1H), 7.21-7.11 (m, 3H),
6.23-6.17 (m, 1H), 5.91-5.78 (m, 2H), 5.23-5.12 (m, 2H), 4.65-4.50
(m, 2H), 3.42-3.39 (m, 2H), 2.79-2.66 (m, 1H), 1.00 (d, J = 6.7 Hz,
3H), 0.54 (d, J = 6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 174.0,
135.2, 134.3, 132.0, 128.3, 126.5, 126.4, 126.3, 123.7, 117.7, 65.4,
54.8, 37.6, 29.7, 18.5, 17.0. HRMS (EI) calculated for C17H20O2
([M]+): 256.1463. Found: 256.1465.
Allyl
3-fluoro-1-isopropylcyclohexa-2,5-dienecarboxylate
1
(1hb). According to general procedure, compound 1ha (600 mg,
3.3 mmol), allyl bromide (0.42 mL, 4.9 mmol), and K2CO3 (540
mg, 3.9 mmol) in dry DMF (10 mL). Compound 1hb was achieved
as colorless liquid without further purification (738 mg, 99%). 1H
without further purification (750 mg, 97%). H NMR (300 MHz,
CDCl3): δ 5.97-5.76 (m, 5H), 5.30 (m, 1H), 5.23-5.19 (m, 1H),
4.59-4.57 (m, 2H) , 2.67-2.64 (m, 2H), 1.35 (s, 3H). 13C NMR (75
MHz, CDCl3): δ 174.8, 132.1, 128.5, 124.5, 117.7, 65.2, 43.8, 27.3,
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The Journal of Organic Chemistry
Page 6 of 13
NMR (300 MHz, CDCl3): δ 5.98-5.71 (m, 3H), 5.38-5.34 (m, 1H),
Allyl
1-isopropyl-2-methyl-4-oxocyclohexa-2,5-
1
2
3
4
5
6
7
8
5.32-5.28 (m, 1H), 5.21-5.26 (m, 1H), 4.61-4.58 (m, 2H), 2.82-2.80
(m, 2H), 2.19-2.10 (m, 1H), 0.83 (d, J = 6.9 Hz, 6H). 13C NMR (75
MHz, CDCl3): δ 173.8, 158.6 (d, J = 255.2 Hz), 131.9, 126.6 (d, J
= 2.8 Hz), 123.7 (d, J = 10.5 Hz), 118.3, 101.6 (d, J = 17.6 Hz),
65.4, 55.0 (d, J = 7.6 Hz),, 35.8, 27.1 (d, J = 26.6 Hz), 17.3. 19F
NMR (282 MHz, CDCl3): δ −102.7 (ddd, J = 17.9, 7.6, 2.8 Hz).
HRMS (EI) calculated for C13H17FO2 ([M]+): 224.1213. Found:
224.1217.
dienecarboxylate (1c). According to general procedure, compound
1cb (500 mg, 2.3 mmol), CuI (14 mg, 0.07 mmol), and TBHP (1.99
mL, 15.9 mmol) in CH3CN (11.35 mL). Purification by flash
column chromatography (EA/ Hexane) to give compound 1c as
1
colorless liquid (268 mg, 50%). H NMR (300 MHz, CDCl3): δ
6.97 (d, J = 10.3 Hz, 1H), 6.46 (d, J = 10.3, 1H), 6.28-6.25 (m, 1H),
5.91-5.78 (m, 1H), 5.31-5.21 (m, 2H), 4.61-4.58 (m, 2H), 2.78-2.69
(m, 1H), 2.01 (s, 3H), 1.12 (d, J = 6.7 Hz, 3H), 0.68 (d, J = 6.9 Hz,
3H). 13C NMR (75 MHz, CDCl3): δ 185.6, 169.5, 156.3, 145.4,
131.1, 130.7, 130.5, 118.9, 66.3, 59.6, 33.7, 19.9, 18.9, 16.4.
HRMS (EI) calculated for C14H18O3 ([M]+): 234.1256. Found:
234.1253.
Allyl 1-hexyl-2-methylcyclohexa-2,5-dienecarboxylate (1ib).
According to general procedure, compound 1ia (500 mg, 2.3
mmol), allyl bromide (0.30 mL, 3.4 mmol), and K2CO3 (373 mg,
2.7 mmol) in dry DMF (10 mL). Compound 1ib was achieved as
colorless liquid with further purification by flash column
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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29
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31
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34
35
36
37
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39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Allyl
1-isopropyl-3-methyl-4-oxocyclohexa-2,5-
1
chromatography (EA/ Hexane) (354 mg, 60%). H NMR (300
dienecarboxylate (1d). According to general procedure, compound
1db (364 mg, 1.8 mmol), CuI (10 mg, 0.05 mmol), and TBHP (1.58
mL, 12.6 mmol) in CH3CN (9.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 1d as colorless
MHz, CDCl3) δ 6.05-5.76 (m, 2H), 5.72-5.58 (m, 1H), 5.45 (d, J=
9.9 Hz, 1H), 5.35-5.13 (m, 2H), 4.67-4.47 (m, 2H), 2.80-2.55 (m,
2H), 1.98-1.80 (m, 1H), 1.56-1.75 (m, 4H), 1.36-1.20 (m, 6H),
1.18-0.93 (m, 2H), 0.92-0.76 (m, 3H). 13C NMR (75 MHz, CDCl3)
δ 174.2, 132.2, 131.1, 127.7, 126.0, 123.1, 117.6, 65.2, 51.7, 34.5,
31.7, 29.5, 26.9, 23.8, 22.6, 19.7, 14.0. HRMS (EI) calculated for
C17H26O2 ([M]+): 262.1933. Found: 262.1923.
1
liquid (219 mg, 52%). H NMR (300 MHz, CDCl3): δ 7.04-6.98
(m, 1H), 6.82-6.79 (m, 1H), 6.41-6.36 (m, 1H), 5.97-5.82 (m, 1H),
5.36-5.23 (m, 2H), 4.65-4.61 (m, 2H), 2.50-2.39 (m, 1H), 1.95-1.93
(m, 3H), 0.93-0.87 (m, 6H). 13C NMR (75 MHz, CDCl3): δ 185.9,
170.5, 146.5, 142.3, 137.4, 131.3, 130.6, 119.0, 66.2, 56.4, 36.6,
17.7, 17.6, 16.1. HRMS (EI) calculated for C14H18O3 ([M]+):
234.1256. Found: 234.1263.
Allyl 1-benzyl-2-methylcyclohexa-2,5-dienecarboxylate (1jb).
According to general procedure, compound 1ja (500 mg, 2.2
mmol), allyl bromide (0.27 mL, 3.3 mmol), and K2CO3 (364 mg,
2.64 mmol) in dry DMF (10 mL). Compound 1jb was achieved
Allyl
1-isopropyl-2,3-dimethyl-4-oxocyclohexa-2,5-
1
without further purification (550 mg, 93%). H NMR (300 MHz,
dienecarboxylate (1e). According to general procedure, compound
1eb (388 mg, 1.7 mmol), CuI (10 mg, 0.05 mmol), and TBHP (1.49
mL, 11.9 mmol) in CH3CN (9.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 1e as colorless
liquid (236 mg, 56%). 1H NMR (300 MHz, CDCl3): δ 6.90 (d, J =
10.2 Hz, 1H), 6.49 (d, J = 10.2 Hz, 1H), 5.91-5.76 (m, 1H), 5.27-
5.19 (m, 2H), 4.6-4.54 (m, 2H), 2.81-2.67 (m, 1H), 1.93 (d, J = 9.3,
6H), 1.11 (d, J = 6.8 Hz, 3H), 0.60 (d, J = 6.9 Hz, 3H). 13C NMR
(75 MHz, CDCl3): δ 185.0, 170.0, 149.7, 144.3, 135.0, 131.3,
130.4, 118.6, 66.0, 59.5, 33.4, 19.1, 16.6, 15.9, 11.2. HRMS (EI)
calculated for C15H20O3 ([M]+): 248.1412. Found: 248.1417.
CDCl3) δ 7.33-7.02 (m, 5H), 6.02-5.85 (m, 1H), 5.84-5.71 (m, 1H),
5.68-5.47 (m, 2H), 5.39-5.15 (m, 2H), 4.77-4.55 (m, 2H), 3.28-3.02
(m, 2H), 2.57-2.37 (m, 1H), 2.13-1.93 (m, 1H), 1.92-1.72 (m, 3H).
13C NMR (75 MHz, CDCl3) δ 173.8, 137.2, 132.1, 130.5, 130.3,
127.3, 126.9, 126.3, 126.0, 124.2, 118.1, 77.4, 77.0, 76.5, 65.5,
53.0, 40.5, 26.5, 20.0. HRMS (EI) calculated for C18H20O2 ([M]+):
268.1463. Found: 268.1469.
Allyl 1-(2-methoxy-2-oxoethyl)cyclohexa-2,5-dienecarboxylate
(1kb).According to general procedure, compound 1ka (500 mg, 2.6
mmol), allyl bromide (0.33 mL, 3.8 mmol), and K2CO3 (422 mg,
3.1 mmol) in dry DMF (10 mL). Compound 1kb was achieved as
Allyl
1-isopropyl-3,5-dimethyl-4-oxocyclohexa-2,5-
1
colorless liquid without further purification (524 mg, 87%). H
dienecarboxylate (1f). According to general procedure, compound
1fb (596 mg, 2.5 mmol), CuI (15 mg, 0.076 mmol), and TBHP
(2.23 mL, 17.8 mmol) in CH3CN (10.00 mL). Purification by flash
column chromatography (EA/ Hexane) to give compound 1f as
NMR (300 MHz, CDCl3): δ 5.97- 5.80 (m, 5H), 5.35-5.28 (m, 1H),
5.24-5.19 (m, 1H), 4.63-4.61 (m, 2H), 3.65 (s, 3H), 2.76 (s, 2H),
2.70-2.66 (m, 2H). 13C NMR (75 MHz, CDCl3): δ 173.1, 170.8,
132.0, 126.4, 126.2, 117.8, 65.7, 51.6, 51.6, 45.7, 44.2, 26.0.
HRMS (EI) calculated for C13H16O4 ([M]+): 236.1044. Found:
236.1052.
Allyl 1-isopropyl-4-oxocyclohexa-2,5-dienecarboxylate (1a).
According to general procedure, compound 1ab (2.1 g, 10.2
mmol), CuI (59 mg, 0.31 mmol), and TBHP (9.87 mL, 71.7 mmol)
in CH3CN (35 mL). Purification by flash column chromatography
(EA/ Hexane) to give compound 1a as colorless liquid (1.3 g, 56%).
1H NMR (300 MHz, CDCl3): δ 7.07-7.04 (d, 2H), 6.43-6.39 (d,
2H), 5.97-5.84 (m, 1H), 5.36-5.26 (m, 2H), 4.66-4.63 (m, 2H),
2.53-2.44 (m, 1H), 0.93 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz,
CDCl3): δ 185.2, 170.0, 147.0, 130.9, 119.3, 109.9, 66.4, 56.5, 36.6,
17.6. HRMS (EI) calculated for C13H16O3 ([M]+): 220.1099. Found:
220.1097.
Allyl 1-methyl-4-oxocyclohexa-2,5-dienecarboxylate (1b).
According to general procedure, compound 1bb (831 mg, 4.7
mmol), CuI (27 mg, 0.14 mmol), and TBHP (3.30 mL, 32.6 mmol)
in CH3CN (23.3 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 1b as colorless
liquid (480 mg, 54%). 1H NMR (300 MHz, CDCl3): δ 7.06 (d, J =
10.2 Hz, 2H), 6.31 (d, J = 10.4 Hz, 2H), 5.95-5.82 (m, 1H), 5.33-
5.24 (m, 2H), 4.64-4.61 (m, 2H), 1.57 (s, 3H). 13C NMR (75 MHz,
CDCl3): δ 184.9, 170.3, 148.8, 131.1, 129.0, 119.0, 66.5, 48.2, 24.8.
HRMS (EI) calculated for C11H12O3 ([M]+): 192.0786. Found:
192.0784.
1
colorless liquid (334 mg, 53%). H NMR (300 MHz, CDCl3): δ
6.79 (s, 2H), 5.98-5.85 (m, 1H), 5.35-5.25 (m, 2H), 4.64-4.62 (m,
2H), 2.47-2.38 (m, 1H), 1.95 (s, 6H), 0.88 (d, J = 6.9 Hz, 6H). 13
C
NMR (75 MHz, CDCl3): δ 186.5, 171.1, 141.9, 137.0, 131.5, 118.9,
66.1, 55.8, 36.6, 29.6, 17.7, 16.3. HRMS (EI) calculated for
C15H20O3 ([M]+): 248.1412. Found: 248.1408.
Allyl 1-isopropyl-4-oxo-1,4-dihydronaphthalene-1-carboxylate
(1g). According to general procedure, compound 1gb (566 mg, 2.2
mmol), CuI (13 mg, 0.066 mmol), and TBHP (1.93 mL, 15.4
mmol) in CH3CN (10.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 1g as colorless
liquid (439 mg, 74%). 1H NMR (300 MHz, CDCl3): δ 8.19 (d, J =
7.8 Hz, 1H), 7.80 (d, J = 8.1 Hz, 1H), 7.62-7.56 (m, 1H), 7.49-7.41
(m, 1H), 7.14 (d, J = 10.5 Hz, 1H), 6.68 (d, J = 10.5 Hz, 1H), 5.87-
5.74 (m, 1H), 5.22-5.14 (m, 2H), 4.67-4.50 (m, 2H), 2.98-2.86 (m,
1H), 1.16 (d, J = 6.8 Hz, 3H), 0.46 (d, J = 6.9 Hz, 3H). 13C NMR
(75 MHz, CDCl3): δ 184.2, 171.4, 145.0, 141.5, 132.9, 132.0,
131.2, 130.5, 127.8, 126.6, 126.4, 118.6, 66.2, 56.3, 38.3, 19.3,
16.5. HRMS (EI) calculated for C17H18O3 ([M]+): 270.1256. Found:
270.1257.
Allyl
3-fluoro-1-isopropyl-4-oxocyclohexa-2,5-
dienecarboxylate (1h). According to general procedure, compound
1hb (738 mg, 3.3 mmol), CuI (19 mg, 0.099 mmol), and TBHP
(2.88 mL, 23.0 mmol) in CH3CN (15.00 mL). Purification by flash
column chromatography (EA/ Hexane) to give compound 1h as
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The Journal of Organic Chemistry
1
colorless liquid (433 mg, 55%). H NMR (300 MHz, CDCl3): δ
7.07 (d, J = 10.1, 1H), 6.61 (d, J = 13.3, 1H), 6.48-6.40 (m, 1H),
5.96-5.84 (m, 1H), 5.37-5.28 (m, 2H), 4.68-4.63 (m, 2H), 2.59-2.47
(m, 1H), 0.95 (d, J = 13.9 Hz, 6H). 13C NMR (75 MHz, CDCl3):
δ177.9 (d, J = 21.7 Hz), 169.4, 154.8 (d, J = 264.5 Hz), 148.1 (d, J
= 2.3 Hz), 130.7 (d, J= 44.25 Hz), 122.5 (d, J = 15.4 Hz), 119.6,
66.8, 57.9 (d, J = 5.5 Hz), 36.9, 17.7 (d, J = 25.0 Hz). 19F NMR
(282 MHz, CDCl3): δ −126.90 (dt, J = 13.4, 7.8 Hz). HRMS (FAB)
calculated for C13H15FO3 ([M]+): 238.1005. Found: 238.1003.
5.85-5.70 (m, 1H), 5.36-5.30 (m, 2H), 4.58 (d, J = 7.0 Hz, 2H), 2.80
(s, 2H), 2.17-2.07 (m, 1H), 1.72 (d, J = 14.5 Hz, 6H), 0.81 (d, J =
6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 174.2, 158.4 (d, J =
255.0 Hz), 139.1, 126.7 (d, J = 2.7 Hz), 123.5 (d, J = 10.8 Hz),
118.4, 101.8 (d, J = 17.4 Hz), 61.8, 54.9 (d, J = 7.5 Hz), 35.8, 29.6,
27.1 (d, J = 26.6 Hz), 26.9, 25.7, 18.0, 17.3 (d, J = 5.4 Hz). 19F
NMR (282 MHz, CDCl3): δ −102.92 (ddd, J = 17.7, 7.7, 3.1 Hz).
HRMS (EI) calculated for C15H21FO2 ([M]+): 252.1526. Found:
252.1530.
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4
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6
7
8
9
Allyl
1-hexyl-2-methyl-4-oxocyclohexa-2,5-dienecarboxylate
But-3-en-2-yl
1-isopropylcyclohexa-2,5-diene-1-carboxylate
(1i). According to general procedure, compound 1ib (300 mg, 1.1
mmol), CuI (7 mg, 0.034 mmol), and TBHP (1.00 mL, 8.0 mmol)
in CH3CN (5.0 mL). Purification by flash column chromatography
(EA/ Hexane) to give compound 1i as colorless liquid (194 mg,
(3cb).According to general procedure, compound 1aa (500 mg, 3.0
mmol), oxalyl chloride (0.6 mL, 6.0 mmol), DMF (catalytic
amount), 3-Buten-2-ol (0.28 mL, 3.3 mmol), pyridine (0.29 mL,
3.6 mmol), and DMAP (catalytic amount) in dry DCM (20 mL).
Purification by flash column chromatography (DCM/ Hexane) to
give compound 3cb as colorless liquid (271 mg, 41%). 1H NMR
(300 MHz, CDCl3): δ 5.94-5.73 (m, 5H), 5.40-5.32 (m, 1H), 5.28-
5.21 (m, 1H), 5.14-5.10 (m, 1H), 2.64-2.59 (m, 2H), 2.17-2.07 (m,
1H), 1.31 (d, J = 6.5 Hz, 3H), 0.83 (d, J = 6.9 Hz, 6H). 13C NMR
(75 MHz, CDCl3): δ 174.0, 137.6, 126.3, 125.8, 115.6, 70.9, 51.9,
35.7, 26.5, 19.8, 17.3. HRMS (EI) calculated for C14H20O2 ([M]+):
220.1463. Found: 220.1466.
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1
62%). H NMR (300 MHz, CDCl3): δ 6.74 (d, J = 10.0 Hz, 1H),
6.38 (d, J = 10.0, 1H), 6.29-6.25 (m, 1H), 5.90-5.77 (m, 1H), 5.30-
5.21 (m, 2H), 4.60-4.56 (m, 2H), 2.17-1.93 (m, 5H), 1.31-1.16 (m,
8H), 0.87-0.83 (m, 3H). 13C NMR (75 MHz, CDCl3): δ 186.1,
169.9, 156.4, 148.0, 131.1, 130.4, 130.1, 119.0, 66.4, 56.0, 34.4,
31.4, 29.1, 23.1, 22.5, 20.2, 13.9. HRMS (EI) calculated for
C17H24O3 ([M]+): 276.1725. Found: 276.1730.
Allyl 1-benzyl-2-methyl-4-oxocyclohexa-2,5-dienecarboxylate
(1j). According to general procedure, compound 1jb (400 mg, 1.5
mmol), CuI (9 mg, 0.045 mmol), and TBHP (1.31 mL, 10.5 mmol)
in CH3CN (5.0 mL). Purification by flash column chromatography
(EA/ Hexane) to give compound 1j as colorless liquid (259 mg,
61%). 1H NMR (300 MHz, CDCl3): δ 7.20-7.16 (m, 3H), 7.04-7.01
(m, 2H), 6.82 (d, J = 10.0 Hz, 1H), 6.25 (d, J = 10.0 Hz, 1H), 6.20-
6.10 (m, 1H), 5.92-5.79 (m, 1H), 5.32-5.22 (m, 2H), 4.69-4.56 (m,
2H), 3.50 (d, J = 13.9 Hz, 1H), 3.28 (d, J = 13.9 Hz, 1H), 2.13 (d,
J = 1.4 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 185.5, 169.6, 155.2,
147.4, 134.4, 130.9, 130.4, 130.0, 129.7, 128.0, 127.2, 119.2, 66.6,
56.8, 41.1, 20.6. HRMS (EI) calculated for C18H18O3 ([M]+):
282.1256. Found: 282.1252.
But-3-en-2-yl
3-fluoro-1-isopropylcyclohexa-2,5-diene-1-
carboxylate (3db). According to general procedure, compound 1ha
(500 mg, 2.7 mmol), oxalyl chloride (0.47 mL, 5.4 mmol), DMF
(catalytic amount), 3-Buten-2-ol (0.26 mL, 3.0 mmol), pyridine
(0.26 mL, 3.3 mmol), and DMAP (catalytic amount) in dry DCM
(20 mL). Purification by flash column chromatography
(DCM/Hexane) to give compound 3db as colorless liquid (336 mg,
52%). 1H NMR (300 MHz, CDCl3): δ 5.89-5.70 (m, 3H), 5.37-5.11
(m, 4H) 2.80 (s, 2H) 2.19-2.09 (m, 1H), 1.31 (d, J = 6.5 Hz, 3H),
0.83 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 173.3,
158.5 (d, J = 254.9 Hz), 137.4, 126.6, 123.6 (d, J = 10.6 Hz), 115.9,
101.7 (d, J = 18.0 Hz), 71.4, 55.1, 35.7, 27.1 (d, J = 26.6 Hz), 19.8,
17.3 (d, J = 6.0 Hz). 19F NMR (282 MHz, CDCl3): δ −102.86 (dd,
J = 17.9, 7.5 Hz). HRMS (EI) calculated for C14H19FO2 ([M]+):
238.1369. Found: 238.1362.
(E)-Hex-2-en-1-yl 1-isopropylcyclohexa-2,5-dienecarboxylate
(3eb). According to general procedure, compound 1aa (1.00 g, 6.0
mmol), oxalyl chloride (0.75 mL, 9.0 mmol), DMF (catalytic
amount), (E)-hex-2-en-1-ol (0.79 mL, 6.6 mmol), pyridine (0.58
mL, 7.2 mmol), and DMAP (catalytic amount) in dry DCM (20
mL). Purification by flash column chromatography (EA/ Hexane)
to give compound 3eb as colorless liquid (1.17 g, 79%). 1H NMR
(300 MHz, CDCl3) δ 5.94-5.89 (m, 2H), 5.78-5.71 (m, 2H), 5.60-
5.51 (m, 1H), 4.54 (d, J = 6.3 Hz, 2H), 2.64-2.60 (m, 2H), 2.17-
1.98 (m, 3H), 1.46-1.34 (m, 2H), 0.91-0.86 (m, 4H), 0.82 (d, J =
6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 174.7, 136.2, 126.3,
125.9, 123.9, 65.4, 51.9, 35.8, 34.3, 26.5, 22.0, 17.3, 13.6. HRMS
(ESI) calculated for C16H24NaO2 ([M+Na]+): 271.1669. Found:
271.1669.
Allyl
1-(2-methoxy-2-oxoethyl)-4-oxocyclohexa-2,5-
dienecarboxylate (1k). According to general procedure, compound
1kb (523 mg, 2.2 mmol), CuI (13 mg, 0.066 mmol), and TBHP
(1.94 mL, 15.5 mmol) in CH3CN (10.0 mL). Purification by flash
column chromatography (EA/ Hexane) to give compound 1k as
1
colorless liquid (360 mg, 65%). H NMR (300 MHz, CDCl3): δ
7.11-7.05 (m, 2H), 6.41-6.36 (m, 2H), 5.94-5.81 (m, 1H), 5.34-5.23
(m, 2H), 4.65-4.63 (m, 2H), 3.70 (s, 3H), 2.89 (s, 2H). 13C NMR
(75 MHz, CDCl3): δ 184.6, 169.7, 169.1, 146.1, 131.0, 130.5,
119.0, 52.2, 49.5, 41.3. HRMS (EI) calculated for C13H14O5 ([M]+):
250.0841. Found: 250.0848.
3-Methylbut-2-en-1-yl
1-isopropylcyclohexa-2,5-diene-1-
carboxylate (3ab). According to general procedure, compound 1aa
(500 mg, 3.0 mmol), oxalyl chloride (0.6 mL, 6.0 mmol), DMF
(catalytic amount), 3-Methyl-2-buten-1-ol (0.33 mL, 3.3 mmol),
pyridine (0.29 mL, 3.6 mmol), and DMAP (catalytic amount) in
dry DCM (20 mL). Purification by flash column chromatography
(DCM/ Hexane) to give compound 3ab as colorless liquid (429 mg,
61%). 1H NMR (300 MHz, CDCl3): δ 5.94-5.88 (m, 2H), 5.77-5.73
(m, 2H), 5.35-5.31 (m, 1H), 4.58 (d, J = 7.1 Hz, 2H), 2.64-2.59 (m,
2H), 2.16-2.03 (m, 1H), 1.72 (d, J = 14.0 Hz, 6H), 0.82 (d, J = 6.9
Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 174.9, 169.8, 138.7, 126.2,
125.9, 118.7, 61.6, 51.9, 35.8, 26.5, 25.7, 18.0, 17.3. HRMS
(APCI) calculated for C15H23O2 ([M]+): 235.1693. Found:
235.1698.
2-Methylallyl
1-isopropylcyclohexa-2,5-diene-1-carboxylate
(3fb). According to general procedure, compound 1aa (1.0 g, 6.0
mmol), oxalyl chloride (0.60 mL, 9.0 mmol), DMF (catalytic
amount), 2-Methyl-2-propen-1-ol (0.56 mL, 6.6 mmol), pyridine
(0.58 mL, 7.2 mmol), and DMAP (catalytic amount) in dry DCM
(20 mL). Purification by flash column chromatography (DCM/
Hexane) to give compound 3fb as colorless liquid (755 mg, 57%).
1H NMR (300 MHz, CDCl3): δ 5.96-5.79 (m, 2H), 5.79-5.74 (m,
2H), 4.99-4.91 (m, 2H), 4.51 (s, 2H), 2.65-2.61 (m, 2H), 2.18-2.09
(m, 1H), 1.76-1.75 (m, 3H), 0.84 (d, J = 6.9 Hz, 6H). 13C NMR (75
MHz, CDCl3): δ 174.4, 139.9, 126.4, 125.7, 112.7, 67.7, 52.1, 35.7,
26.5, 19.5, 17.3. HRMS (EI) calculated for C14H20O2 ([M]+):
220.1463. Found: 220.1467.
3-Methylbut-2-en-1-yl
3-fluoro-1-isopropylcyclohexa-2,5-
diene-1-carboxylate (3bb). According to general procedure,
compound 1ha (500 mg, 2.7 mmol), oxalyl chloride (0.47 mL, 5.4
mmol), DMF (catalytic amount), 3-Methyl-2-buten-1-ol (0.27 mL,
2.7 mmol), pyridine (0.24 mL, 3.0 mmol), and DMAP (catalytic
amount) in dry DCM (20 mL). Purification by flash column
chromatography (DCM/ Hexane) to give compound 3bb as
2-Methylallyl
3-fluoro-1-isopropylcyclohexa-2,5-diene-1-
carboxylate (3gb). According to general procedure, compound 1ha
(1.0 g, 5.4 mmol), oxalyl chloride (0.93 mL, 10.9 mmol), DMF
1
colorless liquid (362 mg, 53%). H NMR (300 MHz, CDCl3): δ
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 13
(catalytic amount), 2-Methyl-2-propen-1-ol (0.51 mL, 6.0 mmol),
3-Methylbut-2-en-1-yl
3-fluoro-1-isopropyl-4-oxocyclohexa-
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3
4
5
6
7
8
pyridine (0.52 mL, 6.5 mmol), and DMAP (catalytic amount) in
dry DCM (20 mL). Purification by flash column chromatography
(DCM/ Hexane) to give compound 3gb as colorless liquid (740 mg,
57%). 1H NMR (300 MHz, CDCl3): δ 5.87-5.71 (m, 2H), 5.34 (d,
J = 18.1 Hz, 1H), 4.95 (d, J = 15.9 Hz, 2H), 4.51 (s, 2H), 2.81 (s,
2,5-diene-1-carboxylate (3b). According to general procedure,
compound 3bb (300 mg, 1.2 mmol), CuI (7 mg, 0.036 mmol), and
TBHP (1.01 mL, 8.4 mmol) in CH3CN (5.00 mL). Purification by
flash column chromatography (EA/ Hexane) to give compound 3b
as colorless liquid (166 mg, 52%). 1H NMR (300 MHz, CDCl3): δ
7.06 (d, J = 10.2 Hz, 1H), 6.62-6.57 (d, J = 13.4 Hz, 1H), 6.42 (d,
J = 10.1 Hz, 1H), 5.35-5.29 (m, 1H), 4.65 (d, J = 7.2 Hz, 2H), 2.56-
2.42 (m, 1H), 1.74 (d, J = 15.4 Hz, 6H), 0.95 (d, J = 6.9 Hz, 3H),
0.91 (d, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 177.9 (d, J
= 21.8 Hz), 169.7, 154.7 (d, J = 264.0 Hz), 148.4, 140.6, 130.2,
122.8 (d, J = 15.4 Hz), 117.4, 63.1, 57.9 (d, J = 5.3 Hz), 25.7, 18.0,
17.6 (d, J = 23.7 Hz). 19F NMR (282 MHz, CDCl3): −127.18 (dd,
J= 14.0, 7.0 Hz). HRMS (EI) calculated for C15H19FO3 ([M]+):
266.1318. Found: 266.1320.
2H), 2.23-2.09 (m, 1H), 1.75 (s, 3H), 0.84 (d, J = 6.9 Hz, 6H). 13
C
NMR (75 MHz, CDCl3): δ 173.8, 158.6 (d, J = 255.3 Hz), 139.7,
126.6, 123.7 (d, J = 10.6 Hz), 113.0, 101.6 (d, J = 19.6 Hz), 68.0,
55.1 (d, J = 7.5 Hz), 35.7, 27.1 (d, J = 26.7 Hz), 19.5, 17.4 (d, J =
3.4 Hz). 19F NMR (282 MHz, CDCl3): δ −102.70 (ddd, J = 17.9,
7.6, 2.7 Hz). HRMS (EI) calculated for C14H19FO2 ([M]+):
238.1369. Found: 238.1364.
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Cinnamyl 1-isopropylcyclohexa-2,5-dienecarboxylate (3hb).
According to general procedure, compound 1aa (0.97 g, 5.8 mmol),
oxalyl chloride (0.75 mL, 8.7 mmol), DMF (catalytic amount), (E)-
3-phenylprop-2-en-1-ol (0.82 mL, 6.4 mmol), pyridine (0.56 mL,
7.0 mmol), and DMAP (catalytic amount) in dry DCM (20 mL).
Purification by flash column chromatography (EA/ Hexane) to give
But-3-en-2-yl
1-isopropyl-4-oxocyclohexa-2,5-diene-1-
carboxylate (3c). According to general procedure, compound 3cb
(225 mg, 1.0 mmol), CuI (6 mg, 0.031 mmol), and TBHP (0.88 mL,
7.1 mmol) in CH3CN (10.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3c as colorless
1
compound 3hb as colorless liquid (1.3 g, 79%). H NMR (300
1
MHz, CDCl3): δ 7.40-7.27 (m, 5H), 6.65 (d, J = 15.9 Hz, 1H), 6.34-
6.24 (m, 1H), 5.97-5.91 (m, 2H), 5.81-5.76 (m, 2H), 4.76 (d, J =
6.3 Hz, 2H), 2.66-2.10 (m, 1H), 0.85 (d, J = 6.9 Hz, 6H). 13C NMR
(75 MHz, CDCl3): δ 174.7, 136.3, 133.9, 128.6, 128.0, 126.6,
126.5, 125.8, 123.3, 65.2, 52.0, 35.9, 26.5, 17.4. HRMS (EI)
calculated for C19H22O2 ([M]+): 282.1620. Found: 282.1628.
Cinnamyl 3-fluoro-1-isopropylcyclohexa-2,5-dienecarboxylate
(3ib). According to general procedure, compound 1ha (500 mg, 2.7
mmol), oxalyl chloride (0.47 mL, 5.4 mmol), DMF (catalytic
amount), (E)-3-phenylprop-2-en-1-ol (0.4 mL, 3.0 mmol), pyridine
(0.26 mL, 3.25 mmol), and DMAP (catalytic amount) in dry DCM
(20 mL). Purification by flash column chromatography (EA/
Hexane) to give compound 3ib as colorless liquid (214 mg, 26%).
1H NMR (300 MHz, CDCl3) δ 7.41-7.29 (m, 5H), 6.66 (d, J = 15.9
Hz, 1H), 6.34-6.22 (m, 1H), 5.87-5.73 (m, 2H), 5.37 (d, J = 18.0
Hz, 1H), 4.76 (d, J = 6.4 Hz, 2H), 2.82 (s, 2H), 2.21-2.12 (m, 1H),
0.84 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 173.9,
158.6 (d, J = 255.3 Hz), 136.2, 134.3, 128.6, 128.1, 126.6, 123.7
(d, J = 10.7 Hz), 122.9, 101.7 (d, J = 16.9 Hz), 65.5, 55.1 (d, J =
7.4 Hz), 35.9, 27.1 (d, J = 26.6 Hz), 17.4 (d, J = 3.3 Hz). 19F NMR
(282 MHz, CDCl3): δ −102.63 (ddd, J = 17.2, 7.3, 2.4 Hz). HRMS
(EI) calculated for C19H21FO2 ([M]+): 300.1526. Found: 300.1520.
1-Phenylallyl 1-isopropylcyclohexa-2,5-dienecarboxylate (3jb).
According to general procedure, compound 1aa (1g, 6.0 mmol),
oxalyl chloride (0.77 mL, 9.0 mmol), DMF (catalytic amount), 1-
phenylprop-2-en-1-ol (085 mL, 6.6 mmol), pyridine (0.58 mL, 7.2
mmol), and DMAP (catalytic amount) in dry DCM (20 mL).
Purification by flash column chromatography (EA/ Hexane) to give
liquid (160 mg, 67%). H NMR (300 MHz, CDCl3): δ 7.07- 7.01
(m, 2H), 6.42-6.36 (m, 2H), 5.81 (d, J = 17.2 Hz, 1H), 5.39 (p, J =
6.5 Hz, 1H), 5.30-5.15 (m, 2H), 2.54-2.40 (m, 1H), 1.34 (d, J = 6.5
Hz, 3H), 0.93 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ
185.2, 169.4, 147.2, 136.6, 130.8, 116.8, 72.8, 56.5, 36.5, 19.7,
17.6. HRMS (EI) calculated for C14H18O3 ([M]+): 234.1256. Found:
234.1252.
But-3-en-2-yl 3-fluoro-1-isopropyl-4-oxocyclohexa-2,5-diene-
1-carboxylate (3d). According to general procedure, compound
3db (324 mg, 1.4 mmol), CuI (8 mg, 0.0041 mmol), and TBHP (1.1
mL, 8.5 mmol) in CH3CN (5.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3d as colorless
1
liquid (158 mg, 46%). H NMR (300 MHz, CDCl3): δ 7.08-7.04
(m, 1H), 6.63-6.57 (m, 1H), 6.46-6.40 (m, 1H), 5.88-5.76 (m, 1H),
5.44-5.17 (m, 3H), 2.55-2.47 (m, 1H), 1.35 (d, J = 6.5 Hz, 3H), 0.97
(d, J = 6.9 Hz, 3H), 0.92 (d, J = 6.9 Hz, 3H). 13C NMR (75 MHz,
CDCl3): δ 177.9 (d, J = 21.7 Hz), 168.9, 154.7 (d, J = 264.5 Hz),
148.2, 136.4, 130.3 (d, J = 4.3 Hz), 122.7 (d, J = 16.0 Hz), 117.1,
73.4, 36.9, 19.8, 17.7, 17.4. 19F NMR (282 MHz, CDCl3): −127.05
(m). HRMS (EI) calculated for C14H17FO3 ([M]+): 252.1162.
Found: 252.1169.
(E)-Hex-2-en-1-yl
1-isopropyl-4-oxocyclohexa-2,5-
dienecarboxylate (3e). According to general procedure, compound
3eb (80 mg, 0.3 mmol), CrO3 (32 mg, 0.3 mmol), and 3,5-DMP (31
mg, 0.3 mmol) in dry DCM (1.60 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3e as colorless
1
liquid (28 mg, 33%). H NMR (300 MHz, CDCl3) δ 7.05 (d, J =
10.4 Hz, 2H), 6.39 (d, J = 10.3 Hz, 2H), 5.84-5.74 (m, 1H), 5.59-
5.50 (m, 1H), 4.59 (d, J = 6.6 Hz, 2H), 2.47 (p, J = 6.9 Hz, 1H),
2.03 (q, J = 7.1 Hz, 2H), 1.40 (h, J = 7.4 Hz, 2H), 0.93-0.89 (m,
9H). 13C NMR (75 MHz, CDCl3): δ 185.4, 170.2, 147.3, 137.7,
130.8, 123.0, 66.7, 56.6, 36.6, 34.2, 21.9, 17.6, 13.6. HRMS (EI)
calculated for C16H22O3 ([M]+): 262.1569. Found: 262.1564.
1
compound 3jb as colorless liquid (440 mg, 26%). H NMR (300
MHz, CDCl3) δ 7.45-7.26 (m, 5H), 6.28 (d, J= 5.9, 1H), 6.09-5.87
(m, 3H), 5.86-5.69 (m, 2H), 5.39-5.18 (m, 2H), 2.76-2.52 (m, 2H),
2.15 (hept, J= 7.0, 1H), 0.79 (d, J= 6.9 Hz, 6H). 13C NMR (75 MHz,
CDCl3) δ 173.6, 138.9, 136.2, 128.4, 127.9, 127.0, 126.4, 125.5,
116.9, 76.0, 52.0, 35.7, 26.5, 17.2. HRMS (EI) calculated for
C19H22O2 ([M]+): 282.1620. Found: 282.1614.
3-Methylbut-2-en-1-yl 1-isopropyl-4-oxocyclohexa-2,5-diene-1-
carboxylate (3a). According to general procedure, compound 3ab
(234 mg, 1.0 mmol), CuI (6 mg, 0.003 mmol), and TBHP (0.88 mL,
7.0 mmol) in CH3CN (5.00 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3a as colorless
liquid (139 mg, 56%).1H NMR (300 MHz, CDCl3): δ 7.07-7.02 (m,
2H), 6.41-6.36 (m, 2H), 5.35-5.30 (m, 1H), 4.63 (d, J = 7.3 Hz,
2H), 2.53-2.39 (m, 1H), 1.73 (d, J = 15.2 Hz, 6H), 0.92 (d, J = 6.9
Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 185.3, 170.3, 147.3, 140.2,
130.8, 117.7, 62.8, 56.5, 36.6, 25.7, 18.0, 17.6. HRMS (EI)
calculated for C15H20O3 ([M]+): 248.1412. Found: 248.1408.
2-Methylallyl
1-isopropyl-4-oxocyclohexa-2,5-diene-1-
carboxylate (3f). According to general procedure, compound 3fb
(620 mg, 2.8 mmol), CuI (16 mg, 0.084 mmol), and TBHP (2.36
mL, 19.7 mmol) in CH3CN (10.00 mL). Purification by flash
column chromatography (EA/ Hexane) to give compound 3b as
1
colorless liquid (348 mg, 53%). H NMR (300 MHz, CDCl3): δ
7.08-7.02 (m, 2H), 6.43-6.38 (m, 2H), 4.97 (s, 2H), 4.56 (s, 2H),
2.54-2.42 (m, 1H), 1.74 (s, 3H), 0.94 (d, J = 7.2 Hz, 6H). 13C NMR
(75 MHz, CDCl3): δ 185.2, 170.0, 147.0, 138.9, 130.9, 113.9, 69.0,
56.6, 36.5, 19.4, 17.6. HRMS (EI) calculated for C14H18O3 ([M]+):
234.1256. Found: 234.1252.
2-Methylallyl 3-fluoro-1-isopropyl-4-oxocyclohexa-2,5-diene-
1-carboxylate (3g). According to general procedure, compound
3gb (710 mg, 3.0 mmol), CuI (17 mg, 0.089 mmol), and TBHP
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The Journal of Organic Chemistry
(2.51 mL, 20.9 mmol) in CH3CN (15.00 mL). Purification by flash
4-(Allyloxy)-1-isopropyl-2-methylbenzene (2c). According to the
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column chromatography (EA/ Hexane) to give compound 3g as
colorless liquid (428 mg, 57%). H NMR (300 MHz, CDCl3): δ
general procedure, compound 1c (100 mg, 0.4 mmol), and
Pd(PPh3)4 (25 mg, 0.021 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2c as
colorless liquid (73 mg, 90%). 1H NMR (300 MHz, CDCl3): δ 7.15
(d, J = 8.2 Hz, 1H), 6.77-6.72 (m, 2H), 6.13-6.01 (m, 1H), 5.41 (d,
J = 17.2, 1H), 5.28 (d, J = 10.5 Hz, 1H), 4.53-4.50 (m, 2H), 3.15-
3.01 (m, 1H), 2.32 (s, 3H), 1.21 (d, J = 6.8 Hz, 6H). 13C NMR (75
MHz, CDCl3): δ 156.2, 139.2, 136.2, 133.6, 133.6, 125.5, 117.3,
116.5, 111.9, 68.7, 28.6, 23.4, 19.4. HRMS (EI) calculated for
C13H18O ([M]+): 190.1358. Found: 190.1358.
1-(Allyloxy)-4-isopropyl-2-methylbenzene (2d). According to
the general procedure, compound 1d (100 mg, 0.4 mmol), and
Pd(PPh3)4 (25 mg, 0.021 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2d as
colorless liquid (75 mg, 92%). 1H NMR (300 MHz, CDCl3): δ 7.01-
6.97 (m, 1H), 6.77-6.74 (m, 1H), 6.14-6.02 (m, 1H), 5.43 (d, J =
17.3 Hz, 1H), 5.27 (d, J = 10.5 Hz, 1H), 4.53 (d, J = 5.0 Hz, 2H),
2.88-2.79 (m, 1H), 2.25 (s, 3H), 1.23 (d, J = 6.9 Hz, 6H). 13C NMR
(75 MHz, CDCl3): δ 154.8, 140.8, 133.8, 128.8, 126.6, 124.1,
116.7, 111.2, 68.8, 33.2, 29.6, 24.2, 16.3. HRMS (EI) calculated
for C13H18O ([M]+): 190.1358. Found: 190.1361.
1-(Allyloxy)-4-isopropyl-2,3-dimethylbenzene (2e). According
to the general procedure, compound 1e (50 mg, 0.2 mmol), and
Pd(PPh3)4 (12 mg, 0.01 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2e as
colorless liquid (28 mg, 69%). 1H NMR (300 MHz, CDCl3): δ 7.05
(d, J = 8.6 Hz, 1H), 6.72 (d, J = 8.6 Hz, 1H), 6.15-6.02 (m, 1H),
5.43 (d, J = 17.3 Hz, 1H), 5.26 (d, J = 10.5Hz, 1H), 4.51 (d, J = 5.1
Hz, 2H), 3.20-3.11 (m, 1H), 2.24 (d, J = 9.1 Hz, 6H), 1.21 (d, J =
6.8 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 154.3, 139.0, 135.1,
134.0, 125.4, 122.2, 116.6, 109.3, 69.1, 29.6, 29.1, 23.5, 15.0, 12.3.
HRMS (EI) calculated for C14H20O ([M]+): 204.1514. Found:
204.1512.
2-(Allyloxy)-5-isopropyl-1,3-dimethylbenzene (2f). According to
the general procedure, compound 1f (50 mg, 0.2 mmol), and
Pd(PPh3)4 (12 mg, 0.01 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2f as
colorless liquid (38 mg, 92%). 1H NMR (300 MHz, CDCl3): δ 6.86
(s, 2H), 6.18-6.05 (m, 1H), 5.43 (d, J = 17.2 Hz, 1H), 5.25 (d, J =
10.4 Hz, 1H), 4.29 (d, J = 5.5 Hz, 2H), 2.84- 2.75 (m, 1H), 2.27 (s,
6H), 1.22 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 153.8,
144.1, 134.3, 130.5, 126.6, 116.9, 73.0, 33.4, 29.6, 24.1, 16.4.
HRMS (EI) calculated for C14H20O ([M]+): 204.1514. Found:
204.1508.
1-(Allyloxy)-4-isopropylnaphthalene (2g). According to the
general procedure, compound 1g (100 mg, 0.4 mmol), and
Pd(PPh3)4 (21 mg, 0.019 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2g as
colorless liquid (65 mg, 77%). 1H NMR (300 MHz, CDCl3): δ 8.38
(d, J = 8.1 Hz, 1H), 8.08 (d, J = 8.3 Hz, 1H), 7.57-7.45 (m, 2H),
7.29 (d, J = 8.0 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.25-6.12 (m,
1H), 5.53 (d, J = 17.3 Hz, 1H), 5.33 (d, J = 10.4 Hz, 1H), 4.71 (d,
J = 5.1 Hz, 2H), 3.73-3.60 (m, 1H), 1.38 (d, J = 6.8 Hz, 6H). 13C
NMR (75 MHz, CDCl3): δ 152.5, 136.6, 133.5, 132.2, 126.1, 124.5,
123.0, 122.7, 121.3, 117.2, 104.7, 68.9, 28.0, 23.6. HRMS (EI)
calculated for C16H18O ([M]+): 226.1358. Found: 226.1356.
1-(Allyloxy)-2-fluoro-4-isopropylbenzene (2h). According to the
general procedure, compound 1h (100 mg, 0.4 mmol), and
Pd(PPh3)4 (24 mg, 0.021 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2h as
colorless liquid (70 mg, 86%). 1H NMR (300 MHz, CDCl3): δ 7.02-
6.80 (m, 3H), 6.13-6.07 (m, 1H), 5.42 (dq, J = 17.2, 1.6 Hz, 1H),
5.29 (d, J = 10.5 Hz, 1H), 4.58 (d, J = 5.4 Hz, 2H), 2.84 (hept, J =
6.8 Hz, 1H), 1.21 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3):
δ 152.7 (d, J = 245.0 Hz), 144.3 (d, J = 10.8 Hz), 142.6 (d, J = 5.6
Hz), 133.1, 121.6, 117.9, 115.4, 114.2 (d, J = 18.4 Hz), 70.4, 33.2,
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7.07 (dd, J = 10.2, 2.7 Hz, 1H), 6.61 (dd, J = 13.3, 2.7 Hz, 1H),
6.44 (dd, J = 10.1, 6.9 Hz, 1H), 4.98 (s, 2H), 4.58 (s, 2H), 2.58-2.48
(m, 1H), 1.75 (s, 3H), 0.98 (d, J = 6.9 Hz, 3H) , 0.93 (d, J = 6.9 Hz,
3H). 13C NMR (75 MHz, CDCl3): δ177.9 (d, J = 21.9 Hz), 169.4,
154.8 (d, J = 264.6 Hz), 148.0, 138.7, 130.4, 122.5 (d, J = 15.3 Hz),
114.2, 69.4, 58.0 (d, J = 5.4 Hz), 36.9, 19.4, 17.7 (d, J = 25.4 Hz).
19F NMR (282 MHz, CDCl3): δ −126.89 (dd, J = 13.3, 6.9 Hz).
HRMS (EI) calculated for C14H17FO3 ([M]+): 252.1162. Found:
252.1156.
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Cinnamyl
1-isopropyl-4-oxocyclohexa-2,5-dienecarboxylate
(3h). According to general procedure, compound 3hb (911 mg, 3.2
mmol), CrO3 (384 mg, 3.84 mmol), and 3,5-DMP (338 mg, 3.52
mmol) in dry DCM (20 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3h as colorless
liquid (304 mg, 32%). 1H NMR (300 MHz, CDCl3) δ 7.51-7.23 (m,
5H), 7.07 (d, J = 10.4 Hz, 2H), 6.67 (d, J = 15.9 Hz, 1H), 6.41 (d,
J = 10.4 Hz, 2H), 6.26 (dt, J = 15.8, 6.6 Hz, 1H), 4.80 (d, J = 6.6
Hz, 2H), 2.50 (hept, J = 6.9 Hz, 1H), 0.94 (d, J = 6.9 Hz, 6H). 13
C
NMR (75 MHz, CDCl3) δ 185.2, 170.1, 147.0, 135.7, 135.3, 130.9,
128.6, 128.3, 126.6, 121.9, 66.5, 56.5, 36.6, 17.6. HRMS (EI)
calculated for C19H20O3 ([M]+): 296.1412. Found: 296.1416.
Cinnamyl
3-fluoro-1-isopropyl-4-oxocyclohexa-2,5-
dienecarboxylate (3i). According to general procedure, compound
3ib (100 mg, 0.3 mmol), CrO3 (7 mg, 0.3 mmol), and 3,5-DMP (32
mg, 0.3 mmol) in dry DCM (1.65 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3i as colorless
liquid (16 mg, 15%). 1H NMR (300 MHz, CDCl3): δ 7.41-7.29 (m,
5H), 7.09 (dd, J = 10.2, 2.7 Hz, 1H), 6.71-6.60 (m, 2H), 6.45 (dd,
J = 9.9, 6.6 Hz, 1H), 6.26 (dt, J = 15.8, 7.0 Hz, 1H), 4.82 (d, J = 6.7
Hz, 2H), 2.54 (dt, J = 13.8, 6.9 Hz, 1H), 0.95 (dd, J = 14.6, 6.9 Hz,
6H). 13C NMR (75 MHz, CDCl3): δ 177.9 (d, J = 21.8 Hz), 169.6,
154.7 (d, J = 264.5 Hz), 148.1, 147.1, 135.8, 130.42, 128.7, 128.4,
126.7, 122.5 (d, J = 15.4 Hz), 121.6, 66.9, 57.9 (d, J = 5.4 Hz),
37.0, 17.7 (d, J = 26.0 Hz). 19F NMR (282 MHz, CDCl3): δ −126.83
(dd, J = 13.0, 6.5 Hz). HRMS (EI) calculated for C19H19FO3 ([M]+):
314.1318. Found: 314.1315.
1-Phenylallyl 1-isopropyl-4-oxocyclohexa-2,5-dienecarboxylate
(3j). According to general procedure, compound 3jb (280 mg, 1
mmol), CrO3 (120 mg, 1.2 mmol), and 3,5-DMP (105 mg, 1.1
mmol) in dry DCM (20 mL). Purification by flash column
chromatography (EA/ Hexane) to give compound 3j as colorless
liquid (70 mg, 15%). 1H NMR (300 MHz, CDCl3): δ 7.49-7.24 (m,
5H), 7.06 (d, J = 10.5 Hz, 2H), 6.41 (d, J = 10.2 Hz, 2H), 6.29 (d,
J = 6.0 Hz, 1H), 6.10 – 5.89 (m, 1H), 5.39-5.20 (m, 2H), 2.48 (hept,
J = 6.9 Hz, 1H), 0.87 (dd, J = 6.9, 3.1 Hz, 6H). 13C NMR (75 MHz,
CDCl3): δ 185.2, 169.2, 146.9, 137.9, 135.3, 130.9, 128.6, 128.5,
127.0, 117.8, 77.8, 56.6, 36.5, 17.5. HRMS (EI) calculated for
C19H20O3 ([M]+): 296.1412. Found: 296.1418.
1-(Allyloxy)-4-isopropylbenzene (2a).23 According to the general
procedure, compound 1a (50 mg, 0.2 mmol), and Pd(PPh3)4 (14
mg, 0.012 mmol) in CH3CN (1 mL). Purification by flash column
chromatography (Hexane) to give compound 2a as colorless liquid
(38 mg, 94%). 1H NMR (300 MHz, CDCl3): δ 7.16-7.11 (m, 2H),
6.88-6.83 (m, 2H), 6.13-6.00 (m, 1H), 5.45-5.37 (m, 1H), 5.30-5.25
(m, 1H), 4.53-4.50 (m, 2H), 2.90-2.81 (m, 1H), 1.22 (d, J = 7.0 Hz,
6H).
1-(Allyloxy)-4-methylbenzene (2b).24 According to the general
procedure, compound 1b (100 mg, 0.5 mmol), and Pd(PPh3)4 (30
mg, 0.026 mmol) in CH3CN (1 mL). Purification by flash column
chromatography (Hexane) to give compound 2b as colorless liquid
(68.4 mg, 89%). 1H NMR (300 MHz, CDCl3): δ 7.10-7.07 (m, 2H),
6.85-6.80 (m, 2H), 6.13-6.00 (m, 1H), 5.45-5.37 (m, 1H), 5.30-5.25
(m, 1H), 4.53-4.50 (m, 2H), 2.29 (s, 3H).
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23.9. 19F NMR (282 MHz, CDCl3): δ −134.42 (m). HRMS (EI)
4c’ (mixture) as colorless liquid (31 mg, 78%, 4c:4c’ = 1:0.31). 1H
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calculated for C12H15FO ([M]+): 194.1107. Found: 194.1099.
4-(Allyloxy)-1-hexyl-2-methylbenzene (2i). According to the
general procedure, compound 1i (100 mg, 0.4 mmol), and
Pd(PPh3)4 (21 mg, 0.018 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2i as
colorless liquid (78 mg, 93%). 1H NMR (300 MHz, CDCl3): δ 7.02
(d, J = 8.2 Hz, 1H), 6.73-6.67 (m, 2H), 6.12-6.01 (m, 1H), 5.40 (d,
J = 17.2 Hz, 1H), 5.27 (d, J = 10.5 Hz, 1H), 4.50 (d, J = 5.3 Hz,
2H), 2.54-2.49 (m, 2H), 2.27 (s, 3H), 1.53-1.48 (m, 1H), 1.38-1.26
(m, 7H), 0.91-0.87 (m, 3H). 13C NMR (75 MHz, CDCl3): δ 156.5,
137.0, 133.6, 133.5, 129.5, 117.3, 116.5, 111.7, 68.7, 32.5, 31.7,
30.5, 29.3, 22.6, 19.5, 14.1. HRMS (EI) calculated for C16H24O
([M]+): 232.1827. Found: 232.1828.
4-(Allyloxy)-1-benzyl-2-methylbenzene (2j). According to the
general procedure, compound 1j (55 mg, 0.20 mmol), and
Pd(PPh3)4 (12 mg, 0.010 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 2j as
colorless liquid (40 mg, 81%). 1H NMR (300 MHz, CDCl3): δ 7.29-
7.10 (m, 5H), 7.00 (d, J = 8.3 Hz, 1Hz), 6.76 (d, J = 2.6 Hz, 1H),
6.70 (d, J = 8.3 Hz, 1H), 6.12-6.01 (m, 1H), 5.41 (d, J = 17.3 Hz,
1H), 5.28 (d, J = 10.5 Hz, 1H), 4.51 (d, J = 5.3 Hz, 2H), 3.92 (s,
2H), 2.20 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 157.0, 140.7,
137.9, 133.4, 131.3, 130.7, 128.5, 128.3, 125.8, 117.5, 116.7,
111.6, 68.7, 38.6, 29.6, 19.9. HRMS (EI) calculated for C17H18O
([M]+): 238.1358. Found: 238.1363.
Methyl 2-(4-(allyloxy)phenyl)acetate (2k). According to the
general procedure, compound 1k (50 mg, 0.2 mmol), and Pd(PPh3)4
(12 mg, 0.010 mmol) in CH3CN (1 mL). Purification by flash
column chromatography (Hexane) to give compound 2k as
colorless liquid (36 mg, 87%). 1H NMR (300 MHz, CDCl3): δ 7.21-
7.16 (m, 2H), 6.90-6.85 (m, 2H), 6.12-5.99 (m, 1H), 5.41 (d, J =
17.3 Hz, 1H), 5.28 (d, J = 10.2 Hz, 1H), 4.52 (d, J = 5.3 Hz, 2H),
3.69 (s, 3H), 3.57 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 172.3,
157.7, 133.2, 130.2, 126.1, 117.6, 114.8, 68.8, 52.0, 40.2, 40.2.
HRMS (EI) calculated for C12H14O3 ([M]+): 206.0943. Found:
206.0953.
NMR (300 MHz, CDCl3): 7.13-7.08 (m, 2H), 6.87-6.81 (m, 2H),
5.99-5.85 (m, 1H), 5.34-5.12 (m, 2H), 4.82-4.71 (m, 1H), 2.92-2.78
(m, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.22 (d, J = 6.9 Hz, 6H). HRMS
(EI) calculated for C13H18O ([M]+): 190.1358. Found: 190.1362.
1-(But-3-en-2-yloxy)-2-fluoro-4-isopropylbenzene (4d), (E)-1-
(but-2-en-1-yloxy)-2-fluoro-4-isopropylbenzene (4d’) (4d:4d’ =
1:0.23). According to the general procedure, compound 3d (50 mg,
0.2 mmol), and Pd(PPh3)4 (11 mg, 0.0099 mmol) in CH3CN (1
mL). Purification by flash column chromatography (Hexane) to
give compound 4d and 4d’ (mixture) as colorless liquid (30 mg,
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73%, 4d:4d’ = 1:0.23). H NMR (300 MHz, CDCl3): δ 7.01-6.81
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(m, 3H), 5.93 (m, 1H), 5.21 (m, 2H), 4.78-4.67 (m, 1H), 2.83 (hept,
J = 6.9 Hz, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.21 (d, J = 6.9 Hz, 6H).
19F NMR (282 MHz, CDCl3): δ −133.27 (dd, J= 13.9, 7.89 Hz)
(4d), −134.46 (m) (4d’). HRMS (EI) calculated for C13H17FO
([M]+): 208.1263. Found: 208.1270.
1-(Hex-1-en-3-yloxy)-4-isopropylbenzene (4e), (E)-1-(hex-2-en-
1-yloxy)-4-isopropylbenzene (4e:4e’ = 1:0.95). According to the
general procedure, compound 4e (28 mg, 0.1 mmol), and Pd(PPh3)4
(6 mg, 0.005 mmol) in CH3CN (0.5 mL). Purification by flash
column chromatography (Hexane) to give compound 4e and 4e’
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(mixture) as colorless liquid (21 mg, 92%, 4e:4e’ = 1:0.95). H
NMR (300 MHz, CDCl3): δ 7.19-7.08 (m, 2H), 6.75-6.91 (m, 2H),
6.00-5.80 (m, 1H), 5.31-5.15 (m, 1H), 4.60-4.52 (m, 4e, 1H), 4.45
(d, J= 6 Hz, 4e’, 2H), 2.90-2.76 (m, 1H), 1.48-1.29 (m, 3H), 1.20-
1.48 (m, 6H), 0.98-0.88 (m, 4H). HRMS (EI) calculated for
C15H22O ([M]+): 218.1671. Found: 218.1676.
1-Isopropyl-4-((2-methylallyl)oxy)benzene (4f). According to
the general procedure, compound 3f (50 mg, 0.2 mmol), and
Pd(PPh3)4 (12 mg, 0.010 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 4f as
colorless liquid (37 mg, 91%).1H NMR (300 MHz, CDCl3): δ 7.16-
7.11 (m, 2H), 6.88-6.83 (m, 2H), 5.09 (s, 1H), 4.98 (s, 1H), 4.41 (s,
2H), 2.91-2.79 (m, 1H), 1.83 (s, 3H), 1.23 (d, J = 6.9 Hz, 6H). 13
C
NMR (75 MHz, CDCl3): δ 156.8, 141.1, 127.1, 114.5, 112.5, 71.8,
33.2, 24.1, 19.4. HRMS (EI) calculated for C13H18O ([M]+):
190.1358. Found: 190.1367.
1-Isopropyl-4-((2-methylbut-3-en-2-yl)oxy)benzene
(4a).
According to the general procedure, compound 3a (20 mg, 0.1
mmol), Pd(dba)2 (4 mg, 0.004 mmol), and PPh3 (2 mg, 0.008
mmol) in CH3CN (0.3 mL). Purification by flash column
chromatography (Hexane) to give compound 4a as colorless liquid
2-Fluoro-4-isopropyl-1-((2-methylallyl)oxy)benzene
(4g).
According to the general procedure, compound 3g (50 mg, 0.2
mmol), and Pd(PPh3)4 (11 mg, 0.0099 mmol) in CH3CN (1 mL).
Purification by flash column chromatography (Hexane) to give
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(12 mg, 70%). H NMR (300 MHz, CDCl3) δ 7.09-7.04 (m, 2H),
compound 4g as colorless liquid (38 mg, 92%). H NMR (300
6.92-6.87 (m, 2H), 6.19-6.09 (m, 1H), 5.19-5.10 (m, 2H), 2.89-2.80
(m, 1H), 1.43 (s, 6H), 1.22 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz,
CDCl3): δ 153.7, 144.6, 142.5, 126.5, 121.6, 113.1, 79.1, 33.3, 26.9,
24.1. HRMS (EI) calculated for C14H20O ([M]+): 204.1514. Found:
204.1512.
MHz, CDCl3): δ 6.97-6.93 (m, 1H), 6.89-6.87 (m, 2H), 5.10 (s,
1H), 4.99 (s, 1H), 4.48 (s, 2H), 2.91-2.77 (m, 1H), 1.84 (s, 3H),
1.21 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ152.7 (d, J
= 245.0 Hz), 144.5 (d, J = 10.8 Hz), 142.6 (d, J = 5.6 Hz), 140.7,
121.7 (d, J = 3.3 Hz), 115.4 (d, J = 2.1 Hz), 114.2 (d, J = 18.1 Hz),
112.9, 73.3, 33.2, 29.6, 23.9, 19.3. 19F NMR (282 MHz, CDCl3): δ
−134.37 (m). HRMS (EI) calculated for C13H17FO ([M]+):
208.1263. Found: 208.1270.
1-(Cinnamyloxy)-4-isopropylbenzene (4h). According to the
general procedure, compound 3h (50 mg, 0.2 mmol), and Pd(PPh3)4
(9.7 mg, 0.0084 mmol) in CH3CN (1 mL). Purification by flash
column chromatography (Hexane) to give compound 4h as white
solid (41 mg, 97%). Compound 3j (40 mg, 0.13 mmol), and
Pd(PPh3)4 (7.5 mg, 0.0065 mmol) in CH3CN (1 mL). Purification
by flash column chromatography (Hexane) to give compound 4h
as white solid (29 mg, 90%). mp = 66-68 °C. 1H NMR (300 MHz,
CDCl3): δ 7.64-7.25 (m, 5H), 7.22 (d, J = 8.4 Hz, 2H), 6.79 (d, J =
16.0 Hz, 2H), 6.79 (d, J = 16.0 Hz, 1H), 6.48 (dt, J = 16.0, 5.8 Hz,
1H), 4.74 (d, J = 7.1 Hz, 2H), 2.94 (hept, J = 6.8 Hz, 1H), 1.31 (d,
J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ 156.6, 141.2, 136.4,
132.7, 128.5, 127.7, 127.2, 126.5, 124.6, 114.5, 68.6, 33.2, 24.1.
HRMS (EI) calculated for C18H20O ([M]+): 252.1514. Found:
252.1506.
2-Fluoro-4-isopropyl-1-((2-methylbut-3-en-2-yl)oxy)benzene
(4b). According to the general procedure, compound 3b (22 mg,
0.05 mmol), Pd(dba)2 (3 mg, 0.0038 mmol), and PPh3 (2 mg,
0.0075 mmol) in CH3CN (0.3 mL). Purification by flash column
chromatography (Hexane) to give compound 4b as colorless liquid
(13 mg, 80%). 1H NMR (300 MHz, CDCl3): δ 6.99-6.80 (m, 3H),
6.18-6.08 (m, 1H), 5.18-5.09 (m, 2H), 2.91-2.77 (m, 1H), 1.44 (s,
6H), 1.21 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ177.9
(d, J = 21.7 Hz), 169.7, 154.6 (d, J = 264.1 Hz), 148.4 (d, J = 2.1
Hz), 140.6, 130.2 (d, J = 4.4 Hz), 122.8 (d, J = 15.3 Hz), 117.5,
63.1, 57.9 (d, J = 5.2 Hz), 36.9, 25.7, 18.0, 17.6 (d, J = 23.5 Hz).
19F NMR (282 MHz, CDCl3): δ −127.20 (dd, J = 13.4, 6.9 Hz).
HRMS (EI) calculated for C14H19FO ([M]+): 222.1420. Found:
222.1425.
1-(But-3-en-2-yloxy)-4-isopropylbenzene (4c), (E)-1-(but-2-en-
1-yloxy)-4-isopropylbenzene (4c’) (4c:4c’ = 1:0.31). According to
the general procedure, compound 3c (50 mg, 0.2 mmol), and
Pd(PPh3)4 (12 mg, 0.010 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (Hexane) to give compound 4c and
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1-(Cinnamyloxy)-2-fluoro-4-isopropylbenzene (4i), 2-fluoro-4-
5.10 (m, 2H), 3.40 (d, J = 6.3 Hz, 2H), 2.83 (sept, J = 6 Hz, 1H),
1.21 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 152.1,
141.4, 136.6, 128.4, 125.5, 124.8, 116.4, 115.6, 35.4, 33.3, 24.2.
HRMS (EI) calculated for C12H16O ([M]+): 176.1201. Found:
176.1200.
2-Allyl-6-fluoro-4-isopropylphenol (5b). According to the
general procedure, compound 2h (100 mg, 0.51 mmol), DMF (1
mL). Compound 5b (98 mg, 98%) was achieved without further
purification. 1H NMR (300 MHz, CDCl3): δ 6.9-6.7 (m, 2H), 6.09-
5.91 (m, 1H), 5.18-5.03 (m, 2H), 3.41 (d, J = 6.5 Hz, 2H), 2.87-
2.72 (m, 1H), 1.20 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3):
δ150.9 (d, J = 235.9 Hz), 141.2 (d, J = 5.7 Hz), 139.2 (d, J = 14.3
Hz), 136.2, 127.9, 123.2 (d, J = 2.5 Hz), 115.9, 110.9 (d, J = 18.2
Hz), 34.1, 33.4, 24.1. 19F NMR (282 MHz, CDCl3): δ −141.30 (d,
J = 11.5 Hz). HRMS (EI) calculated for C12H15FO ([M]+):
194.1107. Found: 194.1101.
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isopropyl-1-((1-phenylallyl)oxy)benzene (4i’) (4i:4i’ = 1:0.57).
According to the general procedure, compound 3i (50 mg, 0.16
mmol), and Pd(PPh3)4 (9.2 mg, 0.008 mmol) in CH3CN (1 mL).
Purification by flash column chromatography (Hexane) to give
compound 4i and 4i’ (mixture) as colorless liquid (41 mg, 95%,
4i:4i’ = 1:0.57). 1H NMR (300 MHz, CDCl3): δ 7.48-7.24 (m, 5H),
7.05-6.83 (m, 3H), 6.51-6.36 (m, 1H), 4.80-4.72 (m, 2H), 2.96-2.75
(m, 1H), 1.24-1.18 (m, 6H). 19F NMR (282 MHz, CDCl3): −134.16
(m). HRMS (EI) calculated for C18H19FO ([M]+): 270.1420. Found:
270.1424.
9
1-(2-Carboxyethyl)cyclohexa-2,5-dienecarboxylic acid (3ka).
According to the general procedure, benzoic acid (5 g, 41 mmol),
3-Bromopropionic acid (18.8 g, 123 mmol), and Li (0.71g, 102.3
mmol). Compound 3ka was achieved after recrystallization as
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white solid (7.8 g, 98%). mp = 162-164 °C. H NMR (300 MHz,
DMSO-d6): δ 12.46-12.16 (broad, 2H), 5.86 (d, J = 10.5 Hz, 2H),
5.61 (d, J = 10.5 Hz, 2H), 2.58 (s, 2H), 2.12-2.00 (m, 2H), 1.88-
1.78 (m, 2H). 13C NMR (75 MHz, DMSO-d6) δ 175.8, 174.8,
127.4, 126.4, 47.1, 34.1, 29.7, 26.2. HRMS (ESI) calculated for
C10H11O4 ([M−H]−): 195.0652. Found: 195.0649.
Methyl 2-(3-allyl-4-hydroxyphenyl)acetate (5c). According to
the general procedure, compound 2k (60 mg, 0.3 mmol), DMF (1
mL). Compound 5c (59 mg, 98%) was achieved without further
1
purification. H NMR (300 MHz, CDCl3): δ 7.17-6.92 (m, 2H),
6.72 (d, J = 8.8 Hz, 1H), 6.11-5.89 (m, 1H), 5.23-5.07 (m, 2H), 3.69
(s, 3H), 3.54 (s, 2H), 3.38 (d, J = 6.4 Hz, 2H). 13C NMR (75 MHz,
CDCl3): δ 172.7, 153.3, 136.2, 131.2, 128.5, 126.0, 125.6, 116.5,
115.9, 52.1, 40.3, 34.9. HRMS (EI) calculated for C12H14O3 ([M]+):
206.0943. Found: 206.0946.
4-Isopropyl-2-(2-methylallyl)phenol (5d). According to the
general procedure, compound 4f (120 mg, 0.63 mmol), DMF (1
mL). Purification by flash column chromatography (EA/Hexane)
to give compound 5d (81.6 mg, 68%). 1H NMR (300 MHz, CDCl3):
δ 7.11-6.87 (m, 2H), 6.77 (d, J = 8.2 Hz, 1H), 4.93 (s, 1H), 4.86 (s,
1H), 3.37 (s, 2H), 2.84 (hept, J = 7.2 Hz, 1H), 1.76 (s, 3H), 1.23 (d,
J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 152.6, 144.8, 141.2,
128.9, 125.6, 124.4, 115.8, 112.2, 40.1, 33.2, 24.2, 22.1. HRMS
(EI) calculated for C13H18O ([M]+): 190.1358. Found: 190.1360.
3-Methylbut-2-en-1-yl
1-(3-((3-methylbut-2-en-1-yl)oxy)-3-
oxopropyl)cyclohexa-2,5-dienecarboxylate (3kb). According to the
general procedure, compound 3ka (2 g, 10.2 mmol), oxalyl
chloride (2.62 mL, 0.6 mmol, 3 equiv.), DMF (catalytic amount),
3-Methyl-2-buten-1-ol (2.56 mL, 25.5 mmol, 2.5 equiv.), pyridine
(1.97 mL, 24.5 mmol, 2.4 equiv.), and DMAP (catalytic amount)
in dry DCM (40 mL). Purification by flash column chromatography
(EA/ Hexane) to give compound 3kb as yellow liquid (3.2 g, 94%).
1H NMR (300 MHz, CDCl3): δ 5.90 (d, J = 10.5 Hz, 2H), 5.68 (d,
J = 10.5 Hz, 2H), 5.36-5.25 (m, 2H), 4.62-4.48 (m, 4H), 2.67-2.58
(m, 2H), 2.27-2.17 (m, 2H), 2.06-1.96 (m, 2H), 1.72 (d, J = 16.9
Hz, 12H). 13C NMR (75 MHz, CDCl3): δ 174.3, 173.5, 139.1,
138.9, 127.2, 126.6, 126.3, 125.7, 118.5, 118.4, 62.0, 61.3, 47.3,
33.7, 29.6, 26.1, 25.8, 18.1, 17.9. HRMS (ESI) calculated for
C20H28NaO4 ([M+Na]+): 355.1880. Found: 355.1884.
3-Methylbut-2-en-1-yl
3-(4-hydroxy-3-(3-methylbut-2-en-1-
yl)phenyl)propanoate (5e). According to general procedure,
compound 4j (40 mg, 0.13 mmol), DMF (1 mL). Compound 5e (40
mg, 99%) was achieved without further purification. 1H NMR (300
MHz, CDCl3) δ 6.99-6.85 (m, 2H) 6.71 (d, J = 8.7 Hz,1H), 5.40-
5.21 (m, 2H), 4.57 (d, J = 7.2 Hz, 2H), 3.31 (d, J = 7.2 Hz, 2H),
2.85(t, J = 7.9 Hz, 2H), 2.58 (t, J = 7.9 Hz, 2H), 1.96-1.58 (m, 12H).
13C NMR (75 MHz, CDCl3) δ 173.2, 152.7, 139.1, 134.6, 132.6,
129.8, 127.1, 126.8, 121.8, 118.5, 115.6, 61.4, 36.3, 30.2, 29.8,
25.8, 17.9, 17.8. HRMS (EI) calculated for C19H26O3 ([M]+):
302.1882. Found: 302.1888.
1 mmol scale test for RSDcA reaction. According to general
procedure, compound 3f (234 mg, 1 mmol), and Pd(PPh3)4 (57.8
mg, 0.05 mmol) in CH3CN (3 mL). Purification by flash column
chromatography (Hexane) to give compound 4f as colorless liquid
(167 mg, 88%).
3-Methylbut-2-en-1-yl
1-(3-((3-methylbut-2-en-1-yl)oxy)-3-
oxopropyl)-4-oxocyclohexa-2,5-dienecarboxylate (3k). According
to general procedure, compound 3kb (320 mg, 0.96 mmol), CuI
(5.5 mg, 0.029 mmol), and TBHP (0.92 mL, 6.72 mmol) in CH3CN
(3.00 mL). Purification by flash column chromatography (EA/
Hexane) to give compound 3k as colorless liquid (183 mg, 55%).
1H NMR (300 MHz, CDCl3): δ 6.99 (d, J = 10.3 Hz, 2H), 6.36 (d,
J = 10.3 Hz, 2H), 5.34-5.22 (m, 2H), 4.62 (d, J = 7.3 Hz, 2H), 4.53
(d, J = 7.3 Hz, 2H), 2.41-2.28 (m, 2H), 2.23-2.12 (m, 2H), 1.71 (d,
J = 19.1 Hz, 12H). 13C NMR (75 MHz, CDCl3): δ 184.9, 172.1,
169.8, 147.2, 140.4, 139.6, 130.8, 118.1, 117.5, 63.2, 61.7, 51.7,
32.4, 28.9, 25.8, 18.1, 17.9. HRMS (ESI) calculated for
C20H26NaO5 ([M+Na]+): 369.1672. Found: 369.1682.
3-Methylbut-2-en-1-yl
3-(4-((2-methylbut-3-en-2-
yl)oxy)phenyl)propanoate (4j). According to the general procedure,
compound 3k (80 mg, 0.23 mmol), Pd(dba)2 (11 mg, 0.012 mmol),
and PPh3 (6.3 mg, 0.024 mmol) in CH3CN (1 mL). Purification by
flash column chromatography (EA/Hexane) to give compound 4j
■ ASSOCIATED CONTENT
Supporting Information
1
as colorless liquid (40 mg, 58%). H NMR (300 MHz, CDCl3): δ
The Supporting Information is available free of charge on the ACS
Publications website.
7.03 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 6.12 (dd, J =
17.6, 10.8 Hz, 1H), 5.38-5.26 (m, 1H), 5.2-5.07 (m, 2H), 4.56 (d, J
= 7.2 Hz, 2H), 2.95-2.80 (m, 2H), 2.67-2.51 (m, 2H), 1.73 (d, J =
18.4 Hz, 6H), 1.42 (s, 6H). 13C NMR (75 MHz, CDCl3): δ 173.1,
154.2, 144.4, 139.1, 134.3, 128.5, 121.8, 118.5, 113.3, 79.3, 61.4,
36.1, 30.2, 29.7, 26.9, 25.8, 18.0. HRMS (EI) calculated for
C19H26O3 ([M]+): 302.1882. Found: 302.1880.
2-Allyl-4-isopropylphenol (5a). According to the general
procedure, compound 2a (50 mg, 0.28 mmol), DMF (1 mL).
Purification by flash column chromatography (EA/Hexane) to give
compound 5a (36 mg, 72%). 1H NMR (300 MHz, CDCl3) δ 7.03-
6.91 (m, 2H), 6.75 (d, J = 8.1 Hz, 1H), 6.11-5.94 (m, 1H), 5.23-
1
Scheme of synthetic methods, H, 13C, and 19F NMR spectra
for all new compounds (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: cmchou@nuk.edu.tw
ORCID
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Page 12 of 13
Practical Organic Chemistry, 5th ed.; Longman Group: London, 1989;
Chih-Ming Chou: 0000-0002-9894-5365
pp 984-986. (c) Kürti, L.; Czakó, B. In Strategic Applications of Named
Reactions in Organic Synthesis; Elsevier: Oxford, 2005; pp 88−90,
484−485. (d) Sanford, E. M.; Lis, C. C.; McPherson, N. R. The
Preparation of Allyl Phenyl Ether and 2-Allylphenol Using the
Williamson Ether Synthesis and Claisen Rearrangement. J. Chem. Edu.
2009, 86, 1422−1423.
(7) (a) Larock, R. C.; Lee, N. H. Synthesis of Allylic Aryl Ethers via
Palladium-Catalyzed Decarboxylation of Allylic Aryl Carbonates.
Tetrahedron Lett. 1991, 32, 6315−6318. (b) Evans, P. A.; Leahy, D. K.
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Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENT
We gratefully thank the National University of Kaohsiung and the
Ministry of Science and Technology of Taiwan (MOST 106-2113-
M-390-001-MY2) for their financial support. We also thank Prof.
J. R. Carey at the Department of Applied Chemistry, National
University of Kaohsiung, Kaohsiung, Taiwan, for helpful
suggestions and discussions.
Regioselective
and
Enantiospecific
Rhodium-Catalyzed
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Intermolecular Allylic Etherification with Ortho-Substituted Phenols.
J. Am. Chem. Soc. 2000, 122, 5012−5013. (c) Austeri, M.; Linder, D.;
Lacour, J. Enantioselective and Regioselective Ruthenium‐Catalyzed
Decarboxylative Etherification of Allyl Aryl Carbonates. Chem. Eur.
J. 2008, 14, 5737−5741. (d) Trivedi, R.; Tunge, J. A. Regioselective
Iron-Catalyzed Decarboxylative Allylic Etherification. Org. Lett. 2009,
11, 5650−5652. (e) Austeri, M.; Linder, D.; Lacour, J.
(Cyclopentadienyl)ruthenium‐Catalyzed Regio‐ and Enantioselective
Decarboxylative Allylic Etherification of Allyl Aryl and Alkyl
Carbonates. Adv. Synth. Catal. 2010, 352, 3339−3347. (f) Kim, D.;
Reddy, S.; Singh, O. V.; Lee, J. S.; Kong, S. B.; Han, H. Ir(I)-Catalyzed
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C; Kleij, A. W. Pd-Catalyzed Enantio- and Regioselective Formation
of Allylic Aryl Ethers. Org. Lett. 2017, 19, 6388−6391.
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