Palladium-Catalyzed Oxidative Cross-Coupling of Conjugated Enynones with Allylarenes: Synthesis of Furyl-Substituted 1,3-Dienes

Article abstract of DOI:10.1021/acs.joc.9b00922

A new method for the synthesis of furyl-substituted 1,3-dienes via palladium-catalyzed oxidative cross-coupling of conjugated enynones with allylarenes is developed. This reaction shows broad substrate scope and good functional group tolerance. Palladium carbene migratory insertion is proposed as the key step for this transformation with conjugated enynones serving as the carbene precursors.

Full text of DOI:10.1021/acs.joc.9b00922

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Note
Palladium-Catalyzed Oxidative Cross-Coupling of Conjugated
Enynones with Allylarenes: Synthesis of Furyl-Substituted 1,3-Dienes
Yifan Ping, Sudong Zhang, Taiwei Chang, and Jianbo Wang
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 22 May 2019
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Page 1 of 27
The Journal of Organic Chemistry
Palladium-Catalyzed Oxidative Cross-Coupling of Conjugated
Enynones with Allylarenes: Synthesis of Furyl-Substituted 1,3-
Dienes
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Yifan Ping,† Sudong Zhang,† Taiwei Chang,† and Jianbo Wang*,†,‡
†Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic
Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking
University, Beijing 100871, China; ‡The State Key Laboratory of Organometallic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, China
ABSTRACT. A new method for the synthesis of furyl-substituted 1,3-dienes via palladium-catalyzed
oxidative cross-coupling of conjugated enynones with allylarenes is developed. This reaction shows
broad substrate scope and good functional group tolerance. Palladium carbene migratory insertion is
proposed as the key step for this transformation with conjugated enynones serving as the carbene
precursors.
Transition-metal-catalyzed carbene-based cross-coupling reactions have emerged as powerful synthetic
methods for the construction of C−C and C−X bonds.1 In these transformations, diazo compounds or N-
tosylhydrazones are the most common carbene precursors and carbene migratory insertion is the key
step in C−C and C−X bond formation.2 Recently, non-diazo carbene precursors have also been applied
to this type of coupling reactions.3 For example, Wang et al. have previously explored the carbene
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coupling with conjugated enynones, which serves as furyl carbene precursors in the classic carbene
transformations.4 The transition-metal-catalyzed coupling of conjugated enynones with a series of
coupling partners, such organohalides, boronic acids, terminal alkynes and diboron compounds, have
been achieved (Scheme 1a).5 These reactions provide efficient methods for the synthesis of furan
derivatives. Besides, the organometallic intermediates generated via C−H activation can also participate
in the carbene coupling.6 For example, in 2017 Chang et al. reported the use of conjugated enynones as
the carbene precursors in the Rh(III)-catalyzed aromatic C−H functionalization via carbene migratory
insertion.7
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On the other hand, palladium-catalyzed allylic C−H activation has become an efficient and atom-
economical strategy in organic synthesis.8 Because of the high reactivity of the allylpalladium
intermediate, a series of methodologies have been disclosed for allylic C−H oxygenation,9 amination,10
alkylation,11 borylation,12 silylation13 and fluorination.14 Since the allylpalladium intermediate can also
undergo carbene migratory insertion,15 Gong et al. have explored the palladium-catalyzed oxidative
cross-coupling of allylic C−H bonds with α-diazo esters.16 More recently, Jiang et al. reported the allylic
C−H bond coupling by using sulfoxonium ylides as the carbene precursors.17
As the continuation of our interest in carbene-based coupling reactions, we envisioned that the
allylpalladium intermediate generated via allylic C−H activation may also participate in the carbene
coupling with conjugated enynones (Scheme 1b). Herein, we report the palladium-catalyzed oxidative
cross-coupling of conjugated enynones with allylarenes. This reaction affords a series of furyl-
substituted 1,3-dienes with high efficiency under mild conditions.
Scheme 1. Transition-Metal-Catalyzed Carbene Coupling Reaction Using Conjugated Enynones
as the Carbene Precursor
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At the outset of this investigation, we employed conjugated enynone 1a and allylbenzene 2a as the
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model substrates. The reaction was carried out in dioxane at 50 C with Pd(OAc)2 as the catalyst, PPh3
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as the ligand, Pr2NEt as the base and 2,6-DMBQ as the oxidant. Gratifyingly, the desired product 3a
could be obtained in 33% yield (Table 1, entry 1). We examined other solvents, however, in these cases
the yields were slightly diminished (entries 2−4). Other palladium catalysts were tested (entries 5-8), but
we didn’t observe any product with these, indicating that the acetate anion and phosphine ligand are
crucial for this reaction. Furthermore, we found that the temperature had a large influence on this
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transformation (entries 9-11), with 70 C being the suitable temperature (entry 10). By increasing the
amount of 2a and oxidant, the yield could be further improved to 72% (entry 12). Finally, we added a
catalytic amount of diphenylphosphate as additive, which may promote the allylic C−H activation,18 and
the reaction gave the desired product in 80% yield (entry 13).
Table 1. Optimization of the Reaction Conditionsa
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entry
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Pd catalyst
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(PPh3)4
Pd2(dba)3
Pd(PPh3)2Cl2
no catalyst
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
ligand
PPh3
PPh3
PPh3
PPh3
--
solvent
dioxane
toluene
THF
temp (oC)
50
yield (%)b
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DCE
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dioxane
dioxane
dioxane
dioxane
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dioxane
dioxane
dioxane
dioxane
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PPh3
--
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PPh3
PPh3
PPh3
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12c
13c,d
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aReaction conditions are the following if not otherwise noted: 1a (0.1 mmol), 2a (0.1 mmol), Pd catalyst
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(5 mol%), ligand (10 mol%), Pr2NEt (2 equiv), 2,6-DMBQ (1.2 equiv) in 1.0 mL of solvent at the
indicated temperature for 16 h. bDetermined by 1H NMR using dibromomethane as the internal standard.
c2a (1.5 equiv), 2,6-DMBQ (1.5 equiv). d(PhO)2PO2H (10 mol%) is added.
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Scheme 2. Scope of Allylarenesa
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aReaction conditions: 1a (0.2 mmol), 2a-u (0.3 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%),
(PhO)2PO2H (10 mol%), iPr2NEt (0.4 mmol), 2,6-DMBQ (0.3 mmol) in dioxane (2 mL) at 70 oC for 16
h. All the yields refer to the isolated yields after column chromatography.
With the optimized reaction conditions in hand, we then examined the scope of the reaction. A
series of allylarenes 2a-u with varied electronic properties were first explored (Scheme 2). Electron-rich
substituents in the para-position of the aromatic ring were tolerated well, affording the products 3b-d in
good yields. The reaction of allylarenes bearing electron-withdrawing groups also proceeded, but the
products 3e-h were formed in slightly diminished yields. It is noteworthy that halide substituents are
compatible with this palladium-catalyzed transformation (3f-h). The position of the substituents had a
marginal influence on this reaction, both meta- and ortho-substituted allylarenes gave the corresponding
products in good yields (3i-l). Poly-substituted allylarenes could also participate in this transformation,
with most of them delivering the corresponding products 3m-q in good yields. However, the tri-
substituted product 3q was obtained in low yield due to the large steric congestion. In addition, the
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reaction is also applicable to heteroaromatic and polyaromatic substrates, affording the corresponding
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products 3r-u in moderate to excellent yields.
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Scheme 3. Scope of Conjugated Enynonesa
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aReaction conditions: 1b-k (0.2 mmol), 2a (0.3 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%),
(PhO)2PO2H (10 mol%), iPr2NEt (0.4 mmol), 2,6-DMBQ (0.3 mmol) in dioxane (2 mL) at 70 oC for 16
h. All the yields refer to the isolated yields after column chromatography
Next, a variety of conjugated enynones 1b-k were investigated to react with allylbenzene 2a under
the same reaction conditions (Scheme 3). The coupling reaction worked smoothly in all cases, affording
the products 4b-k in moderate to good yields. Some functional groups, such as ester (4d-i), phosphate
(4j) and tosyl (4k), were well tolerated. It is notable that conjugated enynones 1d-k were synthesized as
mixtures of Z/E isomers, but interestingly, these reactions afforded single products through cyclization
of the ketone carbonyl oxygen. This indicates that the isomerization of the double bond occurred easily
under the reaction conditions.
To demonstrate the synthetic utility of this methodology, a gram-scale experiment was performed
(Scheme 4). Under the same condition, the furyl-substituted 1,3-diene 3a was successfully obtained in
slightly diminished yield.
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The Journal of Organic Chemistry
Scheme 4. Gram-Scale Synthesis
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To gain insights into the reaction mechanism, kinetic isotope effect studies were carried out (Scheme
5). The coupling reaction between conjugated enynone 1a and allylarene [D1]-2d was first carried out
and an intramolecular KIE (kH/kD = 2.7) was observed (Scheme 5a). Next, two separate reactions of 2d
or [D2]-2d with 1a were conducted in parallel. The rate constants were measured for these two
substrates at low conversion and a moderate KIE valve (kH/kD = 1.9) was observed (Scheme 5b). These
results indicated that the cleavage of C−H bond is likely involved in the rate-determining step.19
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Scheme 5. Kinetic Isotope Effect Studies
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Scheme 6. Proposed Reaction Mechanism
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On the basis of our previous studies5 and KIE experiments, a plausible mechanism is proposed in
Scheme 6. Pd(OAc)2 first undergoes a ligand exchange equilibrium with diphenylphosphate to form
catalytically reactive intermediate A,18 which activates an allylic C−H bond of allylarene 2 to generate π-
allylpalladium species B. Then, the alkyne moiety of conjugated enynone 1 is activated by π-
allylpalladium species B to form furyl palladium-carbene C. Afterwards, carbene migratory insertion
occurs to form intermediate D, followed by −H elimination to produce the final product 3 and Pd(0) E.
Finally, the catalytic active Pd(II) intermediate A is regenerated through oxidation to complete the
catalytic cycle. The exclusive Z-selectivity of the trisubstituted double bond is attributed to distinct steric
hindrances of the furyl and tert-butyl groups in cis −H elimination step (D to E).
In summary, we have developed an oxidative cross-coupling reaction of conjugated enynones with
allylarenes under palladium catalysis. This approach shows good compatibility of Pd-catalyzed allylic
C−H activation with carbene cross-coupling processes. A wide range of substrates were tolerated, and
various furyl-substituted 1,3-dienes were obtained in good yields under mild conditions.
EXPERIMENTAL SECTION
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General Methods. All the palladium-catalyzed reactions were performed under nitrogen
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atmosphere in a flame-dried reaction tube. All the solvents were distilled under nitrogen atmosphere
prior to use. Toluene, dioxane and THF were dried over Na with benzophenone-ketyl intermediate as
indicator. MeCN, MeOH were dried over CaH2. For chromatography, 200–300 mesh silica gel (Qingdao,
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China) was employed. H NMR spectra were recorded on Bruker ARX 400 (400 MHz); 13C NMR
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spectra were recorded on Bruker ARX 400 (101 MHz). The data for NMR spectra were reported as
follows: chemical shifts (δ) were reported in ppm using tetramethylsilane as internal standard when
using CDCl3 as solvent, and coupling constants (J) were in Hertz (Hz). IR spectra were recorded on
Nicolet 5MX–S infrared spectrometer and were reported in terms of frequency of absorption (cm−1).
HRMS were obtained on Bruker APEX IV FTMS.
Preparation of Conjugated Enynones and Allylarenes. The conjugated enynones were prepared
according to our previous reports, and the conjugated enynones 1a, 1c, 1e and 1h are known.5
Allylarenes were synthesized according to the literature procedures.9j
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4-(4,4-Dimethylpent-2-yn-1-ylidene)heptane-3,5-dione (1b). H NMR (400 MHz, CDCl3) δ 6.67 (s,
1H), 2.79 (q, J = 7.2 Hz, 2H), 2.62 (q, J = 7.2 Hz, 2H), 1.26 (s, 9H), 1.15 (t, J = 7.2 Hz, 3H), 1.09 (t, J =
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7.2 Hz, 3H); C {1H} NMR (101 MHz, CDCl3) δ 205.2, 198.3, 149.6, 121.3, 116.1, 75.4, 36.6, 32.5,
30.3, 28.7, 7.9, 7.4; HRMS (ESI, m/z): calcd for C14H21O2 [M+H]+ 221.1536, found 221.1534; IR (film):
2977, 2938, 2205, 1715, 1698, 1669, 1579, 1460, 1377, 807 cm−1.
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Methyl 2-acetyl-6,6-dimethylhept-2-en-4-ynoate (1d). H NMR (400 MHz, CDCl3) δ 6.83 (s, 1H),
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6.80 (s, 1H), 3.86 (s, 3H), 3.79 (s, 3H), 2.46 (s, 3H), 2.35 (s, 3H), 1.27 (s, 18H); C {1H} NMR (101
MHz, CDCl3) δ 199.0, 193.9, 166.0, 164.4, 141.6, 141.3, 125.8, 124.1, 117.4, 116.1, 75.6, 75.2, 52.4,
52.0, 30.4, 30.3, 30.2, 28.8, 28.7, 27.2; HRMS (ESI, m/z): calcd for C12H17O3 [M+H]+ 209.1172, found
209.1174; IR (film): 2975, 2229, 2200, 1725, 1365, 1248 cm−1.
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tert-Butyl 2-acetyl-6,6-dimethylhept-2-en-4-ynoate (1f). 1H NMR (400 MHz, CDCl3) Major isomer:
δ 6.69 (s, overlapping, 1H), 2.31 (s, 3H), 1.57 (s, 9H), 1.28 (s, 9H); Minor isomer: δ 6.69 (s, overlapping,
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1H), 2.42 (s, 3H), 1.49 (s, 9H), 1.26 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 199.4, 193.8, 165.0,
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162.9, 143.7, 142.4, 123.2, 122.4, 115.5, 114.6, 82.4, 82.2, 75.3, 75.1, 30.3, 30.20, 30.16, 28.6, 28.5,
28.0, 27.9, 27.0; HRMS (ESI, m/z): calcd for C15H23O3 [M+H]+ 251.1642, found 251.1640; IR (film):
2977, 2224, 1718, 1586, 1372, 1250, 1162, 846 cm−1.
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Benzyl 2-acetyl-6,6-dimethylhept-2-en-4-ynoate (1g). H NMR (400 MHz, CDCl3) Major isomer: δ
7.45–7.27 (m, overlapping, 5H), 6.80 (s, 1H), 5.30 (s, 2H), 2.30 (s, 3H), 1.18 (s, 9H); Minor isomer: δ
13
7.45–7.27 (m, overlapping, 5H), 6.84 (s, 1H), 5.21 (s, 2H), 2.44 (s, 3H), 1.25 (s, 9H); C {1H} NMR
(101 MHz, CDCl3) δ 198.5, 193.7, 165.2, 163.6, 141.5, 141.0, 135.1, 128.41, 128.38, 128.2, 128.10,
128.07, 127.9, 125.5, 124.2, 117.3, 116.1, 75.4, 75.2, 66.88, 66.85, 30.2, 30.0, 28.54, 28.52, 27.0;
HRMS (ESI, m/z): calcd for C18H21O3 [M+H]+ 285.1485, found 285.1487; IR (film): 2970, 2224, 1723,
1598, 1250, 1196, 753, 702 cm−1.
Methyl 2-(cyclopropanecarbonyl)-6,6-dimethylhept-2-en-4-ynoate (1i). 1H NMR (400 MHz, CDCl3)
Major isomer: δ 6.86 (s, 1H), 3.79 (s, 3H), 2.33–2.22 (m, overlapping, 1H), 1.26 (s, 9H), 1.25–1.21 (m,
2H), 1.06–1.00 (m, 2H); Minor isomer: δ 6.83 (s, 1H), 3.87 (s, 3H), 2.33–2.22 (m, overlapping, 1H),
1.28 (s, 9H), 1.17–1.12 (m, 2H), 1.00–0.95 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 201.8, 196.3,
166.1, 164.4, 142.0, 141.6, 124.7, 123.9, 116.5, 115.2, 75.6, 75.2, 52.3, 52.0, 30.3, 30.2, 28.9, 28.6, 21.9,
18.2, 12.5, 12.2; HRMS (ESI, m/z): calcd for C14H19O3 [M+H]+ 235.1329, found 235.1328; IR (film):
2977, 2222, 1725, 1598, 1389, 1248, 1004 cm−1.
1
Dimethyl (7,7-dimethyl-2-oxooct-3-en-5-yn-3-yl)phosphonate (1j). H NMR (400 MHz, CDCl3)
Major isomer: δ 6.97 (d, J = 22.0 Hz, 1H), 3.78 (d, J = 11.6 Hz, 6H), 2.53 (s, 3H), 1.29 (s, 9H); Minor
isomer: δ 7.14 (d, J = 42.0 Hz, 1H), 3.83 (d, J = 11.6 Hz, 6H), 2.45 (s, 3H), 1.31 (s, 9H); 13C {1H} NMR
(101 MHz, CDCl3) δ 198.1 (d, J = 7.9 Hz), 196.3 (d, J = 14.0 Hz), 139.1 (d, J = 177.6 Hz), 137.4 (d, J =
178.2 Hz), 134.3 (d, J = 2.1 Hz), 131.0 (d, J = 11.2 Hz), 119.7, 117.3, 76.2 (d, J = 10.1 Hz), 75.9 (d, J =
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30.2 Hz), 52.9 (d, J = 5.9 Hz), 52.6 (d, J = 6.0 Hz), 30.5 (d, J = 4.1 Hz), 30.0, 29.9, 28.8, 28.6, 28.4;
HRMS (ESI, m/z): calcd for C12H20O4P [M+H]+ 259.1094, found 259.1098; IR (film): 2972, 2219, 1703,
1574, 1365, 1265, 1060, 1033, 831, 780 cm−1.
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(E)-7,7-Dimethyl-3-tosyloct-3-en-5-yn-2-one (1k). H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.0
Hz, 2H), 7.41 (s, 1H), 7.32 (d, J = 8.0 Hz, 2H), 2.52 (s, 3H), 2.42 (s, 3H), 1.29 (s, 9H); C {1H} NMR
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(101 MHz, CDCl3) δ 194.0, 148.6, 144.7, 137.0, 129.6, 128.7, 127.6, 121.7, 74.9, 31.2, 30.0, 29.1, 21.6;
HRMS (ESI, m/z): calcd for C17H21O3S [M+H]+ 305.1206, found 305.1212; IR (film): 2975, 2224, 2188,
1681, 1586, 1321, 1158, 1089, 712, 680 cm−1.
General Procedure for Palladium-Catalyzed Oxidative Cross-Coupling of Conjugated
Enynones with Allylarenes. Pd(OAc)2 (2.2 mg, 0.01 mmol, 5 mol%), PPh3 (5.3 mg, 0.02 mmol, 10
mol%), (PhO)2PO2H (5.0 mg, 0.02 mmol, 10 mol%) and 2,6-dimethyl-1,4-benzoquinone (40.8 mg, 0.3
mmol, 1.5 equiv) were added to a flame-dried 10 mL Schlenk reaction tube. The reaction tube was
i
degassed three times with nitrogen, then dry dioxane (2 mL, 0.1 M) was added using a syringe. Pr2NEt
(51.6 mg, 0.4 mmol, 2 equiv), allylarene 2 (0.3 mmol, 1.5 equiv) and conjugated enynone 1 (0.2 mmol)
o
were added by syringe successively. The reaction tube was stirred at 70 C in the oil bath for 16 h, then
cooled to room temperature. The mixture was filtered through a short plug of silica gel and washed with
Et2O as the eluent. Solvent was then removed in vacuo to leave a crude mixture, which was purified by
silica gel column chromatography to afford pure product 3.
1-(5-((3Z,5E)-2,2-Dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one (3a). Yield:
1
80% (48.2 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.35–7.25 (m, 4H), 7.23–7.17 (m, 1H), 6.79
(dd, J = 15.6, 10.6 Hz, 1H), 6.65 (d, J = 15.6 Hz, 1H), 6.50 (d, J = 10.4 Hz, 1H), 6.44 (s, 1H), 2.64 (s,
3H), 2.44 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.3, 157.6, 150.2, 141.2, 137.3,
133.6, 129.4, 128.6, 127.6, 126.6, 126.4, 122.0, 110.8, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd
for C21H25O2 [M+H]+ 309.1849, found 309.1850; IR (film): 2975, 1679, 1589, 1559, 1367, 1228, 972,
948, 751, 695 cm−1.
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1-(5-((3Z,5E)-6-(4-Methoxyphenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3b). Yield: 79% (54.0 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.27–7.23 (m, 2H), 6.86–6.80 (m,
2H), 6.65 (dd, J = 15.4 Hz, 9.4 Hz, 1H), 6.59 (d, J = 15.2 Hz, 1H), 6.48 (d, J = 9.2 Hz, 1H), 6.43 (s, 1H),
3.79 (s, 3H), 2.64 (s, 3H), 2.44 (s, 3H), 1.17 (s, 9H); 13C NMR (101 MHz, CDCl3) δ 194.4, 159.3, 157.5,
150.4, 140.1, 133.3, 130.1, 129.6, 127.7, 124.6, 122.0, 114.1, 110.6, 55.3, 36.2, 29.8, 29.2, 14.6; HRMS
(ESI, m/z): calcd for C22H27O3 [M+H]+ 339.1955, found 339.1961; IR (film): 2961, 1674, 1606, 1507,
1251, 1173, 1037, 972, 824 cm−1.
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1-(5-((3Z,5E)-6-(4-(tert-Butyl)phenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-
one (3c). Yield: 74% (53.7 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.32 (d, J = 8.4 Hz, 2H), 7.25
(d, J = 8.4 Hz, 2H), 6.75 (dd, J = 15.6, 10.4 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.49 (d, J = 10.4 Hz,
1H), 6.43 (s, 1H), 2.64 (s, 3H), 2.44 (s, 3H), 1.30 (s, 9H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz,
CDCl3) δ 194.3, 157.5, 150.7, 150.4, 140.6, 134.6, 133.5, 129.5, 126.2, 126.0, 125.5, 122.0, 110.8, 36.2,
34.6, 31.2, 29.7, 29.2, 14.5; HRMS (ESI, m/z): calcd for C25H33O2 [M+H]+ 365.2475, found 365.2483;
IR (film): 2958, 1677, 1581, 1365, 1229, 969, 944, 818, 734 cm−1.
1-(5-((3Z,5E)-6-([1,1'-Biphenyl]-4-yl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-
1
one (3d). Yield: 78% (60.2 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.2 Hz, 2H),
7.53 (d, J = 8.0 Hz, 2H), 7.45–7.36 (m, 4H), 7.35–7.30 (m, 1H), 6.84 (dd, J = 15.6, 10.8 Hz, 1H), 6.68
(d, J = 15.6 Hz, 1H), 6.52 (d, J = 10.8 Hz, 1H), 6.46 (s, 1H), 2.65 (s, 3H), 2.45 (s, 3H), 1.19 (s, 9H); 13C
{1H} NMR (101 MHz, CDCl3) δ 194.3, 157.6, 150.3, 141.3, 140.6, 140.3, 136.4, 133.2, 129.4, 128.8,
127.31, 127.26, 126.9, 126.8, 126.7, 122.1, 110.9, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for
C27H29O2 [M+H]+ 385.2162, found 385.2163; IR (film): 2955, 1677, 1585, 1486, 1229, 972, 765, 734,
700 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-(4-(trifluoromethyl)phenyl)hexa-3,5-dien-3-yl)-2-methylfuran-3-
1
yl)ethan-1-one (3e). Yield: 49% (36.6 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.0
Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 6.88 (dd, J = 15.6, 10.8 Hz, 1H), 6.66 (d, J = 15.6 Hz, 1H), 6.51 (d, J
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= 10.8 Hz, 1H), 6.46 (s, 1H), 2.65 (s, 3H), 2.45 (s, 3H), 1.20 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3)
δ 194.2, 157.8, 149.9, 143.1, 140.8, 131.9, 129.1 (q, J = 32.3 Hz), 129.0, 128.8, 126.5, 125.5 (q, J = 4.0
Hz), 124.1 (q, J = 272.7 Hz), 122.1, 111.1, 36.4, 29.6, 29.2, 14.6; HRMS (ESI, m/z): calcd for
C22H24F3O2 [M+H]+ 377.1723, found 377.1720; IR (film): 2962, 1684, 1328, 1170, 1126, 1067, 970,
953, 819 cm−1.
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1-(5-((3Z,5E)-6-(4-Chlorophenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3f). Yield: 72% (49.3 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.25–7.20 (m, 4H), 6.75 (dd, J =
15.6 Hz, 10.4 Hz, 1H), 6.59 (d, J = 15.6 Hz, 1H), 6.48 (d, J = 10.8 Hz, 1H), 6.44 (s, 1H), 2.64 (s, 3H),
2.44 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.2, 157.6, 150.1, 141.9, 135.8, 133.1,
132.2, 129.1, 128.8, 127.6, 127.1, 122.1, 110.9, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for
C21H24ClO2 [M+H]+ 343.1459, found 343.1458; IR (film): 2952, 1677, 1581, 1489, 1405, 1229, 1090,
969, 808 cm−1.
1-(5-((3Z,5E)-6-(4-Bromophenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3g). Yield: 50% (38.9 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.4 Hz, 2H), 7.17 (d,
J = 8.8 Hz, 2H), 6.76 (dd, J = 15.4, 10.6 Hz, 1H), 6.57 (d, J = 15.6 Hz, 1H), 6.48 (d, J = 10.4 Hz, 1H),
6.44 (s, 1H), 2.64 (s, 3H), 2.44 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.3, 157.7,
150.1, 142.0, 136.3, 132.3, 131.7, 129.1, 127.9, 127.3, 122.1, 121.3, 110.9, 36.4, 29.7, 29.2, 14.6;
HRMS (ESI, m/z): calcd for C21H24BrO2 [M+H]+ 387.0954, found 387.0957; IR (film): 2955, 1677,
1588, 1486, 1229, 1071, 969, 805, 651 cm−1.
1-(5-((3Z,5E)-6-(4-Fluorophenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
1
(3h). Yield: 55% (36.1 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.30–7.24 (m, 2H), 6.97 (t, J =
8.6 Hz, 2H), 6.69 (dd, J = 15.4, 10.2 Hz, 1H), 6.60 (d, J = 15.6 Hz, 1H), 6.48 (d, J = 10.4 Hz, 1H), 6.44
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(s, 1H), 2.64 (s, 3H), 2.44 (s, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 194.3, 162.3 (d, J
= 248.4 Hz), 157.6, 150.2, 141.3, 133.5 (d, J = 3.6 Hz), 132.4, 129.2, 127.9 (d, J = 8.0 Hz), 126.3 (d, J =
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2.4 Hz), 122.1, 115.6 (d, J = 21.6 Hz), 110.8, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for
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C21H24FO2 [M+H]+ 327.1755, found 327.1756; IR (film): 2961, 1680, 1507, 1229, 1155, 969, 814 cm−1.
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1-(5-((3Z,5E)-6-(3-Methoxyphenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3i). Yield: 73% (49.2 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.21 (t, J = 8.0 Hz, 1H), 6.92 (d, J
= 7.6 Hz, 1H), 6.84 (t, J = 1.8 Hz, 1H), 6.80–6.73 (m, 2H), 6.62 (d, J = 15.2 Hz, 1H), 6.49 (d, J = 10.4
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Hz, 1H), 6.44 (s, 1H), 3.79 (s, 3H), 2.64 (s, 3H), 2.44 (s, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz,
CDCl3) δ 194.3, 159.8, 157.6, 150.2, 141.5, 138.8, 133.5, 129.6, 129.3, 127.0, 122.0, 119.1, 112.9,
112.2, 110.9, 55.2, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for C22H27O3 [M+H]+ 339.1955,
found 339.1953; IR (film): 2964, 2918, 1674, 1585, 1232, 1155, 910, 734, 651 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-(m-tolyl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3j).
Yield: 67% (43.7 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.18 (t, J = 7.4 Hz, 1H), 7.14−7.10 (m,
2H), 7.02 (d, J = 7.2 Hz, 1H), 6.77 (dd, J = 15.4, 10.6 Hz, 1H), 6.61 (d, J = 15.6 Hz, 1H), 6.49 (d, J =
10.4 Hz, 1H), 6.44 (s, 1H), 2.64 (s, 3H), 2.44 (s, 3H), 2.32 (s, 3H), 1.18 (s, 9H); C {1H} NMR (101
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MHz, CDCl3) δ 194.4, 157.6, 150.3, 141.0, 138.1, 137.3, 133.8, 129.4, 128.5, 128.4, 127.3, 126.4, 123.5,
122.0, 110.8, 36.3, 29.7, 29.2, 21.4, 14.6; HRMS (ESI, m/z): calcd for C22H27O2 [M+H]+ 323.2006,
found 323.1998; IR (film): 2961, 1677, 1581, 1393, 1229, 969, 951, 777 cm−1.
1-(5-((3Z,5E)-6-(2-Methoxyphenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3k). Yield: 62% (42.2 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.36–7.30 (m, 1H), 7.22-7.16 (m,
1H), 6.99 (d, J = 15.6 Hz, 1H), 6.92–6.77 (m, 3H), 6.54 (d, J = 10.8 Hz, 1H), 6.44 (s, 1H), 3.84 (s, 3H),
2.63 (s, 3H), 2.43 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.4, 157.5, 156.7, 150.5,
140.5, 130.2, 128.6, 128.4, 127.4, 126.6, 126.4, 122.0, 120.7, 110.8, 110.7, 55.4, 36.2, 29.8, 29.2, 14.6;
HRMS (ESI, m/z): calcd for C22H27O3 [M+H]+ 339.1955, found 339.1952; IR (film): 2952, 1677, 1581,
1486, 1241, 1031, 947, 749, 654 cm−1.
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1-(5-((3Z,5E)-2,2-Dimethyl-6-(o-tolyl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3l).
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Yield: 65% (41.9 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.36–7.31 (m, 1H), 7.14-7.10 (m, 3H),
6.87 (d, J = 15.6 Hz, 1H), 6.69 (dd, J = 15.2 Hz, 10.4 Hz, 1H), 6.54 (d, J = 10.8 Hz, 1H), 6.44 (s, 1H),
2.63 (s, 3H), 2.43 (s, 3H), 2.36 (s, 3H), 1.19 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.3, 157.6,
150.2, 141.1, 136.2, 135.6, 131.3, 130.4, 129.7, 127.8, 127.5, 126.1, 125.3, 122.0, 110.8, 36.3, 29.7,
29.2, 19.8, 14.6; HRMS (ESI, m/z): calcd for C22H27O2 [M+H]+ 323.2006, found 323.2002; IR (film):
2958, 1677, 1585, 1232, 969, 753, 654 cm−1.
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1-(5-((3Z,5E)-6-(3,5-Dimethylphenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-
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one (3m). Yield: 68% (46.3 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 6.93 (s, 2H), 6.86 (s, 1H),
6.75 (dd, J = 15.6 Hz, 10.4 Hz, 1H), 6.58 (d, J = 15.6 Hz, 1H), 6.48 (d, J = 10.8 Hz, 1H), 6.44 (s, 1H),
2.64 (s, 3H), 2.44 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.5, 157.6, 150.3, 140.7,
138.0, 137.2, 134.0, 129.5, 129.4, 126.2, 124.3, 122.0, 110.8, 36.3, 29.7, 29.2, 21.2, 14.6; HRMS (ESI,
m/z): calcd for C23H29O2 [M+H]+ 337.2162, found 337.2161; IR (film): 2952, 1680, 1585, 1390, 1229,
969, 827, 651 cm−1.
1-(5-((3Z,5E)-6-(3,4-Dimethoxyphenyl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-
1
one (3n). Yield: 81% (59.5 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 6.92–6.88 (m, 1H), 6.85-
6.78 (m, 2H), 6.68 (dd, J = 15.4, 10.2 Hz, 1H), 6.60 (d, J = 15.2 Hz, 1H), 6.48 (d, J = 10.0 Hz, 1H), 6.45
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(s, 1H), 3.87 (s, 3H), 3.86 (s, 3H), 2.64 (s, 3H), 2.44 (s, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz,
CDCl3) δ 194.3, 157.5, 150.4, 149.0, 148.9, 140.2, 133.9, 130.5, 129.4, 125.0, 122.0, 119.5, 111.2,
110.8, 109.2, 55.9, 55.8, 36.2, 29.8, 29.2, 14.6; HRMS (ESI, m/z): calcd for C23H29O4 [M+H]+ 369.2060,
found 369.2061; IR (film): 2967, 1677, 1510, 1266, 1139, 1025, 966 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-(perfluorophenyl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
1
(3o). Yield: 59% (47.2 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.16 (dd, J = 16.0 Hz, 10.8 Hz,
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1H), 6.57–6.41 (m, 3H), 2.64 (s, 3H), 2.45 (s, 3H), 1.21 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ
194.1, 157.2, 149.6, 144.8, 144.5 (d, J = 249.6 Hz), 138.9 (m), 136.4 (m), 135.4, 128.7, 122.0, 116.7 (d,
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J = 3.5 Hz), 112.6 (m), 111.6, 36.5, 29.6, 29.2, 14.5; HRMS (ESI, m/z): calcd for C21H20F5O2 [M+H]+
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399.1378, found 399.1373; IR (film): 2965, 1681, 1523, 1496, 1232, 1002, 960 cm−1.
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1-(5-((3Z,5E)-6-Mesityl-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one (3p). Yield:
29% (20.3 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 6.84 (m, 2H), 6.65 (d, J = 16.0 Hz, 1H), 6.50
(d, J = 10.4 Hz, 1H), 6.39 (s, 1H), 6.26 (dd, J = 15.8 Hz, 10.6 Hz, 1H), 2.58 (s, 3H), 2.40 (s, 3H), 2.26 (s,
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6H), 2.25 (s, 3H), 1.19 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 194.2, 157.4, 150.4, 140.4, 136.4,
135.9, 133.7, 132.0, 131.4, 129.7, 128.9, 121.8, 110.4, 36.1, 29.7, 29.1, 21.1, 20.9, 14.5; HRMS (ESI,
m/z): calcd for C24H31O2 [M+H]+ 351.2319, found 351.2319; IR (film): 2970, 1686, 1586, 1233, 980,
953, 858, 663 cm−1.
1-(5-((3Z,5E)-6-(Benzo[d][1,3]dioxol-5-yl)-2,2-dimethylhexa-3,5-dien-3-yl)-2-methylfuran-3-
yl)ethan-1-one (3q). Yield: 69% (48.5 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 6.83 (s, 1H), 6.77
(d, J = 8.0 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H), 6.60 (dd, J = 15.4 Hz, 9.4 Hz, 1H), 6.55 (d, J = 15.2 Hz,
1H), 6.46 (d, J = 9.6 Hz, 1H), 6.43 (s, 1H), 5.94 (s, 2H), 2.64 (s, 3H), 2.45 (s, 3H), 1.17 (s, 9H); 13C {1H}
NMR (101 MHz, CDCl3) δ 194.3, 157.5, 150.3, 148.0, 147.3, 140.5, 133.3, 131.8, 129.4, 125.0, 122.0,
121.4, 110.7, 108.4, 105.5, 101.1, 36.2, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for C22H25O4 [M+H]+
353.1747, found 353.1745; IR (film): 2965, 1679, 1506, 1491, 1447, 1260, 1231, 1041, 972, 953, 804,
731 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-(thiophen-2-yl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3r). Yield: 66% (41.6 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.17–7.10 (m, 1H), 6.97-6.91 (m,
2H), 6.78 (d, J = 15.2 Hz, 1H), 6.63 (dd, J = 15.4 Hz, 10.6 Hz, 1H), 6.46 – 6.39 (m, 2H), 2.64 (s, 3H),
2.44 (s, 3H), 1.18 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 194.3, 157.6, 150.1, 142.9, 141.0, 128.6,
127.6, 126.6, 126.3, 125.8, 124.5, 122.0, 111.1, 36.3, 29.8, 29.2, 14.5; HRMS (ESI, m/z): calcd for
C19H23O2S [M+H]+ 315.1413, found 315.1413; IR (film): 2961, 1680, 1581, 1396, 1232, 963, 829, 703
cm−1.
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1-(5-((3Z,5E)-2,2-Dimethyl-6-(naphthalen-1-yl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
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(3s). Yield: 78% (55.6 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 8.0 Hz, 1H), 7.83 (d,
J = 8.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.53–7.39 (m, 5H), 6.85 (dd, J = 14.8 Hz, 10.8 Hz, 1H), 6.66
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(d, J = 10.8 Hz, 1H), 6.47 (s, 1H), 2.64 (s, 3H), 2.42 (s, 3H), 1.22 (s, 9H); C {1H} NMR (101 MHz,
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CDCl3) δ 194.3, 157.6, 150.2, 141.6, 134.7, 133.7, 131.1, 130.4, 129.7, 129.4, 128.6, 128,0, 126.0,
125.8, 125.6, 123.6, 123.5, 122.1, 110.9, 36.3, 29.7, 29.2, 14.6; HRMS (ESI, m/z): calcd for C25H27O2
[M+H]+ 359.2006, found 359.2009; IR (film): 2961, 1677, 1585, 1390, 1226, 951, 780 cm−1.
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1-(5-((3Z,5E)-2,2-Dimethyl-6-(naphthalen-2-yl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3t). Yield: 75% (54.1 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.79–7.66 (m, 4H), 7.53–7.37 (m,
3H), 6.92 (dd, J = 15.6 Hz, 10.4 Hz, 1H), 6.81 (d, J = 15.6 Hz, 1H), 6.56 (d, J = 10.4 Hz, 1H), 6.48 (s,
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1H), 2.66 (s, 3H), 2.46 (s, 3H), 1.20 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 194.4, 157.7, 150.3,
141.4, 134.9, 133.8, 133.6, 133.0, 129.4, 128.2, 127.9, 127.7, 127.0, 126.5, 126.3, 125.9, 123.4, 122.1,
110.9, 36.3, 29.8, 29.2, 14.6; HRMS (ESI, m/z): calcd for C25H27O2 [M+H]+ 359.2006, found 359.2007;
IR (film): 2961, 1677, 1581, 1387, 1229, 972, 811, 743, 651 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-(phenanthren-9-yl)hexa-3,5-dien-3-yl)-2-methylfuran-3-yl)ethan-1-one
(3u). Yield: 66% (54.0 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 8.71 (d, J = 7.6 Hz, 1H), 8.63 (d,
J = 8.4 Hz, 1H), 8.20 (d, J = 7.6 Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.74 (s, 1H), 7.69–7.54 (m, 4H), 7.43
(d, J = 15.2 Hz, 1H), 6.92 (dd, J = 15.2 Hz, 10.8 Hz, 1H) 6.69 (d, J = 10.8 Hz, 1H), 6.50 (s, 1H), 2.65 (s,
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3H), 2.43 (s, 3H), 1.24 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 194.3, 157.7, 150.2, 141.7, 133.6,
131.6, 131.0, 130.5, 130.4, 130.1, 129.9, 129.5, 128.7, 126.8, 126.60, 126.57, 126.5, 124.51, 124.48,
123.1, 122.5, 122.1, 111.0, 36.4, 29.8, 29.2, 14.6; HRMS (ESI, m/z): calcd for C29H29O2 [M+H]+
409.2162, found 409.2160; IR (film): 2958, 1684, 1584, 1399, 1231, 972, 948, 751, 731 cm−1.
1-(5-((3Z,5E)-2,2-Dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-ethylfuran-3-yl)propan-1-one (4b). Yield:
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75% (50.3 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.34–7.25 (m, 4H), 7.23–7.17 (m, 1H), 6.84
(dd, J = 15.6 Hz, 10.4 Hz, 1H), 6.65 (d, J = 15.6 Hz, 1H), 6.50 (d, J = 10.8 Hz, 1H), 6.45 (s, 1H), 3.08
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(q, J = 7.6 Hz, 2H), 2.78 (q, J = 7.2 Hz, 2H), 1.29 (t, J = 7.2 Hz, 3H), 1.23–1.13 (m, 12H); C {1H}
NMR (101 MHz, CDCl3) δ 197.3, 162.4, 150.2, 141.4, 137.4, 133.5, 128.9, 128.6, 127.5, 126.7, 126.4,
120.4, 110.5, 36.3, 34.5, 29.7, 21.7, 12.0, 7.9; HRMS (ESI, m/z): calcd for C23H29O2 [M+H]+ 337.2162,
found 337.2162; IR (film): 2975, 1681, 1589, 1557, 1467, 1211, 970, 929, 751, 695, 663 cm−1.
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(5-((3Z,5E)-2,2-Dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-phenylfuran-3-yl)(phenyl)methanone (4c).
Yield: 73% (63.1 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 7.6 Hz, 2H), 7.82 (d, J =
6.8 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.43–7.28 (m, 9H), 7.24–7.19 (m, 1H), 7.07 (dd, J = 15.4, 10.6 Hz,
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1H), 6.69 (d, J = 15.2 Hz, 1H), 6.59–6.51 (m, 2H), 1.29 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ
191.9, 154.8, 151.3, 140.7, 138.3, 137.3, 134.0, 132.9, 129.8, 129.7, 129.3, 128.9, 128.6, 128.39, 128.35,
127.6, 127.2, 126.6, 126.5, 121.4, 114.9, 36.5, 29.9; HRMS (ESI, m/z): calcd for C31H29O2 [M+H]+
433.2162, found 433.2160; IR (film): 2967, 1664, 1598, 1486, 1450, 1243, 975, 894, 731, 692 cm−1.
Methyl 5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-carboxylate (4d).
Yield: 62% (40.4 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.34–7.24 (m, 4H), 7.22–7.17 (m, 1H),
6.79 (dd, J = 15.6, 10.8 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.52-6.44 (m, 2H), 3.84 (s, 3H), 2.63 (s, 3H),
1.17 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 164.7, 158.4, 150.3, 141.3, 137.4, 133.6, 129.3, 128.5,
127.5, 126.7, 126.5, 113.8, 111.0, 51.3, 36.3, 29.7, 13.9; HRMS (ESI, m/z): calcd for C21H25O3 [M+H]+
325.1798, found 325.1800; IR (film): 2953, 1720, 1611, 1445, 1228, 1089, 975, 780, 753, 656 cm−1.
Ethyl 5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-carboxylate (4e). Yield:
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60% (40.6 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.35–7.23 (m, 4H), 7.22-7.16 (m, 1H), 6.80
(dd, J = 15.6 Hz, 10.4 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.52–6.43 (m, 2H), 4.31 (q, J = 7.2 Hz, 2H),
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2.63 (s, 3H), 1.37 (t, J = 7.2 Hz, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 164.3, 158.2,
150.2, 141.4, 137.4, 133.5 129.3, 128.5, 127.5, 126.8, 126.5, 114.1, 111.0, 60.1, 36.3, 29.7, 14.4, 13.4;
HRMS (ESI, m/z): calcd for C22H27O3 [M+H]+ 339.1955, found 339.1959; IR (film): 2962, 1720, 1603,
1231, 1084, 970, 782, 753, 692 cm−1.
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tert-Butyl 5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-carboxylate (4f).
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Yield: 85% (62.6 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.35–7.24 (m, 4H), 7.22–7.16 (m, 1H),
6.80 (dd, J = 15.4 Hz, 10.6 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.47 (d, J = 10.4 Hz, 1H), 6.43 (s, 1H),
2.59 (s, 3H), 1.58 (s, 9H), 1.17 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 163.7, 157.5, 149.9, 141.5,
137.4, 133.4, 129.1, 128.5, 127.5, 126.9, 126.5, 115.6, 111.3, 80.5, 36.3, 29.7, 28.3, 13.4; HRMS (ESI,
m/z): calcd for C24H31O3 [M+H]+ 367.2268, found 367.2269; IR (film): 2965, 1713, 1367, 1233, 1167,
1087, 972, 780, 751, 692 cm−1.
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Benzyl 5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-carboxylate (4g).
Yield: 60% (47.5 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.46–7.12 (m, 10H), 6.79 (dd, J = 15.4
Hz, 10.6 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.51 (s, 1H), 6.48 (d, J = 10.8 Hz, 1H), 5.31 (s, 2H), 2.62 (s,
3H), 1.17 (s, 9H); 13C {1H} NMR (101 MHz, CDCl3) δ 164.0, 158.6, 150.4, 141.2, 137.4, 136.2, 133.6,
129.3, 128.6, 128.5, 128.2, 128.1, 127.5, 126.7, 126.5, 113.8, 111.0, 65.9, 36.3, 29.7, 14.1; HRMS (ESI,
m/z): calcd for C27H29O3 [M+H]+ 401.2111, found 401.2108; IR (film): 2967, 1720, 1231, 1080, 975,
787, 753, 695 cm−1.
Methyl 5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-ethylfuran-3-carboxylate (4h). Yield:
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70% (46.9 mg); yellow oil; H NMR (400 MHz, CDCl3) δ 7.35–7.24 (m, 4H), 7.23–7.17 (m, 1H), 6.83
(dd, J = 15.6 Hz, 10.8 Hz, 1H), 6.64 (d, J = 15.6 Hz, 1H), 6.52–6.43 (m, 2H), 3.84 (s, 3H), 3.07 (q, J =
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7.6 Hz, 2H), 1.29 (t, J = 7.6 Hz, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 164.6, 163.3,
150.3, 141.3, 137.4, 133.5, 129.0, 128.5, 127.5, 126.8, 126.4, 112.8, 111.0, 51.3, 36.3, 29.7, 21.2, 12.3;
HRMS (ESI, m/z): calcd for C22H27O3 [M+H]+ 339.1955, found 339.1947; IR (film): 2953, 1720, 1603,
1442, 1243, 1092, 1043, 970, 751, 692 cm−1.
Methyl 2-cyclopropyl-5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)furan-3-carboxylate (4i).
Yield: 97% (68.0 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.35–7.26 (m, 4H), 7.23–7.16 (m, 1H),
6.85 (dd, J = 15.6 Hz, 10.8 Hz, 1H), 6.62 (d, J = 15.6 Hz, 1H), 6.47 (s, 1H), 6.44 (d, J = 10.8 Hz, 1H),
3.85 (s, 3H), 2.88–2.78 (m, 1H), 1.14 (s, 9H), 1.09–1.03 (m, 4H); 13C {1H} NMR (101 MHz, CDCl3) δ
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164.9, 162.6, 149.1, 140.9, 137.4, 133.5, 128.8, 128.6, 127.5, 126.7, 126.4, 113.3, 111.5, 51.3, 36.3,
29.7, 9.2, 8.9; HRMS (ESI, m/z): calcd for C23H27O3 [M+H]+ 351.1955, found 351.1956; IR (film):
2958, 1720, 1601, 1447, 1233, 1072, 968, 814, 751, 692 cm−1.
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Dimethyl (5-((3Z,5E)-2,2-dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methylfuran-3-yl)phosphonate (4j).
Yield: 72% (54.1 mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.35–7.23 (m, 4H), 7.22-7.15 (m, 1H),
6.78 (dd, J = 15.4 Hz, 10.6 Hz, 1H), 6.63 (d, J = 15.6 Hz, 1H), 6.49 (d, J = 10.8 Hz, 1H), 6.28 (d, J =
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2.8 Hz, 1H), 3.78 (d, J = 11.2 Hz, 6H), 2.58 (s, 3H), 1.18 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ
159.7 (d, J = 26.9 Hz), 151.4 (d, J = 16.2 Hz), 141.0, 137.3, 133.6, 129.3, 128.5, 127.5, 126.6, 126.3,
112.4 (d, J = 11.7 Hz), 106.0 (d, J = 216.8 Hz), 52.3 (d, J = 5.7 Hz), 36.2, 29.7, 13.6; HRMS (ESI, m/z):
calcd for C21H28O4P [M+H]+ 375.1720, found 375.1724; IR (film): 2960, 1257, 1028, 829, 780, 751,
663 cm−1.
5-((3Z,5E)-2,2-Dimethyl-6-phenylhexa-3,5-dien-3-yl)-2-methyl-3-tosylfuran (4k). Yield: 48% (39.6
mg); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.29-
7.18 (m, 5H), 6.70–6.57 (m, 2H), 6.47 (d, J = 8.4 Hz, 1H), 6.40 (s, 1H), 2.62 (s, 3H), 2.45 (s, 3H), 1.14
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(s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 155.3, 151.3, 143.9, 140.4, 139.9, 137.1, 134.0, 129.9,
129.8, 128.5, 127.7, 126.8, 126.4, 126.1, 123.3, 110.0, 36.2, 29.7, 21.6, 13.1; HRMS (ESI, m/z): calcd
for C26H29O3S [M+H]+ 421.1832, found 421.1830; IR (film): 2955, 1321, 1160, 970, 753, 680 cm−1.
ASSOCIATED CONTENT
AUTHOR INFORMATION
Corresponding Author
*Email: wangjb@pku.edu.cn.
ORCID
Jianbo Wang: 0000-0002-0092-0937
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Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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The project is supported by National Basic Research Program of China (973 Program, No.
2015CB856600) and NSFC (Grant 21871010).
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Supporting Information
Copies of 1H and 13C spectra for all products. This material is available free of charge via the Internet at
http://pubs.acs.org.
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