Palladium-Catalyzed Aerobic Oxygenation of Allylarenes

Article abstract of DOI:10.1021/acs.joc.7b01729

An efficient and practical protocol for the synthesis of (E)-allylethers from readily available olefins with alcohols or phenols was developed. This aerobic oxidative allylic C-H oxygenation protocol features mild conditions, broad substrate scope, and hi

Full text of DOI:10.1021/acs.joc.7b01729

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Article
Palladium-Catalyzed Aerobic Oxygenation of Allylarenes
Chunsheng Li, Meng Li, Jianxiao Li, Jianhua Liao, Wanqing Wu, and Huanfeng Jiang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01729 • Publication Date (Web): 07 Sep 2017
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Palladium-Catalyzed Aerobic Oxygenation of
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Allylarenes
Chunsheng Li, Meng Li, Jianxiao Li, Jianhua Liao, Wanqing Wu* and Huanfeng
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Jiang*
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of
Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640,
China
Fax: (+) (+86) 20ꢀ8711ꢀ2906; Eꢀmail: cewuwq@scut.edu.cn, jianghf@scut.edu.cn
Abstract: An efficient and practical protocol for the synthesis of (E)ꢀallylethers from
readily available olefins with alcohols or phenols has been developed. This aerobic
oxidative allylic CꢀH oxygenation protocol features mild conditions, broad substrate
scope, as well as high atomꢀ and stepꢀeconomy, making it a valuable and convenient
synthetic method. Notably, molecular oxygen is the sole oxidant in this novel
transformation.
INTRODUCTION
Palladiumꢀcatalyzed oxidative allylic CꢀH functionalization is a wellꢀestablished
method that has played a vital role in synthetic chemistry due to its broad
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applicability1,2, leading to allylic CꢀH oxygenation,3 alkylation,4 amination,5
carbonylation,6 silylation7 and dehydrogenation8. This new procedure shows that
unnecessary functional group manipulations (FGMs) can be bypassed, which presents
a highly efficient approach for the synthesis of functionalized olefins, reducing
synthetic steps and increasing overall yield. Recently, our group has reported an
efficient and convenient procedure for the synthesis of cinnamic aldehydes via
aerobic oxidative oxygenation of allylarenes (Scheme 1a).9 More recently, we have
also developed aerobic oxidative double allylic CꢀH oxygenation of alkenes for the
construction of βꢀenoic acid esters and α,βꢀunsaturated esters with high
regioselectivity (Scheme 1b).10 However, these emerging methods utilize palladium
catalysts in combination with stoichiometric oxidants, such as BQ, DDQ, PhI(OAc)2,
CuII , etc. Replacement of these oxidants with molecular oxygen represents a
fundamental challenge that has important implications for environmentally benign
and potential synthetic applications of these methods.11
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Ether compounds serve as versatile reactants in classical organic reactions or
protecting reagents in organic synthesis.12 Accordingly, many methods for the
construction of ethers have been wellꢀdeveloped in recent years.13 Generally, the
traditional coupling of alkali metal alkoxide and alkyl halide predominated the
synthesis of ether compounds due to its practicability.14 In 2014, Hu’s group
presented a stepꢀeconomic conversion of cinnamylbromide to the corresponding
allylethers.15 However, the harsh reaction conditions and requirement of leaving
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groups prohibited their applications in organic synthesis. Based on our enduring
interest in palladiumꢀcatalyzed aerobic oxidative allylic CꢀH functionalization, we
present an atomꢀeconomic and concise strategy for the synthesis of (E)ꢀallylethers via
palladiumꢀcatalyzed oxidative allylic CꢀH oxygenation of olefins with alcohols or
phenols with the employment of atmospheric pressure of oxygen as the sole oxidant
(Scheme 1c).
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Scheme 1. Pdꢀcatalyzed oxidative allylic C–H functionalization
RESULTS AND DISCUSSION
Table 1. Screening reactions for the synthesis of (E)ꢀallylether a
Entry
Catalyst
Pd(OAc)2
PdCl2
Oxidant
O2
Solvent
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Yield (%)b
1
2
3
4
5
6
7
8
41
30
8
O2
Pd(TFA)2
Pd(CH3CN)2Cl2
Pd(allyl)2Cl2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
O2
O2
trace
7
O2
DDQ
BQ
5
trace
9
PhI(OAc)2
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Pd(OAc)2
K2S2O8
O2
DMSO
8
17
10
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
DMA
Toluene
DMF
11
O2
trace
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12
O2
13
O2
1,4ꢀDioxane
DMSO
16
14c
15d
16e
O2
21
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O2
DMSO
DMSO
90
O2
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a
Unless otherwise noted, all reactions were performed with 1a (0.25 mmol), 2a (0.25 mL), Pd
catalyst (10 mol %), oxidant (1 equiv) or O2 balloon in the indicated anhydrous solvent (1.0 mL)
o
b
c
at 100 C for 24 h. Determined by GC using dodecane as the internal standard. The reaction
was performed at 120 oC. d The reaction was performed at 80 oC; e The reaction was performed at
60 oC.
We began our study by investigating the model reaction with allylbenzene (1a) and
nꢀbutanol (2a). Initially, various palladium catalysts were examined including PdCl2,
Pd(TFA)2, Pd(PhCN)2Cl2, and Pd(allyl)2Cl2, and they were less effective than
Pd(OAc)2 (Table 1, entries 1ꢀ5). Furthermore, the screening of oxidants, such as DDQ,
BQ, PhI(OAc)2 and K2S2O8, revealed that the molecular oxygen promoted this
oxygenation reaction dramatically (Table 1, entries 6ꢀ10). Moreover, based on our
initial works, the intermediate allylpalladium complex would be captured by water
rather than alcohol in the presence of water.9 Therefore, various anhydrous solvents
were used for this transformation (Table 1, entries 1, 10ꢀ13), and DMSO was
identified as the optimal solvent for the formation of 3a. Further attempts to optimize
the reaction condition by increasing temperature were unsuccessful (Table 1, entry 14).
Fortunately, decreasing the temperature resulted in higher yields of the desired
product (Table 1, entries 15 and 16). Thus, the optimal condition was obtained as
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Pd(OAc)2 (10 mol %) in anhydrous DMSO (2.0 mL) at 80 oC under molecular oxygen
(1 atm) for 24 h.
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After establishing the optimized reaction conditions, the generality and substrate
scope of olefins and alcohol derivatives were investigated, and the results are
summarized in Scheme 2. Gratifyingly, the allylbenzenes were amenable to a range of
electronꢀdonating groups or electronꢀdeficient groups at the aromatic ring to generate
the desired products (3b-3i) in moderate to good yields. Remarkably, the reaction of
4ꢀCl substituted allylbenzene proceeded effectively and afforded the corresponding
product 3g in good yield, highlighting the compatibility of this reaction. Additionally,
2ꢀnaphthylpropene (1j) could be transformed to the desired product in 83% yield.
Furthermore, a series of alcohols were also found to be suitable substrates under the
optimized conditions. The substrates of cyclobutanol (2k), cyclopentꢀ3ꢀenꢀ1ꢀol (2l),
cyclopentanol (2m), cyclohexanol (2n) and cycloheptanol (2o) were all allowed to
react with 1a, affording the corresponding (E)ꢀallylether derivatives 3k-3o in good
yields. It is noteworthy that 2ꢀadamantanol (2s), Lꢀmenthol (2t) and benzyl alcohol
(2u) could also undergo this transformation, furnishing the desired allylic ester
products in 48% , 56% and 72% yields, respectively.
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Scheme 2. Substrate scope of various allylbenzenes and alcohols a, b
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a
Unless otherwise noted, all reactions were performed with 1 (0.25 mmol), 2 (0.25 mL),
Pd(OAc)2 (10 mol %), in anhydrous DMSO (1.0 mL) with O2 balloon at 80 oC for 24 h. b Isolated
yields based on 1.
Subsequently, for further demonstrating the synthetic potential of this
transformation, various phenols were introduced to this oxygenation reaction. Under
the optimal conditions for alcohols, a trace amount of 5a was detected by GCꢀMS.
Encouraged by this result, efforts were made to optimize the reaction conditions. As
shown in Table 2, a range of Pd salts were examined, which demonstrated the
effectiveness of Pd2(dba)3 as the catalyst, while a survey of solvents indicated that
toluene was the most valid for this reaction (Table 2, entry 5). Subsequently, after the
investigation of different ligands, PPh3 was found to be the superior choice compared
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to dppf, dppe, 1,2ꢀbis(phenylsulfinyl)ethane, 1,2ꢀbis(phenylsulphonyl)ethane and
5
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7
o
4,4'ꢀbipyridine (Table 2, entries 11ꢀ16). Finally, declining the temperature to 50 C
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gave higher yield of 5a (Table 2, entries 17 and 18).
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Table 2. Screening reaction conditions for the synthesis of (E)ꢀallylethers a
Entry
1
Catalyst
Pd(OAc)2
PdCl2
Ligand
Solvent
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Yield (%)b
N.D.
N.D.
N.D.
N.D.
18
ꢀ
2
ꢀ
3
Pd(TFA)2
Pd(CH3CN)2Cl2
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
ꢀ
4
ꢀ
5
ꢀ
6
ꢀ
17
7
ꢀ
DMA
12
8
ꢀ
Toluene
MeCN
30
9
ꢀ
25
10
11
12
13
ꢀ
1,4ꢀDioxane
Toluene
Toluene
Toluene
trace
67
PPh3
dppf
36
dppe
1,2ꢀbis(phenylsulfinyl)et
hane
45
14
15
Pd2(dba)3
Pd2(dba)3
Toluene
Toluene
trace
trace
1,2ꢀbis(phenylsulphonyl)
ethane
16
17c
18d
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
4,4'ꢀbipyridine
PPh3
Toluene
Toluene
Toluene
trace
79
PPh3
91
a
Unless otherwise noted, all reactions were performed with 1a (0.25 mmol), 4a (0.1 mmol), Pd
catalyst (10 mol %), and ligand (1 equiv) in the indicated solvent (1.0 mL) with O2 balloon at 100
oC for 24 h. b Determined by isolated yields. N.D. = not detected. c The reaction was performed at
80 oC; d The reaction was performed at 50 oC
.
With the above reaction conditions in hand, we sought to explore the scope and
generality of different olefins. Representative results are summarized in Scheme 3.
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Generally, this process is compatible with a range of allylbenzenes with
electronꢀdonating groups, giving products 5bꢀ5c in good yields. Different
allylbenzenes with electronꢀdeficient groups (5d, 5f) are also tolerated in this process.
Pleasingly, the reaction of 1ꢀallylnaphthalene (1h) proceeded efficiently to give the
desired product 5h. Additionally, it is noteworthy that another impressive feature of
the current procedure is its high tolerance for αꢀmethylstyrene (5i). Subsequently, a
series of phenols were also found to be suitable in this transformation. Phenols with
electronꢀwithdrawing (5jꢀ5l) and ꢀdonating groups (5mꢀ5n) are perfectly compatible
with the established reaction conditions. Carvacrol (4p) and sesamol (4r) were
allowed to react with 1a, affording the corresponding (E)ꢀallylether derivatives in
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good
yields.
Moreover,
2,3ꢀdihydroꢀ1Hꢀindenꢀ5ꢀol
(4s)
and
5,6,7,8ꢀtetrahydronaphthalenꢀ2ꢀol (4t) smoothly converted into the desired products in
80% and 83% yields, respectively.
Scheme 3. Substrate scope of various olefins and phenols a, b
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5
Pd2(dba)3 (10 mol %)
PPh3 (20 mol %)
R2
R3
R1
O
R1
HO
R3
O2 balloon, Toluene
R2
6
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4
5
7
8
tBu
tBu
tBu
tBu
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O
O
O
O
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Me
F
Me
5d, 68%
5c, 81%
5a, 88%
5b, 78%
tBu
tBu
Me
tBu
tBu
O
O
O
O
F3C
tBu
MeO
Me
5g, 90%
5h, 79%
5f, 66%
5e, 83%
OMe
OPh
O
O
O
O
5k, 75%
5l, 69%
5j, 91%
5i, 62%
Cl
CF3
O
O
iPr
O
O
Ph
5p, 82%
5m, 90%
5n, 61%
5o, 71%
O
O
O
O
O
O
5s, 80%
5q, 91%
5r, 72%
5t, 83%
a
Unless otherwise noted, all reactions were performed with 1 (0.25 mmol), 4 (0.1 mmol),
Pd2(dba)3 (10 mol %), PPh3 (20 mol %) in toluene (1.0 mL) with O2 balloon at 80 C for 24 h. b
o
Isolated yields based on 4.
Scheme 4. Proposed Mechanism
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On the basis of the current results and previous literatures, we proposed a plausible
mechanism as shown in Scheme 4. Initially, palladium coordinated with olefins to
generate the intermediate 5 . Next, the corresponding πꢀallylpalladium species II was
formed by the oxidative cleavage of allylic CꢀH bond.16ꢀ17 Subsequently, alcohols or
phenols would undergo nucleophilic attacking to the πꢀallylpalladium species.1hꢀi, 18
Finally, (E)ꢀallylether was obtained through the reductive elimination process.
Similarly, oxygen played a vital role in the regeneration of the active PdII species.19
In conclusion, we have developed an efficient approach to expedient and
regioselective synthesis of (E)ꢀallylethers from readily available olefins and alcohols
or phenols via palladiumꢀcatalyzed aerobic oxidative allylic CꢀH oxygenation. This
transformation provides a new synthetic strategy for the construction of
(E)ꢀallylethers from simple starting materials with broad substrate scope and excellent
functional group tolerance.
Experimental Section
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General method. Melting points were measured using a melting point instrument and
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1
are uncorrected. H and 13C NMR spectra were recorded on a 400 MHz NMR
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spectrometer. The chemical shifts are referenced to signals at 7.24 and 77.0 ppm,
respectively, and chloroform was used as a solvent with TMS as the internal standard.
IR spectra were obtained with an infrared spectrometer on either potassium bromide
pellets or liquid films between two potassium bromide pellets. GC−MS data were
obtained using electron ionization. HRMS was carried out on a highꢀresolution mass
spectrometer (LCMSꢀITꢀTOF). TLC was performed using commercially available
100−400 mesh silica gel plates (GF254). Unless otherwise noted, purchased chemicals
were used without further purification.
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General procedure for synthesis of (E)-allylethers 3: olefin derivatives (0.25
mmol), Pd(OAc)2 (10 mol %, 0.025 mmol), and alcohol derivatives (0.25 mL) were
added to anhydrous DMSO (1 mL). The mixture was stirred with O2 balloon at 80 oC
for the desired reaction time. After that, water was added and extracted with ethyl
acetate twice. The combined organic phase was dried over MgSO4 and concentrated.
The residue was eventually purified by flash column chromatography on a silica gel
(hexanes/ethyl acetate) to afford the product.
General procedure for synthesis of (E)-allylether (5): olefin derivatives (0.25
mmol), Pd2(dba)3 (10 mol %, 0.010 mmol), PPh3 (20 mol %) and phenol derivatives
(0.1 mmol) were added to toluene (1 mL). The mixture was stirred under with O2
o
balloon at 50 C for the desired reaction time. After that, water was added and
extracted with ethyl acetate twice. The combined organic phase was dried over
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MgSO4 and concentrated. The residue was eventually purified by flash column
chromatography on a silica gel (hexanes/ethyl acetate) to afford the product.
(E)-(3-Butoxyprop-1-en-1-yl)benzene (3a)10: Yield: 88% (41.8 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.39 (d, J =8.0 Hz, 2H), 7.31 (t, J =
7.6 Hz, 2H), 7.23 (dd, J = 12.0, 4.2 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, 6.0 Hz,
1H), 4.13 (d, J = 6.0 Hz, 2H), 3.48 (t, J = 6.6 Hz, 2H), 1.65 ꢀ 1.56 (m, 2H), 1.40 (dd, J = 14.4, 7.2
Hz, 2H), 0.93 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 136.8, 132.1, 128.5, 127.6,
126.5, 71.8, 70.9, 70.3, 31.9, 19.4, 14.0 ppm; νmax(KBr)/cmꢀ1 2930, 2835, 1720, 1425, 1099, 745.
MS (EI) m/z 57, 78, 91, 104, 119, 130, 190.
(E)-1-(3-Butoxyprop-1-en-1-yl)-4-methylbenzene (3b)10: Yield: 81% (41.3 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.31 ꢀ 7.24 (m, 2H), 7.11 (d, J = 7.2
Hz, 2H), 6.56 (d, J = 16.0 Hz, 1H), 6.31 ꢀ 6.19 (m, 1H), 4.11 (d, J = 6.0 Hz, 2H), 3.47 (t, J = 6.4
Hz, 2H), 2.33 (s, 2H), 1.59 (t, J = 10.0 Hz, 2H), 1.40 (dq, J = 14.4, 7.2 Hz, 2H), 0.93 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 137.4, 134.1, 132.1, 129.2, 126.4, 125.4, 71.5, 70.2, 31.9,
21.2, 19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2925, 2845, 1652, 1450, 1117, 739; HRMSꢀESI (m/z): calcd
for C14H20ONa, [M+Na]+: 227.1406, found 227.1408.
(E)-1-(3-Butoxyprop-1-en-1-yl)-2-methylbenzene (3c): Yield: 84% (42.8 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 4.0 Hz, 1H), 7.14 (s, 3H),
6.81 (d, J = 16.0 Hz, 1H), 6.18 (dt, J = 16.0, 6.0 Hz, 1H), 4.15 (d, J = 6.0 Hz, 2H), 3.49 (t, J = 6.4
Hz, 2H), 1.65 ꢀ 1.54 (m, 2H), 1.40 (dt, J = 14.4, 7.2 Hz, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 135.9, 135.4, 130.2, 129.9, 127.8, 127.5, 126.1, 125.8, 71.6, 70.2, 31.9, 19.8,
19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2924, 2853, 1651, 1457, 1265, 740. HRMSꢀESI (m/z): calcd for
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C14H20ONa, [M+Na]+: 227.1406, found 227.1405.
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(E)-1-(3-Butoxyprop-1-en-1-yl)-3-methylbenzene (3d)10: Yield: 82% (41.8 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.19 (d, J = 5.4 Hz, 1H), 7.05 (d, J =
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4.0 Hz, 3H), 6.57 (d, J = 16.0 Hz, 1H), 6.28 (dt, J = 16.0, 6.0 Hz, 1H), 4.12 (d, J = 6.0 Hz, 1H),
3.48 (t, J = 6.6 Hz, 2H), 2.34 (s, 3H), 1.64 ꢀ 1.56 (m, 2H), 1.40 (dq, J = 14.4, 7.2 Hz, 2H), 0.93 (t,
J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 138.1, 136.8, 132.2, 128.4, 127.2, 126.3, 123.6,
71.4, 70.2, 31.9, 21.4, 19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2931, 2890, 1641, 1330, 1160, 744.
HRMSꢀESI (m/z): calcd for C14H20ONa, [M+Na]+: 227.1406, found 227.1403.
(E)-1-(3-Butoxyprop-1-en-1-yl)-4-fluorobenzene (3e)10: Yield: 55% (28.6 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.34 (dd, J = 8.0, 5.6 Hz, 2H), 6.99 (t,
J = 8.4 Hz, 2H), 6.56 (d, J = 16.0 Hz, 1H), 6.21 (dt, J = 16.0, 6.0 Hz, 1H), 4.11 (d, J = 6.0 Hz, 2H),
3.48 (t, J = 6.4 Hz, 2H), 1.65 ꢀ 1.53 (m, 2H), 1.46 ꢀ 1.34 (m, 1H), 0.93 (t, J = 7.23 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 162.3 (d, J = 245.2 Hz), 133.0, 130.9, 127.9 (d, J = 8.0 Hz), 126.2 (d,
J = 2.1 Hz), 115.4 (d, J = 21.6 Hz), 71.30, 70.3, 31.9, 19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2920, 2851,
1730, 1459, 1009, 730. HRMSꢀESI (m/z): calcd for C13H17OFNa, [M+Na]+: 231.1156, found
231.1156.
(E)-1-(3-Butoxyprop-1-en-1-yl)-4-chlorobenzene (3f)10: Yield: 79% (44.3 mg) as a yellow oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.29 (dd, J = 15.2, 8.4 Hz, 4H), 6.55
(d, J = 16.0 Hz, 1H), 6.27 (dt, J = 16.0, 6.0 Hz, 1H), 4.11 (d, J = 6.0 Hz, 2H), 3.48 (t, J = 6.4 Hz,
2H), 1.64 ꢀ 1.55 (m, 2H), 1.47 ꢀ 1.34 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 135.4, 133.2, 130.7, 128.7, 127.7, 127.2, 71.2, 70.4, 31.9, 19.4, 13.9 ppm;
νmax(KBr)/cmꢀ1 2935, 2845, 1720, 1415, 1118, 730; HRMSꢀEI (m/z): calcd for C13H17ClO,
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[M+Na]+: 224.0968, found 224.0961.
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(E)-1-(3-Butoxyprop-1-en-1-yl)-4-(trifluoromethyl)benzene (3g): Yield: 82% (52.9 mg) as a
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yellow oil; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.0 Hz, 2H),
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7.47 (d, J = 8.0 Hz, 2H), 6.64 (d, J = 16.0 Hz, 1H), 6.39 (dt, J = 16.0, 6.0 Hz, 1H), 4.15 (d, J = 5.6
Hz, 1H), 3.50 (t, J = 6.6 Hz, 2H), 1.66 ꢀ 1.56 (m, 2H), 1.40 (dt, J = 14.4, 7.2 Hz, 1H), 0.94 (t, J =
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 140.4, 130.2, 129.5, 129.4, 129.2, 126.6, 125.5 (dd, J
= 7.7, 3.9 Hz), 70.9, 70.6, 31.8, 19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2928, 2860, 1639, 1325, 1166,
741; HRMSꢀEI (m/z): calcd for C14H17F3O, [M+Na]+: 258.1231, found 258.1225.
(E)-1-(3-Butoxyprop-1-en-1-yl)-3,5-dimethylbenzene (3h): Yield: 85% (46.3 mg) as colorless
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oil; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.01 (s, 2H), 6.88 (s, 1H), 6.53
(d, J = 16.0 Hz, 1H), 6.26 (dt, J = 16.0, 6.0 Hz, 1H), 4.12 (d, J = 6.0 Hz, 2H), 3.47 (t, J = 6.4 Hz,
2H), 2.30 (s, 6H), 1.62 ꢀ 1.53 (m, 2H), 1.39 (dt, J = 14.4, 7.2 Hz, 2H), 0.93 (t, J = 7.2 Hz, 3H); 13
C
NMR (100 MHz, CDCl3) δ 137.9, 136.7, 132.3, 129.3, 126.1, 124.4, 71.5, 70.1, 31.9, 21.2, 19.4,
13.9 ppm; νmax(KBr)/cmꢀ1 2956, 2923, 2856, 1639, 747. HRMSꢀESI (m/z): calcd for C15H22ONa,
[M+Na]+: 241.1563, found 241.1569.
(E)-4-(3-Butoxyprop-1-en-1-yl)-1,2-dimethoxybenzene (3i): Yield: 65% (40.6 mg) as colorless
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oil; hexanes/ethyl acetate =25:1; H NMR (400 MHz, CDCl3) δ 6.90 ꢀ 6.81 (m, 2H), 6.74 (d, J =
8.0 Hz, 1H), 6.46 (d, J = 16.0 Hz, 1H), 6.10 (dt, J = 16.0, 6.0 Hz, 1H), 4.04 (d, J = 5.4 Hz, 2H),
3.81 (d, J = 6.0 Hz, 6H), 3.41 (t, J = 6.4 Hz, 2H), 1.58 ꢀ 1.46 (m, 2H), 1.33 (dq, J = 14.4, 7.2 Hz,
2H), 0.86 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 149.0, 148.9, 131.9, 129.9, 124.5,
119.7, 111.1, 108.9, 71.5, 70.2, 55.9, 55.8, 31.9, 19.4, 13.9 ppm; νmax(KBr)/cmꢀ1 2928, 2860, 1639,
1325, 967, 741; HRMSꢀESI (m/z): calcd for C15H22O3Na, [M+Na]+: 273.1461, found 273.1459.
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(E)-2-(3-Butoxyprop-1-en-1-yl)naphthalene (3j)10: Yield: 83% (49.8 mg) as colorless oil;
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hexanes/ethyl acetate =100 :1; H NMR (400 MHz, CDCl3) δ 7.78 (t, J = 6.4 Hz, 3H), 7.73 (s, 1H),
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1H), 4.18 (d, J = 6.0 Hz, 2H), 3.51 (t, J = 6.4 Hz, 2H), 1.61 (dd, J = 17.2, 10.4 Hz, 2H), 1.43 (dt, J
= 14.4, 7.2 Hz, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 134.3, 133.6, 133.0,
132.1, 128.2, 127.9, 127.7, 126.9, 126.4, 126.2, 125.9, 123.7, 71.5, 70.4, 31.9, 19.4, 13.9 ppm;
νmax(KBr)/cmꢀ1 2933, 2860, 1714, 1425, 1089, 729. HRMSꢀESI (m/z): calcd for C17H20ONa,
[M+Na]+: 263.1406, found 263.1404.
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(E)-(3-Cyclobutoxyprop-1-en-1-yl)benzene (3k): Yield: 68% (31.9 mg) as colorless oil;
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hexanes/ethyl acetate =100 :1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.0 Hz, 2H), 7.30 (t, J =
7.2 Hz, 2H), 7.23 (dd, J = 12.0, 5.4 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H), 6.28 (dt, J = 16.0, 6.0 Hz,
1H), 4.05 (d, J = 6.0 Hz, 2H), 4.02 ꢀ 3.97 (m, 1H), 2.23 (dd, J = 16.0, 7.8 Hz, 2H), 1.98 (q, J = 9.2
Hz, 2H), 1.71 (q, J = 10.2 Hz, 1H), 1.51 (dd, J = 18.8, 9.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ 136.8, 132.2, 128.5, 127.6, 126.5, 126.4, 72.8, 68.5, 30.6 , 12.6 ppm; νmax(KBr)/cmꢀ1 2922, 2854,
1640, 1459, 768, 729; HRMSꢀESI (m/z): calcd for C13H16ONa, [M+Na]+: 211.1093, found
211.1093.
(E)-(3-(Cyclopent-3-en-1-yloxy)prop-1-en-1-yl)benzene (3l): Yield: 70% (35.0 mg) as colorless
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oil; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 1H), 7.30 (t,
J = 7.2 Hz, 1H), 7.22 (t, J = 7.2 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, 6.0 Hz, 1H),
5.70 (s, 1H), 4.31 (d, J = 2.4 Hz, 1H), 4.14 (d, J = 6.0 Hz, 1H), 2.61 (dd, J = 16.0, 6.0 Hz, 1H),
2.44 (d, J = 17.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 136.8, 132.1, 128.5, 128.4, 127.6, 126.5,
126.5, 78.8, 69.5, 39.3 ppm; νmax(KBr)/cmꢀ1 2922, 2853, 1642, 1265, 965, 741; HRMSꢀESI (m/z):
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calcd for C14H16ONa, [M+Na]+: 223.1093, found 223.1087.
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(E)-(3-(Cyclopentyloxy)prop-1-en-1-yl)benzene (3m)13e: Yield: 55% (27.8 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.6 Hz, 2H), 7.30 (t, J =
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7.6 Hz, 2H), 7.22 (t, J = 7.2 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H), 6.29 (dt, J = 16.0, 6.0 Hz, 1H),
4.10 (d, J = 6.0 Hz, 2H), 4.00 (s, 1H), 1.78 ꢀ 1.68 Hz (m, 6H), 1.53 (d, J = 6.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 136.9, 131.8, 128.5, 127.5, 126.9, 126.5, 80.9, 69.5, 32.4, 23.6 ppm;
νmax(KBr)/cmꢀ1 3027, 2954, 1639, 1169, 965, 734; HRMSꢀESI (m/z): calcd for C14H18ONa,
[M+Na]+: 225.1250, found 225.1244.
(E)-(3-(Cyclohexyloxy)prop-1-en-1-yl)benzene (3n)13a: Yield: 63% (34.0 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 2H), 7.30 (t, J =
7.2 Hz, 2H), 7.22 (t, J = 7.2 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, 6.0 Hz, 1H),
4.17 (d, J = 6.0 Hz, 2H), 3.34 (td, J = 8.8, 4.0 Hz, 1H), 1.95 (d, J = 12.0 Hz, 2H), 1.76 (d, J = 6.0
Hz, 2H), 1.55 (dd, J = 14.4, 8.0 Hz, 1H), 1.37 ꢀ 1.28 (m, 3H), 1.21 (d, J = 13.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 136.9, 131.6, 128.5, 127.5, 127.2, 126.5, 68.4, 32.4, 25.8, 24.2 ppm;
νmax(KBr)/cmꢀ1 2925, 2855, 1724, 1455, 1112, 738; MS (EI) m/z 55, 91, 92, 105, 117, 134, 216.
(E)-(3-(Cycloheptyloxy)prop-1-en-1-yl)benzene (3o): Yield: 59% (33.9 mg) as a yellow oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.0 Hz, 2H), 7.30 (t, J =
7.2 Hz, 2H), 7.21 (t, J = 7.2 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H), 6.29 (dt, J = 16.0, 6.0 Hz, 1H),
4.13 (d, J = 6.0 Hz, 2H), 3.59 ꢀ 3.45 (m, 1H), 2.00 ꢀ 1.85 (m, 2H), 1.72 ꢀ 1.60 (m, 5H), 1.54 (s,
4H), 1.43 ꢀ 1.34 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 137.0, 131.5, 128.5, 127.5, 127.2, 126.5,
79.6, 68.8, 33.9, 28.5, 23.0 ppm; νmax(KBr)/cmꢀ1 2935, 2850, 1714, 1450, 960, 740; HRMSꢀESI
(m/z): calcd for C16H22ONa, [M+Na]+: 253.1563, found 253.1556.
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(Cinnamyloxy)cyclooctane (3p): Yield: 61% (37.2 mg) as a colorless oil; hexanes/ethyl acetate
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=100:1; H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.0 Hz, 2H), 7.27 (t, J = 8.0 Hz, 2H), 7.19 (dd,
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J = 8.0, 6.0 Hz, 1H), 6.57 (d, J = 16.0 Hz, 1H), 6.28 (dd, J = 16.0, 6.0 Hz, 1H), 4.11 (dd, J = 6.0,
1.2 Hz, 2H), 3.52 ꢀ 3.48 (m, 1H), 1.88 ꢀ 1.81 (m, 2H), 1.77 ꢀ 1.66 (m, 4H), 1.62 ꢀ 1.39 (m, 8H);
13C NMR (100 MHz, CDCl3) δ 136.8, 131.4, 128.3, 127.3, 127.0, 126.3, 79.1, 68.6, 31.4, 27.3,
25.4, 23.0 ppm; HRMSꢀESI (m/z): calcd for C17H24ONa, [M+Na]+: 267.1719, found 267.1722.
(Cinnamyloxy)cyclododecane (3q): Yield: 55% (41.3 mg) as a colorless oil; hexanes/ethyl
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acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.0 Hz, 2H), 7.19 (t, J = 8.0 Hz, 2H),
7.11 (dd, J = 10.0, 4.0 Hz, 1H), 6.50 (d, J = 16.0 Hz, 1H), 6.19 (dt, J = 16.0, 6.0 Hz, 1H), 4.04 (dd,
J = 6.0, 0.8 Hz, 2H), 3.45 ꢀ 3.41 (m, 1H), 1.59 ꢀ 1.52 (m, 2H), 1.45 ꢀ 1.39 (m, 2H), 1.35 ꢀ 1.24 (m,
18H); 13C NMR (100 MHz, CDCl3) δ 136.9, 131.6, 128.4, 127.3, 127.0, 126.3, 76.3, 68.9, 28.8,
24.6, 24.2, 23.1, 23.0, 20.6 ppm; HRMSꢀESI (m/z): calcd for C21H32ONa, [M+Na]+: 323.2345,
found 323.2350.
(Cinnamyloxy)cyclopentadecane (3r): Yield: 50% (42.8 mg) as a colorless oil; hexanes/ethyl
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acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 8.0 Hz, 2H), 7.28 (t, J = 8.0 Hz, 2H),
7.22 ꢀ 7.18 (m, 1H), 6.58 (d, J = 16.0 Hz, 1H), 6.28 (dt, J = 16.0, 5.6 Hz, 1H), 4.12 (d, J = 4.0 Hz,
2H), 3.40 (p, J = 5.8 Hz, 1H), 1.59 ꢀ 1.55 (m, 4H), 1.37 ꢀ 1.26 (m, 24H); 13C NMR (100 MHz,
CDCl3) δ 136.9, 131.6, 128.4, 127.4, 127.0, 126.4, 77.9, 68.9, 31.9, 27.4, 26.8, 26.7, 26.6, 26.5,
23.1 ppm; HRMSꢀESI (m/z): calcd for C24H38ONa, [M+Na]+: 365.2815, found 365.2811.
(1r,3r,5r,7r)-2-(Cinnamyloxy)adamantane (3s): Yield: 48% (32.2 mg) as a colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.0 Hz, 2H), 7.21 (t, J =
8.0 Hz, 2H), 7.14 ꢀ 7.10 (m, 1H), 6.53 (d, J = 16.0 Hz, 1H), 6.24 (dt, J = 16.0, 5.6 Hz, 1H), 4.07
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(dd, J = 5.6, 1.2 Hz, 2H), 3.44 (s, 1H), 2.04 ꢀ 1.97 (m, 4H), 1.78 ꢀ 1.72 (m, 4H), 1.63 ꢀ 1.56 (m,
4H), 1.41 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 136.9, 131.1, 128.4, 127.3, 126.4,
81.1, 67.9, 37.6, 36.5, 31.8, 31.5, 27.4, 27.4 ppm; HRMSꢀESI (m/z): calcd for C19H24ONa,
[M+Na]+: 291.1719, found 291.1721.
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((E)-3-(((1S,2S,4R)-2-Isopropyl-4-methylcyclohexyl)oxy)prop-1-en-1-yl)benzene (3t)13a: Yield:
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56% (38.1 mg) as colorless oil; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.38
(d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.2 Hz, 2H), 7.22 (t, J = 7.2 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H),
6.30 (dt, J = 16.0, 6.0 Hz, 1H), 4.29 (dd, J = 12.6, 6.0 Hz, 1H), 4.06 (dd, J = 12.0, 6.0 Hz, 1H),
3.14 (td, J = 10.0, 4.0 Hz, 1H), 2.27 (dd, J = 13.4, 6.6 Hz, 1H), 2.14 (d, J = 12.0 Hz, 1H), 1.62 (dd,
J = 26.2, 16.0 Hz, 4H), 1.05 ꢀ 0.86 (m, 9H), 0.84 ꢀ 0.74 (m, 4H); 13C NMR (100 MHz, CDCl3) δ
136.9, 131.7, 128.5, 127.5, 127.2, 126.5, 78.7, 69.1, 48.3, 40.6, 34.6, 31.6, 25.6, 23.4, 22.4, 21.0,
16.3 ppm; νmax(KBr)/cmꢀ1 3045, 2921, 2854, 1600, 1489, 835, 767, 693; HRMSꢀESI (m/z): calcd
for C19H28ONa, [M+Na]+: 295.2032, found 295.2025.
(E)-(3-(benzyloxy)prop-1-en-1-yl)benzene (3u)13a: Yield: 72% (40.3 mg) as colorless oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.52 ꢀ 7.44 (m, 6H), 7.40 (t, J = 8.0
Hz, 3H), 7.32 (t, J = 8.0 Hz, 1H), 6.72 (d, J = 16.0 Hz, 1H), 6.42 (dt, J = 16.0, 6.0 Hz, 1H), 4.66 (s,
2H), 4.28 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 138.3, 136.7, 132.4, 128.5, 128.3,
127.7, 127.6, 127.6, 126.4, 126.1, 72.1, 70.9.ppm; νmax(KBr)/cmꢀ1 3025, 2928, 1714, 1450, 757,
673.
1-(tert-Butyl)-4-(cinnamyloxy)benzene (5a) 13f:Yield: 88% (23.4 mg) as yellow solid; mp = 77 ꢀ
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78 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.35 ꢀ 7.31 (m, 2H), 7.26 ꢀ
7.22 (m, 4H), 7.19 ꢀ 7.16 (m, 2H), 6.85 ꢀ 6.80 (m, 1H), 6.65 (d, J = 16.0 Hz, 1H), 6.34 (dt, J =
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16.0, 6.0 Hz, 1H), 4.61 (dd, J = 6.0, 1.6 Hz, 2H), 1.23 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
156.4, 143.6, 136.5, 132.8, 128.6, 127.8, 126.6, 126.2, 124.8, 114.3, 68.7, 34.1, 31.5 ppm;
νmax(KBr)/cmꢀ1 3632, 2964, 1724, 1628, 1254, 1143, 1074, 751; HRMSꢀESI (m/z): calcd for
C19H22ONa, [M+Na]+: 289.1563, found 289.1558.
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(E)-1-(3-(4-(tert-Butyl)phenoxy)prop-1-en-1-yl)-2-methylbenzene (5b): Yield: 78% (21.8 mg)
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as yellow solid; mp = 73 ꢀ 74 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ
7.48 (dd, J = 5.0, 3.6 Hz, 1H), 7.35 ꢀ 7.33 (m, 1H), 7.32 ꢀ 7.30 (m, 1H), 7.20 ꢀ 7.14 (m, 3H), 6.99 ꢀ
6.88 (m, 3H), 6.31 (dt, J = 16.0, 6.0 Hz, 1H), 4.72 (dd, J = 6.0, 1.6 Hz, 2H), 2.35 (s, 3H), 1.32 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 156.4, 143.6, 135.7, 135.6, 130.9, 130.3, 127.7, 126.3, 126.1,
126.1, 125.9, 114.4, 68.9, 34.1, 31.5, 19.6 ppm; νmax(KBr)/cmꢀ1 3485, 2963, 1723, 1624, 1251,
1141, 803, 750; HRMSꢀESI (m/z): calcd for C20H24ONa, [M+Na]+: 303.1719, found 303.1720.
(E)-1-(tert-Butyl)-4-((3-(p-tolyl)allyl)oxy)benzene (5c): Yield: 81% (22.7 mg) as yellow solid;
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mp = 110 ꢀ 111 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.34 ꢀ 7.30 (m,
4H), 7.14 (d, J = 8.0 Hz, 2H), 6.93 ꢀ 6.91 (m, 1H), 6.91 ꢀ 6.88 (m, 1H), 6.71 (d, J = 16.0 Hz, 1H),
6.38 (dt, J = 16.0, 6.0 Hz, 1H), 4.68 (dd, J = 6.0, 1.6 Hz, 2H), 2.35 (s, 3H), 1.32 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 156.4, 143.5, 137.7, 133.7, 132.9, 129.3, 126.5, 126.2, 123.7, 114.3, 68.8,
34.1, 31.5, 21.2 ppm; νmax(KBr)/cmꢀ1 3035, 2954, 2862, 1604, 1509, 1240, 1185, 1005;
HRMSꢀESI (m/z): calcd for C20H24ONa, [M+Na]+: 303.1719, found 303.1714.
(E)-1-(tert-Butyl)-4-((3-(4-fluorophenyl)allyl)oxy)benzene (5d): Yield: 68%; (19.3 mg) as
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yellow solid; mp = 114 ꢀ 115 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ
7.41 ꢀ 7.36 (m, 2H), 7.34 ꢀ 7.29 (m, 2H), 7.05 ꢀ 6.98 (m, 2H), 6.93 ꢀ 6.88 (m, 2H), 6.70 (d, J =
16.0 Hz, 1H), 6.35 (dt, J = 16.0, 6.0 Hz, 1H), 4.68 (dd, J = 6.0, 1.6 Hz, 2H), 1.31 (s, 9H); 13C
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NMR (100 MHz, CDCl3) δ 162.5 (d, J = 247.2 Hz), 156.4, 143.7, 132.7 (d, J = 3.3 Hz), 131.7,
128.1 (d, J = 8.0 Hz), 126.3, 124.6 (d, J = 2.2 Hz), 115.49 (d, J = 21.7 Hz), 114.2, 68.6, 34.1, 31.5
ppm; νmax(KBr)/cmꢀ1 3459, 3059, 2959, 2862, 1612, 1507, 1237, 1015; HRMSꢀESI (m/z): calcd
for C19H21FONa, [M+Na]+: 307.1469, found 307.1473.
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(E)-1-(tert-Butyl)-4-((3-(4-methoxyphenyl)allyl)oxy)benzene (5e): Yield: 83% (24.6 mg) as
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yellow solid; mp = 125 ꢀ 126 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ
7.40 ꢀ 7.29 (m, 4H), 6.95 ꢀ 6.83 (m, 4H), 6.68 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, 6.0 Hz, 1H),
4.67 (dd, J = 6.0, 1.6 Hz, 2H), 3.82 (s, 3H), 1.32 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 159.4,
156.5, 143.5, 132.6, 129.3, 127.8, 126.2, 122.5, 114.2, 113.9, 68.9, 55.3, 34.1, 31.5 ppm;
νmax(KBr)/cmꢀ1 3546, 2956, 1723, 1610, 1511, 1246, 1011, 833; HRMSꢀESI (m/z): calcd for
C20H24O2Na, [M+Na]+: 319.1669, found 319.1662.
(E)-1-(tert-Butyl)-4-((3-(4-(trifluoromethyl)phenyl)allyl)oxy)benzene (5f): Yield: 66% (22.1
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mg) as yellow solid; mp = 77 ꢀ 78 oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3)
δ 7.57 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.8 Hz, 2H), 6.90 (d, J = 8.8 Hz,
2H), 6.76 (d, J = 16.0 Hz, 1H), 6.51 (dt, J = 16.0, 5.6 Hz, 1H), 4.70 (dd, J = 6.0, 1.6 Hz, 2H), 1.30
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 156.2, 143.8, 140.0, 130.9, 127.6, 126.7, 126.3, 125.5 (dd,
J = 7.5, 3.7 Hz), 114.2, 68.2, 34.1, 31.5 ppm; νmax(KBr)/cmꢀ1 2959, 1608, 1511, 1328, 1235, 1167,
1115, 837; HRMSꢀESI (m/z): calcd for C20H21F3ONa, [M+Na]+: 357.1437, found 357.1441.
(E)-1-(3-(4-(tert-Butyl)phenoxy)prop-1-en-1-yl)-3,5-dimethylbenzene (5g): Yield: 90% (26.5
1
mg) as yellow oil; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.33 ꢀ 7.27 (m,
2H), 7.03 (s, 2H), 6.92 ꢀ 6.86 (m, 3H), 6.65 (d, J = 16.0 Hz, 1H), 6.38 (dt, J = 16.0, 6.0 Hz, 1H),
4.66 (dd, J = 6.0, 1.6 Hz, 2H), 2.30 (s, 6H), 1.30 (s, 9H); 13C NMR (101 MHz, CDCl3) δ 156.4,
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143.5, 137.9, 132.9, 129.6, 126.2, 124.5, 124.4, 114.2, 68.8, 34.1, 31.5, 21.2 ppm; νmax(KBr)/cmꢀ1
3606, 2958, 1724, 1615, 1510, 1245, 1138, 826; HRMSꢀESI (m/z): calcd for C21H26ONa,
[M+Na]+: 317.1876, found 317.1872.
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(E)-2-(3-(4-(tert-Butyl)phenoxy)prop-1-en-1-yl)naphthalene (5h): Yield: 79% (25.0 mg) as
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yellow solid; mp = 83 ꢀ 84 oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 8.10 ꢀ
8.01 (m, 1H), 7.87 ꢀ 7.81 (m, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 7.2 Hz, 1H), 7.46 (m, 4H),
7.33 (d, J = 8.8 Hz, 2H), 6.95 (d, J = 8.8 Hz, 2H), 6.43 (dt, J = 16.0, 5.6 Hz, 1H), 4.79 (d, J = 5.6
Hz, 2H), 1.31 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 156.4, 143.6, 134.3, 133.6, 131.1, 129.9,
128.5, 128.1, 127.9, 126.3, 126.1, 125.8, 125.6, 124.0, 123.8, 114.4, 68.8, 34.1, 31.5 ppm;
νmax(KBr)/cmꢀ1 3542, 3049, 2956, 1510, 1240, 1182, 1015, 781; HRMSꢀESI (m/z): calcd for
C23H24ONa, [M+Na]+: 339.1719, found 339.1721.
1-(tert-Butyl)-4-((2-phenylallyl)oxy)benzene (5i): Yield: 62% (16.5 mg) as yellow oil;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 7.2 Hz, 2H), 7.39 ꢀ 7.30
(m, 6H), 6.92 (d, J = 8.8 Hz, 2H), 5.62 (s, 1H), 5.48 (s, 1H), 4.89 (s, 2H), 1.32 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 156.4, 143.7, 143.2, 138.4, 128.4, 127.9, 126.2, 126.0, 114.8, 114.3, 69.9,
34.1, 31.5 ppm; νmax(KBr)/cmꢀ1 3632, 2956, 1725, 1613, 1509, 1460, 1243, 1023; HRMSꢀESI
(m/z): calcd for C19H22ONa, [M+Na]+: 289.1563, found 289.1567.
(Cinnamyloxy)benzene (5j)13f: Yield: 91% (19.2 mg) as yellow solid; mp = 66 ꢀ 67 oC;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 7.2 Hz, 2H), 7.36 ꢀ 7.17
(m, 5H), 6.94 (dd, J = 13.2, 5.6 Hz, 3H), 6.72 (d, J = 16.0 Hz, 1H), 6.41 (dt, J = 16.0, 6.0 Hz, 1H),
4.68 (dd, J = 6.0, 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 158.6, 136.5, 132.9, 129.5, 128.6,
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127.9, 126.6, 124.6, 120.9, 114.8, 68.5 ppm; νmax(KBr)/cmꢀ1 3057, 2919, 2855, 1587, 1492, 1225,
1008, 744; HRMSꢀESI (m/z): calcd for C15H14ONa, [M+Na]+: 233.0937, found 233.0935.
1-(Cinnamyloxy)-4-methoxybenzene (5k)13g: Yield: 75% (18.0 mg) as yellow solid; mp = 86 ꢀ
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87 oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.42 ꢀ 7.38 (m, 2H), 7.31 (dd,
J = 8.0, 6.4 Hz, 2H), 7.28 ꢀ 7.20 (m, 1H), 6.94 ꢀ 6.86 (m, 2H), 6.86 ꢀ 6.81 (m, 2H), 6.71 (d, J =
16.0 Hz, 1H), 6.40 (dt, J = 16.0, 6.0 Hz, 1H), 4.64 (dd, J = 6.0, 1.6 Hz, 2H), 3.76 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 153.9, 152.8, 136.5, 132.8, 128.6, 127.8, 126.5, 124.8, 115.8, 114.7,
69.4, 55.7 ppm; νmax(KBr)/cmꢀ1 3473, 2918, 2855, 1507, 1451, 1234, 1028, 826; HRMSꢀESI (m/z):
calcd for C16H16O2Na, [M+Na]+: 263.1043, found 263.1045.
1-(Cinnamyloxy)-4-phenoxybenzene (5l): Yield: 69% (20.8 mg) as yellow solid; mp = 103 ꢀ 104
oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.50 ꢀ 7.45 (m, 2H), 7.42 ꢀ 7.28
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(m, 5H), 7.13 ꢀ 7.08 (m, 1H), 7.07 ꢀ 6.98 (m, 6H), 6.80 (d, J = 16.0 Hz, 1H), 6.48 (dt, J = 16.0, 6.0
Hz, 1H), 4.74 (dd, J = 6.0, 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 158.4, 154.9, 150.4, 136.4,
133.0, 129.6, 128.6, 127.9, 126.6, 124.5, 122.5, 120.7, 117.7, 115.8, 69.1 ppm; νmax(KBr)/cmꢀ1
3447, 2922, 1723, 1600, 1240, 964, 748, 692; HRMSꢀESI (m/z): calcd for C21H18O2Na, [M+Na]+:
325.1199, found 325.1197.
1-Chloro-4-(cinnamyloxy)benzene (5m): Yield: 90% (21.9 mg) as yellow solid; mp = 95 ꢀ 96 oC;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.40 ꢀ 7.36 (m, 2H), 7.31 (dd, J = 8.0,
6.8 Hz, 2H), 7.27 ꢀ 7.19 (m, 3H), 6.91 ꢀ 6.81 (m, 2H), 6.70 (d, J = 16.0 Hz, 1H), 6.36 (dt, J = 16.0,
6.0 Hz, 1H), 4.64 (dd, J = 6.0, 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 157.2, 136.3, 133.2,
129.3, 128.6, 127.9, 126.6, 125.7, 123.9, 116.1, 68.9 ppm; νmax(KBr)/cmꢀ1 3456, 2914, 1594, 1491,
1240, 1011, 964, 830;
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1-(Cinnamyloxy)-4-(trifluoromethyl)benzene (5n)13f: Yield: 61% (17.0 mg) as yellow solid; mp
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o
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= 78 ꢀ 79 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.8 Hz,
2H), 7.41 ꢀ 7.38 (m, 2H), 7.32 (dd, J = 10.4, 4.8 Hz, 2H), 7.28 ꢀ 7.22 (m, 1H), 6.99 (d, J = 8.4 Hz,
2H), 6.72 (d, J = 16.0 Hz, 1H), 6.38 (dt, J = 16.0, 6.0 Hz, 1H), 4.71 (dd, J = 6.0, 1.6 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 161.1, 136.2, 133.6, 128.6, 128.1, 126.9 (q, J = 3.7 Hz), 126.6, 123.6,
114.8, 68.8 ppm; νmax(KBr)/cmꢀ1 2925, 1612, 1330, 1252, 1162, 1110, 970, 836;
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2-(Cinnamyloxy)-1,1'-biphenyl (5o): Yield: 71% (20.3 mg) as yellow solid; mp = 67 ꢀ 68 C;
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hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 7.6 Hz, 2H), 7.41 (t, J =
7.6 Hz, 2H), 7.36 ꢀ7.27 (m, 7H), 7.22 (t, J = 6.8 Hz, 1H), 7.08 ꢀ 6.99 (m, 2H), 6.63 (d, J = 16.0 Hz,
1H), 6.31 (dt, J = 16.0, 6.0 Hz, 1H), 4.69 (dd, J = 6.0, 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
155.5, 138.5, 136.6, 131.9, 131.3, 130.9, 129.6, 128.6, 128.5, 127.9, 127.7, 126.9, 126.5, 124.6,
121.3, 113.2, 69.1 ppm; νmax(KBr)/cmꢀ1 3852, 3471, 2922, 1639, 1481, 1258, 989, 747;
HRMSꢀESI (m/z): calcd for C21H18ONa, [M+Na]+: 309.1250, found 309.1248.
2-(Cinnamyloxy)-4-isopropyl-1-methylbenzene (5p): Yield: 82% (21.8 mg) as yellow solid; mp
o
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= 83 ꢀ 84 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.6 Hz,
2H), 7.32 (t, J = 7.6 Hz, 2H), 7.24 (d, J = 2.8 Hz, 1H), 7.07 (d, J = 8.0 Hz, 1H), 6.74 (dd, J = 10.4,
5.2 Hz, 3H), 6.43 (dt, J = 16.0, 5.6 Hz, 1H), 4.70 (d, J = 5.6 Hz, 2H), 2.86 (dt, J = 13.6, 6.8 Hz,
1H), 2.23 (s, 3H), 1.23 (d, J = 6.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 156.7, 147.9, 136.7,
132.3, 130.5, 128.6, 127.8, 126.5, 125.2, 124.4, 118.3, 110.1, 68.7, 34.1, 24.1, 15.9 ppm;
νmax(KBr)/cmꢀ1 3472, 2960, 1725, 1620, 1456, 1252, 1132, 750; HRMSꢀESI (m/z): calcd for
C19H22ONa, [M+Na]+: 289.1563, found 289.1565.
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1-(Cinnamyloxy)-3,5-dimethylbenzene (5q): Yield: 91% (21.7 mg) as yellow solid; mp = 69 ꢀ
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o
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70 C; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.42 ꢀ 7.38 (m, 2H), 7.35 ꢀ
7.29 (m, 2H), 7.24 (tt, J = 6.8, 1.2 Hz, 1H), 6.72 (d, J = 16.0 Hz, 1H), 6.60 (d, J = 6.8 Hz, 3H),
6.41 (dt, J = 16.0, 6.0 Hz, 1H), 4.66 (dd, J = 6.0, 1.6 Hz, 2H), 2.29 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 158.7, 139.2, 136.6, 132.7, 128.6, 127.8, 126.6, 124.8, 122.7, 112.6, 68.5, 21.4 ppm;
νmax(KBr)/cmꢀ1 3032, 2920, 2859, 1597, 1491, 1319, 1167, 747; HRMSꢀESI (m/z): calcd for
C17H18ONa, [M+Na]+: 261.1250, found 261.1257.
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5-(Cinnamyloxy)benzo[d][1,3]dioxole (5r): Yield: 72% (18.3 mg) as yellow oil; hexanes/ethyl
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acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 7.2 Hz, 2H), 7.31 (t, J = 7.2 Hz, 2H),
7.24 (t, J = 7.2 Hz, 1H), 6.73 ꢀ 6.67 (m, 2H), 6.55 (d, J = 2.4 Hz, 1H), 6.43 ꢀ 6.33 (m, 2H), 5.90 (s,
2H), 4.61 (dd, J = 6.0, 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 154.2, 148.3, 141.8, 136.5,
132.9, 128.6, 127.9, 126.6, 124.6, 107.9, 106.2, 101.1, 98.4, 69.7 ppm; νmax(KBr)/cmꢀ1 2913, 1616,
1487, 1380, 1243, 1182, 1032, 743; HRMSꢀESI (m/z): calcd for C16H14O3Na, [M+Na]+: 277.0835,
found 277.0840.
5-(Cinnamyloxy)-2,3-dihydro-1H-indene (5s): Yield: 80% (20.0 mg) as yellow solid; mp = 90 ꢀ
1
91 oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.42 ꢀ 7.38 (m, 2H), 7.31 (dd,
J = 10.0, 4.8 Hz, 2H), 7.24 (dd, J = 6.0, 4.0 Hz, 1H), 7.11 (d, J = 8.0 Hz, 1H), 6.84 (s, 1H), 6.74
(dd, J = 16.0, 9.2 Hz, 2H), 6.41 (dt, J = 16.0, 6.0 Hz, 1H), 4.66 (dd, J = 6.0, 1.6 Hz, 2H), 2.93 ꢀ
2.78 (m, 4H), 2.16 ꢀ 1.97 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.6, 145.7, 136.6, 136.4,
132.7, 128.5, 127.8, 126.5, 124.9, 124.7, 112.8, 110.9, 68.9, 33.2, 31.9, 25.8 ppm; νmax(KBr)/cmꢀ1
2927, 1725, 1605, 1457, 1254, 1073, 1024, 749; HRMSꢀESI (m/z): calcd for C18H18ONa,
[M+Na]+: 273.1250, found 273.1248.
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6-(Cinnamyloxy)-1,2,3,4-tetrahydronaphthalene (5t): Yield: 83% (21.9 mg) as yellow solid;
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6
7
1
mp = 93 ꢀ 94 oC; hexanes/ethyl acetate =100:1; H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.0 Hz,
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9
2H), 7.31 (t, J = 8.0 Hz, 2H), 7.25 (t, J = 4.0 Hz, 1H), 6.97 (d, J = 8.0 Hz, 1H), 6.75 ꢀ 6.64 (m, 3H),
6.41 (dt, J = 16.0, 6.0 Hz, 1H), 4.66 (dd, J = 5.6, 1.6 Hz, 2H), 2.72 (d, J = 16.0 Hz, 4H), 1.83 ꢀ
1.69 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 156.5, 138.2, 136.6, 132.7, 129.9, 129.6, 128.5,
127.8, 126.6, 124.9, 114.8, 112.6, 68.7, 29.7, 28.6, 23.4, 23.2 ppm; νmax(KBr)/cmꢀ1 3562, 2923,
2854, 1609, 1499, 1252, 964, 749; HRMSꢀESI (m/z): calcd for C19H20ONa, [M+Na]+: 287.1406,
found 287.1409.
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Acknowledgments
The authors thank the National Natural Science Foundation of China (21490572, 21502055 and
21420102003), the Fundamental Research Funds for the Central Universities (2015ZY001), the
Fundamental Research Funds for the Central Universities ( 2015ZM150).
.
Supporting Information
1
Copies of H and 13C NMR spectra data for all compounds. This material is available free of
charge via the Internet at http://pubs.acs.org.
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