Synthesis of Oxatricyclooctanes via Photoinduced Intramolecular Oxa-[4+2] Cycloaddition of Substituted o-Divinylbenzenes

Article abstract of DOI:10.1021/acs.joc.7b01055

The photolysis of substituted o-divinylbenzenes promotes a one-step and metal-free conversion to oxatricycles at room temperature. Irradiation o-divinylbenzenes results in an pericyclic reaction to form cyclic o-quinodiemthane intermediates, which subsequently undergo intramolecular oxa-[4+2] cycloaddition to form oxacyclic derivatives.

Full text of DOI:10.1021/acs.joc.7b01055

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Article
Synthesis of Oxatricyclooctanes via Photoinduced Intramolecular
Oxa-[4+2] Cycloaddition of Substituted o-Divinylbenzenes
Qiang Liu, Junlei Wang, Dazhi Li, Guo-Lin Gao, Chao Yang, Yuan (Y.) Gao, and Wujiong Xia
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01055 • Publication Date (Web): 12 Jul 2017
Downloaded from http://pubs.acs.org on July 12, 2017
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Synthesis of Oxatricyclooctanes via Photoinduced
Intramolecular Oxa-[4+2] Cycloaddition of Substituted
o-Divinylbenzenes
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Qiang Liu†, Junlei Wang†, Dazhi Li†, GuoꢀLin Gao†, Chao Yang, †,* Yuan (Y.) Gao‡ and Wujiong
Xia†,*
†State Key Lab of Urban Water Resource and Environment, School of Chemistry and Chemical
Engineering, Harbin Institute of Technology, Harbin 150080
‡School of Chemistry and chemical Engineering, Yantai University, #30 Qingquan RD, Laishan
District, Yantai, China 264005
*Eꢀmail: xyyang@hit.edu.cn
*Eꢀmail: xiawj@hit.edu.cn
ABSTRACT: The photolysis of substituted oꢀdivinyl benzenes promotes a oneꢀstep and
metalꢀfree conversion to oxatricycles at room temperature. Irradiation oꢀdivinylbenzenes results in
an pericyclic reaction to form cyclic oꢀquinodiemthane intermediates, which subsequently undergo
intramolecular oxaꢀ[4+2] cycloaddition to form oxacyclic derivatives.
INTRODUCTION
Photoinduced organic reaction is a significant and powerful tool for the generation of carboꢀ
and heteroꢀcyclic frameworks in the synthesis of complex polycyclic compounds1 or natural
products2 possessing a broad range of significant biological activities, which, however, would be
difficult to access with the classical methods in the ground state. More specifically, photochemical
reaction is an environmentally friendly way for syntheses of various natural products and
unnatural compounds because it often does not require activation reagents such as acids, bases,
metals or enzymes.3
The complicated oxacyclic compounds are widely present in numerous biologically
active natural products such as przewalskin and carnosol (Figure 1).4 For example, compound A
(Figure 1) which was reported by Chao et al. exhibits significant antiꢀHCV (antiꢀhepatitis C virus)
activity (EC50 = 7.5 ꢁM) with nontoxicity (IC50 = 419.2 ꢁM) and has a higher therapeutic index
(TI) value (TI = 55.9).5 However, current synthetic examples often need multiple steps to build the
oxaꢀskeletons and only a few methods that use transition metals, e.g. Rh, Pt or Au as catalysts, are
reported (Scheme 1).6 For instance, Adams and coꢀworker have developed a cyclopropanation
reaction promoted by [Rh(OAc)2]2 to generate such tricyclic compound (Scheme 1, a).6a
Subsequently, Oh’s group developed the PtCl2 catalysed cyclization reaction to afford fused
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cyclopropanes (Scheme 1, b).6b Besides, Liu et al. have demonstrated tandem
oxacyclization/[4+2]ꢀcycloaddition cascade reaction for the synthesis of highly substituted
oxacyclic compounds catalysed by Au (Scheme 1, c).6c With our continues on the photochemical
methodologies7, especially the work for construction of benzobicyclo[2.2.2]octane skeletons using
oꢀdivinylbenzenes and olefins7d, we found that such oꢀdivinylbenzenes can generate
oxatricyclooctanes under UV light when there was no dienophile in the reaction system. It is a
convenient, transitionꢀmetalꢀfree and stepꢀeconomical approach for the rapid construction of such
bridgedꢀring compounds through photoinduced intramolecular oxaꢀ[4+2] reactions of substituted
oꢀdivinylbenzenes (Scheme 1, d).
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Figure 1. Natural products with complicated oxacyclic skeletons
Scheme 1. Approaches for the complicated oxacyclic skeletons
RESULTS AND DISCUSSION
Our investigation was initially carried out by the irradiation of substituted orthoꢀdivinylbenzene
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a1 in MeCN under air using 350 nm wavelength as light source at room temperature. The desired
product b1 containing cis/trans stereoisomers were obtained in 80% isolated yield (Table 1, entry
1). Subsequently, light source was screened, and it indicated that the suitable wavelength was
proved to be 350 nm or 500 W medium pressure mercury lamp with a Pyrex filter (Table 1, entries
1ꢀ4). The reaction did not take place in the blue LEDs (Table 1, entry 5). Further, a set of solvents
was examined and the reaction performed in MeCN provided the best result (Table 1, entries 1,
6ꢀ12). Other strong polar solvents, such as MeOH and DMF were proved to be ineffective for this
transformation (Table 1, entries 8ꢀ9). Wet MeCN also proceeded smoothly with a decreased yield,
which meant that this reaction was not sensitive to moisture (Table 1, entry 13). Further
investigation showed that higher yield could be obtained when the reaction was carried out under
a N2 atmosphere (Table 1, entry 14).
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Table 1. Optimization of Reaction Conditions a
To investigate the scope of this protocol, a variety of substituted
oꢀdivinylbenzenes
derivatives were prepared and subjected to the optimized reaction conditions, and the
representative results were listed in Table 2. As expected, the reaction worked well in the
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cases of alkyl ketones to afford the target products in good to excellent yields (Table 2, b1
,
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b2). Sterically bulky groups, such as butyl or phenyl on substrate could also furnish the
corresponding products but in lower yields as 52% and 45%, respectively (Table 2, b3 b4),
,
which might be due to the groups that had large steric hindrance and might cause other side
reactions, e.g. Norrish type I/II reaction.8
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Table 2. Study of reaction scope a
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Then we examined the substrates containing ester groups which, as expected, led to the
corresponding products in good yields (Table 2, b5-b14). The aryl groups with different
groups were also tolerated under the reaction conditions. For example, both
electronꢀdonating substituents (MeO, Me) and electronꢀwithdrawing substituents (F, Cl) on
the phenyl ring were suitable for this reaction, leading to the corresponding products in
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moderate to good yields (Table 2, b15-b20, b33-b37). Substituted 1,2ꢀdivinylnaphthalene
also worked well under the reaction conditions to afford the desired product in 53% yield
(Table 2, b21). Next we turned our attention to the investigation of substrate containing a
cyano group, which worked smoothly to get the product in 78% yield (Table 2, b22). We
examined the substrates with aldehyde groups, and it was found that the reactions were
completed within shorter reaction time, which was probably due to the aldehyde group that
was easy to be excited by UV light (Table 2, b23-b37). Furthermore, the substrate
containing two ester groups could furnish the corresponding products with lower yield,
probably due to the fact that the carbonꢀoxygen double bond of ester group was not a good
dienophile compared with carbonyl group or aldehyde group in this reaction (Table 2, b38).
The structure of all obtained photoproducts was assigned on the basis of 1H, 13C, 2D NMR,
and mass spectrometry analysis. Two of the products b6’ and b22’ (Table 2) were suitable
for Xꢀray singleꢀcrystal structure analysis (Xꢀray crystallography data see SI), allowing
unambiguous determination of the structure and relative configuration.9
Before the mechanism was proposed, a survey of literatures was conducted and showed
that the photochemistry of stilbeneꢀlike compound trended to form the
benzobicyclo[2.1.1]hexene photoproduct via a freeꢀradical process.10 However, Marija
ŠindlerꢀKulyk group did not observe such a product, but benzo[f]quinolone derivatives
instead when they studied the photochemistry of stilbeneꢀlike compound with a different
substituted group.11 The study from Škorić’s group on the photochemistry of butadiene
derivatives showed that a sixꢀmembered ring closure followed by a sigmatropic 1,5ꢀH shift
was involved in the reaction and the cyclic
oꢀquinodimethane (oꢀQDM) was the key
intermediate (Scheme 2, eq. 1)12, which might be helpful for us to map out the reaction
mechanism. To collect more information, we then carried out a few control experiments.
At first, a radical scavenger, (2,2,6,6ꢀtetramethylpiperidinꢀ1ꢀyl)oxidanyl (TEMPO), was
added to the reaction of 1a in order to determine whether the process of the formation of
oxatricyclootanes is a radical pathway or not. Consequently, compound b1' was obtained
as a single product which meant this process of the formation photoproduct is not a radical
pathway, and its stereoisomer b1'' was vanished (Scheme 2, eq. 2) which was owing to
TEMPO that could prevent the photochemical cis/trans isomerization. Another control
experiment was conducted by adding excess amount of butylated hydroxytoluene (BHT) to
the reaction of 1a which afforded the products smoothly (Scheme 2, eq. 3) which also
meant the process of the formation oxatricyclooctanes is not a radical pathway. The above
experimental results indicated that a radical pathway could be excluded in this
photoinduced reaction. To add more credence, four more control experiments were
conducted by addition of cyclohexaꢀ1,3ꢀdiene, transꢀstilbene, phenylacetylene, anthracene
as a triplet quencher in the solution of a1 in MeCN, which had no effects on this reaction
efficiency. In addition, we successfully obtained the benzobicyclo[2.2.2]octane derivative
c1 and c5 in good yield when we added dienophile such as maleic anhydride and
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NꢀMethylmaleimide into the system to trap the reactive intermediate cyclic
oꢀQDM
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(Scheme 2, eq. 4,5). Such a result revealed that a highly reactive intermediate cyclic
o
ꢀQDM might be formed via a conrotatory sixꢀmembered ring closure process according to
WoodwordꢀHoffmann rules13 which was consistent with the work of Škorić’s group
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(Scheme 2, eq. 1).
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Scheme 2. Previous work and control experiments
Scheme 3. Plausible mechanism
Based upon these observations, we propose the mechanism depicted in Scheme 3. Under
the irradiation of UV light, the double bond of trans
pericyclic reaction to form a highly reactive intermediate cyclicꢀ
reactive intermediate, the intermediate ꢀQDM can react with carbonꢀoxygen double bond
via a DielsꢀAlder reaction to form the final product.14 In addition, carbonꢀcarbon double
,
trans-a was excited to cause a
oꢀQDM. As a highly
o
bond can undergo photochemical cis/trans isomerization reaction to form cis,trans-a which
could furnish the minor stereoisomer product in same manner.
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Scheme 4. Synthetic transformation of compound b10
The synthetic application of the products has been demonstrated by catalytic
hydrogenation of the product b10 as a representative compound which led to the
oxaꢀbicyclic product d10 in 90% yield via opening of the cyclopropane ring (Scheme 4).
Scheme 5. Reaction of a1 at gram scale
To demonstrate the potential utility of this methodology, a gram scale reaction of a1 was
carried out. The desired product was isolated in 78% yield under the standard reaction
conditions (Scheme 5).
CONCLUSION
In summary, we have developed a facile and metalꢀfree procedure for the syntheses of
complicated oxacyclic skeleton compounds via photoinduced intramolecular oxaꢀ[4+2]
reactions of substituted oꢀdivinylbenzenes under mild condition. This reaction undergoes a
pericyclic reaction through a conrotatory sixꢀmembered ring closure process to form
o
ꢀquinodimethane as the key intermediate. In addition, the gram scale reaction
demonstrated the synthetic value and utility of this protocol.
EXPERIMENTAL SECTION
General Information. Reagents were purchased at the highest commercial quality and used
without further purification, unless otherwise stated. Flash column chromatography was
1
performed using 200ꢀ300 mesh silica gel. H NMR (400 MHz or 600 MHz) and 13C NMR (100
MHz or 150 MHz) spectra were obtained in CDCl3 or DMSOꢀd6 with TMS as internal standard.
Highꢀresolution mass spectra (HRMS) were recorded on a QꢀTOF (ESI) mass spectrometer.
Lowꢀresolution Mass spectra were obtained from GCꢀMS system. The 350 nm light is from the
phosphorꢀcoated lamps (emission centered at 350 nm). The 500 W medium pressure mercury
lamp is a mercury arc lamp. A Pyrex filter works as a filter for a shorter wavelength of UV (~<280
nm). The wavelength of the blue LED is 450 nm and its intensity is 6 W.
General Procedure for Preparation of Substrates
General Procedure for Syntheses of Compound a1-a4
A solution of the 1ꢀbromopropanꢀ2ꢀone (1.0 g, 7.3 mmol) and triphenylphosphine (1.9 g, 7.3
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mmol) were refluxed in toluene (50 mL) for 4 h. After completion, the reaction mixture was
allowed to cool to room temperature and the phosphonium salt was filtered and washed with Et2O
(3×50 mL). The phosponium salt was then dissolved in H2O: DCM (1:1) 150 mL and 4 M. aq.
NaOH (50 mL) was added. The mixture was stirred for 2 h and then extracted with DCM (3×100
mL). The combined organic phases were washed with brine, dried (Na2SO4) and concentrated in
vacuo to afford 1ꢀ(triphenylphosphoranylidene)propanꢀ2ꢀone as a white solid.15 To a solution of
phthaldialdehyde (402 mg, 3.0 mmol) in THF (30 mL) was added the
1ꢀ(triphenylphosphoranylidene)propanꢀ2ꢀone (7.2 mmol). The mixture was stirred at room
temperature for 16 h and concentrated in vacuo. Purification of the residue by column
chromatography (petroleum ether/EtOAc = 5/1) afforded the compound a1 as a white solid.16
Yield 79% (based on phthaldialdehyde). Compounds a2-a4 are prepared following the general
procedure above.
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General Procedure for Syntheses of Compound a5-a14
To a solution of phthaldialdehyde (5.0 mmol) in THF (60 mL) was added the ethyl
2ꢀ(triphenylphosphoranylidene)acetate (5.0 mmol). The mixture was stirred at room temperature
for 16 h and concentrated in vacuo. Purification of the residue by column chromatography
(petroleum ether/EtOAc: 9/1) afforded the (E)ꢀethyl 3ꢀ(2ꢀformylphenyl)acrylate.16 To a solution
of (E)ꢀethyl 3ꢀ(2ꢀformylphenyl)acrylate (4.0 mmol) in THF (60 mL) was added the
1ꢀ(triphenylphosphoranylidene)propanꢀ2ꢀone (5.0 mmol). The mixture was stirred at room
temperature for 16 h and concentrated in vacuo. Purification of the residue by column
chromatography (petroleum ether/EtOAc: 5/1) afforded the compound a6.16 Yield 64%. (based on
phthaldialdehyde for two steps). Compounds a5, a7-a14 are prepared following the general
procedure above.
General Procedure for Syntheses of Compound a15-a22
To a solution of the 2ꢀbromoꢀ5ꢀfluorobenzaldehyde (10.0 mmol) in anhydrous toluene (100 mL)
were successively added Pd(OAc)2 (0.2 mmol), triphenylphosphine (0.4 mmol), ethyl acrylate (20
mmol) and triethylamine (25 mmol) at room temperature. The reaction mixture was heated at
reflux for 24h, cooled to r.t., diluted with ether and filtered through a thin pad of Celite. The
filtrate was diluted with water and extracted with ether. The organic layers were combined, dried
over MgSO4, and concentrated under vacuum. The dark thick oil obtained was purified by flash
silica chromatography employing mixtures of nꢀhexane and ethyl acetate as eluents to get the
(E)ꢀethyl
3ꢀ(4ꢀfluoroꢀ2ꢀformylphenyl)acrylate.17
To
a
solution
of
(E)ꢀethyl
3ꢀ(4ꢀfluoroꢀ2ꢀformylphenyl)acrylate (5.0 mmol) in THF (60 mL) was added
1ꢀ(triphenylphosphoranylidene)propanꢀ2ꢀone (6.0 mmol). The mixture was stirred at room
temperature for 16 h and concentrated in vacuo. Purification of the residue by column
chromatography (petroleum ether/EtOAc: 9/1) afforded the compound a15.16 Yield 45% (based on
2ꢀbromoꢀ5ꢀfluorobenzaldehyde for two steps). Compounds a16-a22 are prepared following the
general procedure above (For Compounds a16-a22 the starting material 5.0 mmol).
General Procedure for Syntheses of Compound a23-a38
To a solution of phthaldialdehyde (5.0 mmol) in THF (60 mL) was added the ethyl
2ꢀ(triphenylphosphoranylidene)acetate (11.0 mmol). The mixture was stirred at room temperature
for 16 h and concentrated in vacuo. Purification of the residue by column chromatography
(petroleum ether/EtOAc: 9/1) afforded the (E)ꢀ3ꢀ[2ꢀ{(E)ꢀ2ꢀEthoxycarbonylvinyl}phenyl]acrylic
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acid ethyl ester.16 To a solution of the the (E)ꢀ3ꢀ[2ꢀ{(E)ꢀ2ꢀEthoxycarbonylvinyl}phenyl]acrylic
acid ethyl ester (3 mmol) in dry THF (20 mL) at −78 °C was added DIBALꢀH (6.2 mL of a 1.0 M
solution in toluene, 6.2 mmol) slowly. After stirring for 1 h, the reaction mixture was allowed to
return to 0 °C. Four hours later, the reaction was quenched with methanol (3 mL). Then 20 mL
aqueous solution of 0.5 M HCl was added. One hour later, the layers were separated and the
aqueous layer was extracted with EtOAc (3 × 20 mL). The combined organic extracts were
washed with brine, dried over Na2SO4, and concentrated. Purification of the crude product by
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chromatography on silica gel
(
EtOAc/hexane, 1/3
)
gave the (E)ꢀethyl
3ꢀ(2ꢀ((E)ꢀ3ꢀhydroxypropꢀ1ꢀenꢀ1ꢀyl)phenyl)acrylate as a clear oil.18 To a solution of oxalyl chloride
( 2.4 mmol ) in dry CH2Cl2 (10 mL) cooled at −78 °C was added dropwise a solution of
dimethylsulfoxide (DMSO 2.3 mmol ) in CH2Cl2 (10 mL). After 5 min, a solution of the (E)ꢀethyl
3ꢀ(2ꢀ((E)ꢀ3ꢀhydroxypropꢀ1ꢀenꢀ1ꢀyl)phenyl)acrylate (2 mmol ) in CH2Cl2 (10 mL) was added. The
reaction mixture was then stirred for 15 min at −78 °C and triethylamine (10 mmol ) was added in
one portion. After 10 min at −78 °C, the mixture was allowed to warm to room temperature and
diluted with CH2Cl2 (40 mL). The organic layer was successively washed with a saturated aqueous
solution of NH4Cl (20 mL) and brine (20 mL). The combined organic extracts were dried over
MgSO4, filtered, and concentrated under reduced pressure. Purification by flash chromatography
on silica gel (petroleum ether/EtOAc: 9/1) afforded the aldehyde a24. Yield 36% (based on
phthaldialdehyde for three steps). Compounds a23, a25-a38 are prepared following the general
procedure above.
General Procedures for Preparation of Products.
A quartz glass tube was charged with substrate a (0.5 mmol) and then charged with N2 three times.
Then anhydrous MeCN (50 mL) was added. The mixture was allowed to expose to 350
nm mercury lamp for 0.5ꢀ18h (monitored by TLC). After the substrate was consumed. The
reaction was cooled to room temperature. Then, the solvent was removed in vacuo, the residue
was purified by column chromatography to give the product b.
Gram scale reactions: A quartz glass tube was charged with substrate a1 (1.0 g) and then charged
with N2 three times. Then anhydrous MeCN (200 mL) was added. The mixture was allowed to
expose to 300nm mercury lamp with Pyrex filter for 8 h (monitored by TLC). After the substrate
a1 was consumed. The reaction was cooled to room temperature. Then, the solvent was removed
in vacuo, the residue was purified by column chromatography to give the product b1.
(3E,3'E)-4,4'-(1,2-phenylene)bis(but-3-en-2-one) a1.16 White solid. 507 mg. Yield 79%. Mp.
89ꢀ90 oC. 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 16.0 Hz, 2H), 7.60 (dd, J = 5.7, 3.5 Hz, 2H),
7.43 (dd, J = 5.8, 3.3 Hz, 2H), 6.64 (d, J = 16.0 Hz, 2H), 2.41 (s, 6H). 13C NMR (150 MHz,
CDCl3) δ 197.9, 139.8, 134.6, 130.4, 130.3, 127.8, 28.1. HRMS (ESI): calcd for C14H15O2, [M+H]
+, 215.1067; found, 215.1069.
1
(1E,1'E)-1,1'-(1,2-phenylene)bis(pent-1-en-3-one) a2. White solid. 544 mg. Yield 75%. H NMR
(400 MHz, CDCl3) δ 7.91 (d, J = 16.0 Hz, 2H), 7.59 (dd, J = 5.7, 3.5 Hz, 2H), 7.41 (dd, J = 5.8,
3.3 Hz, 2H), 6.65 (d, J = 16.0 Hz, 2H), 2.72 (q, J = 7.3 Hz, 4H), 1.19 (t, J = 7.3 Hz, 6H). 13C NMR
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(150 MHz, CDCl3) δ 200.4, 138.7, 134.7, 130.1, 129.4, 127.7, 34.5, 8.1. HRMS (ESI): calcd for
C16H19O2, [M+H] +, 243.1380; found, 243.1387.
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(1E,1'E)-1,1'-(1,2-phenylene)bis(4,4-dimethylpent-1-en-3-one) a3. White solid. 625 mg. Yield
70%. Mp. 92ꢀ93 oC. 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 15.5 Hz, 2H), 7.75 – 7.52 (m, 2H),
7.40 (dd, J = 5.6, 3.4 Hz, 2H), 6.98 (d, J = 15.5 Hz, 2H), 1.23 (s, 18H). 13C NMR (150 MHz,
CDCl3) δ 203.7, 140.2, 135.48, 129.78, 128.28, 124.8, 43.2, 26.3. HRMS (ESI): calcd for
C20H27O2, [M+H] +, 299.2006; found, 299.2010.
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(2E,2'E)-3,3'-(1,2-phenylene)bis(1-phenylprop-2-en-1-one) a4.16 Yellow solid. 578 mg. Yield 57%.
Mp 125ꢀ126 oC. 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 15.6 Hz, 2H), 8.03 (d, J = 7.6 Hz, 4H),
7.72 (dd, J = 5.5, 3.5 Hz, 2H), 7.59 (t, J = 7.3 Hz, 2H), 7.55 – 7.46 (m, 4H), 7.43 (d, J = 15.6 Hz, 2H).
13C NMR (100 MHz, CDCl3) δ 190.11 , 141.75 , 137.94 , 135.44 , 132.99 , 130.15 , 128.72 , 128.63 ,
128.22 , 126.14 . HRMS (ESI): calcd for C24H19O2, [M+H] +, 339.1380; found, 339.1375.
(E)-methyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a5. White solid. 782 mg. Yield 68%. Mp.
46ꢀ47 oC. 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 15.8 Hz, 1H), 7.87 (d, J = 16.0 Hz, 1H), 7.58
(dd, J = 9.0, 5.1 Hz, 2H), 7.42 (ddd, J = 6.1, 4.0, 2.1 Hz, 2H), 6.63 (d, J = 16.1 Hz, 1H), 6.36 (dd,
J = 15.8, 0.7 Hz, 1H), 3.83 (d, J = 0.7 Hz, 3H), 2.41 (d, J = 0.7 Hz, 3H). 13C NMR (150 MHz,
CDCl3) δ 192.6, 161.5, 136.1, 134.5, 129.1, 128.9, 125.1, 124.9, 124.8, 122.4, 122.3, 116.3, 46.6,
22.6. HRMS (ESI): calcd for C14H15O3, [M+H] +, 231.1016; found, 231.1020.
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(E)-ethyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a6. White solid. 780 mg. Yield 64%. H
NMR (400 MHz, CDCl3) δ 8.03 (d, J = 15.8 Hz, 1H), 7.87 (d, J = 16.1 Hz, 1H), 7.70 – 7.52 (m,
2H), 7.52 – 7.33 (m, 2H), 6.62 (d, J = 16.1 Hz, 1H), 6.36 (dd, J = 15.8, 0.8 Hz, 1H), 4.29 (qd, J =
7.1, 0.7 Hz, 2H), 2.41 (d, J = 0.8 Hz, 3H), 1.35 (td, J = 7.1, 0.7 Hz, 3H). 13C NMR (150 MHz,
CDCl3) δ 192.7, 161.1, 135.9, 134.6, 129.2, 128.9, 125.1, 124.9, 124.8, 122.4, 122.3, 116.8, 55.4,
22.5, 9.0. HRMS (ESI): calcd for C15H17O3, [M+H] +, 245.1172; found, 245.1177.
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(E)-butyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a7. White solid. 816 mg. Yield 60%. H
NMR (400 MHz, CDCl3) δ 8.03 (d, J = 15.8 Hz, 1H), 7.87 (d, J = 16.1 Hz, 1H), 7.58 (dd, J = 6.1,
2.7 Hz, 2H), 7.41 (dd, J = 5.7, 3.5 Hz, 2H), 6.62 (d, J = 16.1 Hz, 1H), 6.36 (d, J = 15.8 Hz, 1H),
4.24 (t, J = 6.7 Hz, 2H), 2.41 (s, 3H), 1.80 – 1.62 (m, 2H), 1.58 – 1.35 (m, 2H), 0.98 (t, J = 7.4 Hz,
3H). 13C NMR (150 MHz, CDCl3) δ 192.7, 161.2, 135.8, 134.6, 129.2, 128.9, 125.1, 124.94,
124.79, 122.46, 122.36, 116.7, 59.3, 25.4, 22.3, 13.9, 8.46. HRMS (ESI): calcd for C17H21O3,
[M+H] +, 273.1485; found, 273.1490.
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(E)-tert-butyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a8. White solid. 788 mg. Yield 58%.
Mp. 85ꢀ86 oC. 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 15.8 Hz, 1H), 7.87 (d, J = 16.1 Hz, 1H),
7.65 – 7.48 (m, 2H), 7.48 – 7.11 (m, 2H), 6.60 (d, J = 16.1 Hz, 1H), 6.29 (d, J = 15.8 Hz, 1H),
2.40 (s, 3H), 1.55 (s, 9H). 13C NMR (150 MHz, CDCl3) δ 197.9, 165.6, 139.98, 139.96, 134.56,
134.1, 130.3, 130.2, 129.8, 127.6, 127.5, 123.8, 80.8, 28.1, 27.6. HRMS (ESI): calcd for C17H21O3,
[M+H] +, 273.1485; found, 273.1489.
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(E)-phenyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a9. White solid. 730 mg. Yield 50%. Mp.
73ꢀ74 oC. 1H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 15.8 Hz, 1H), 7.90 (d, J = 16.1 Hz, 1H), 7.67
(dd, J = 5.4, 3.7 Hz, 1H), 7.62 (dd, J = 5.5, 3.7 Hz, 1H), 7.49 – 7.43 (m, 2H), 7.41 (d, J = 8.2 Hz,
2H), 7.31 – 7.23 (m, 1H), 7.22 – 7.09 (m, 2H), 6.65 (d, J = 16.1 Hz, 1H), 6.57 (d, J = 15.8 Hz, 1H),
2.41 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 197.9, 164.8, 150.6, 143.1, 139.7, 134.5, 134.1, 130.7,
130.5, 130.3, 129.5, 127.9, 127.8, 125.9, 121.6, 121.0, 27.8. HRMS (ESI): calcd for C19H17O3,
[M+H] +, 293.1172; found, 293.1173.
(E)-cyclohexyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a10. White solid. 774 mg. Yield 52%.
1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 15.8 Hz, 1H), 7.87 (d, J = 16.1 Hz, 1H), 7.59 (dd, J =
5.4, 3.8 Hz, 2H), 7.47 – 7.35 (m, 2H), 6.62 (d, J = 16.1 Hz, 1H), 6.35 (d, J = 15.8 Hz, 1H), 5.13 –
4.73 (m, 1H), 2.41 (s, 3H), 1.93 (m 2H), 1.77 (m, 2H), 1.62 – 1.16 (m, 6H). 13C NMR (150 MHz,
CDCl3) δ 192.7, 160.5, 135.5, 134.7, 129.2, 128.9, 125.1, 124.9, 124.7 122.4, 122.3, 117.3, 67.7,
26.4, 22.3, 20.1, 18.5. HRMS (ESI): calcd for C19H23O3, [M+H] +, 299.1642; found, 299.1644.
(E)-benzyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a11. White solid. 765 mg. Yield 50%. 1H
NMR (400 MHz, CDCl3) δ 8.08 (d, J = 15.8 Hz, 1H), 7.85 (d, J = 16.1 Hz, 1H), 7.68 – 7.49 (m,
2H), 7.49 – 7.31 (m, 7H), 6.61 (d, J = 16.1 Hz, 1H), 6.41 (d, J = 15.8 Hz, 1H), 5.27 (s, 2H), 2.39
(s, 3H). 13C NMR (150 MHz, CDCl3) δ 198.0, 166.2, 141.8, 139.9, 135.8, 134.3, 130.6, 130.27,
130.25, 128.6, 128.39, 128.35, 127.76, 127.74, 121.6, 66.6, 27.7. HRMS (ESI): calcd for
C20H19O3, [M+H] +, 307.1329; found, 307.1330.
(E)-4-fluorobenzyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a12. White solid. 842 mg. Yield
52%. Mp. 79ꢀ80 oC. 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 15.8 Hz, 1H), 7.85 (d, J = 16.1 Hz,
1H), 7.71 – 7.48 (m, 2H), 7.41 (dt, J = 5.8, 4.0 Hz, 4H), 7.18 – 6.95 (m, 2H), 6.61 (d, J = 16.1 Hz,
1H), 6.39 (d, J = 15.8 Hz, 1H), 5.23 (s, 2H), 2.39 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 197.9,
166.1, 162.72 (d, J = 247.1 Hz), 141.9, 139.8, 134.34 (d, J = 11.8 Hz), 131.74 (d, J = 3.2 Hz),
130.5, 130.4, 130.3, 130.29, 130.27, 127.76, 127.74, 121.45, 115.59 (d, J = 21.6 Hz), 65.87, 27.8.
HRMS (ESI): calcd for C20H18FO3, [M+H] +, 325.1234; found, 325.1233.
(E)-4-(trifluoromethyl)benzyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a13. White solid. 991
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mg. Yield 53%. H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 15.8 Hz, 1H), 7.86 (d, J = 16.1 Hz,
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1H), 7.65 (d, J = 8.2 Hz, 1H), 7.62 – 7.57 (m, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.46 – 7.40 (m, 1H),
6.62 (d, J = 16.0 Hz, 1H), 6.42 (d, J = 15.8 Hz, 1H), 5.32 (s, 1H), 2.39 (s, 2H). 13C NMR (150
MHz, CDCl3) δ 192.5, 160.7, 137.0, 134.6, 134.51 (q, J = 27.7 Hz), 134.4, 129.1, 128.8, 125.2,
125.0, 125.0, 124.9, 122.9, 122.4, 120.3 (q, J = 3.5 Hz), 118.7 (d, J = 272.0 Hz), 115.7, 60.2, 22.5.
HRMS (ESI): calcd for C21H18F3O3, [M+H] +, 375.1203; found, 375.1204.
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(E)-4-methoxybenzyl 3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a14. White solid. 789 mg.
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Yield 47%. H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 15.8 Hz, 1H), 7.85 (d, J = 16.1 Hz, 1H),
7.70 – 7.50 (m, 2H), 7.47 – 7.32 (m, 4H), 6.92 (d, J = 8.5 Hz, 2H), 6.60 (d, J = 16.1 Hz, 1H), 6.38
(d, J = 15.8 Hz, 1H), 5.21 (s, 2H), 3.82 (s, 3H), 2.39 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 198.0,
166.3, 159.7, 141.6, 139.9, 134.4, 134.3, 130.5, 130.2, 130.1, 127.9, 127.75, 127.71, 121.8, 114.0,
66.4, 55.3, 27.7. HRMS (ESI): calcd for C21H21O4, [M+H] +, 337.1434; found, 337.1435.
(E)-ethyl 3-(4-fluoro-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a15. White solid. 1179 mg. Yield
45%. Mp. 64ꢀ65 oC. 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 15.8 Hz, 1H), 7.81 (d, J = 16.0 Hz,
1H), 7.58 (dd, J = 8.7, 5.7 Hz, 1H), 7.27 (dd, J = 9.3, 2.6 Hz, 1H), 7.12 (td, J = 8.4, 2.5 Hz, 1H),
6.61 (d, J = 16.0 Hz, 1H), 6.31 (d, J = 15.8 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 2.41 (s, 3H), 1.35 (t,
J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 197.5, 166.2, 163.4 (d, J = 251.6 Hz), 139.9,
138.5 (d, J = 1.8 Hz), 136.4 (d, J = 8.2 Hz), 131.0 , 130.7 (d, J = 3.0 Hz), 129.8 (d, J = 8.3 Hz),
121.9, 117.5 (d, J = 22.0 Hz), 114.1 (d, J = 22.8 Hz), 60.8, 28.1, 14.3. HRMS (ESI): calcd for
C15H16O3F, [M+H] +, 263.1078; found, 263.1076.
(E)-ethyl 3-(4-chloro-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a16. White solid. 695 mg. Yield
50%. Mp. 101ꢀ102 oC. 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 15.8 Hz, 1H), 7.78 (d, J = 16.0
Hz, 1H), 7.56 (d, J = 1.8 Hz, 1H), 7.52 (d, J = 8.4 Hz, 1H), 7.37 (dd, J = 8.4, 1.7 Hz, 1H), 6.62 (d,
J = 16.0 Hz, 1H), 6.34 (d, J = 15.8 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 2.41 (s, 3H), 1.35 (t, J = 7.1
Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 197.5, 166.2, 139.9, 138.3, 136.1, 135.8, 132.8, 131.1,
+
130.2, 129.0, 127.5, 122.5, 60.9, 28.2, 14.3. HRMS (ESI): calcd for C15H16ClO3, [M+H] ,
279.0782; found, 279.0785.
(E)-ethyl 3-(4-methoxy-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a17. Yellow solid. 643 mg.
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Yield 47%. Mp. 74ꢀ75 C. 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 15.7 Hz, 1H), 7.87 (d, J =
16.1 Hz, 1H), 7.56 (d, J = 8.7 Hz, 1H), 7.05 (d, J = 2.6 Hz, 1H), 6.96 (dd, J = 8.7, 2.6 Hz, 1H),
6.60 (d, J = 16.1 Hz, 1H), 6.27 (d, J = 15.7 Hz, 1H), 4.28 (q, J = 7.1 Hz, 2H), 3.86 (s, 3H), 2.42 (s,
3H), 1.34 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 198.0, 166.8, 160.9, 140.6, 139.9,
135.9, 130.7, 129.2, 127.1, 119.6, 116.7, 111.9, 60.6, 55.5, 27.7, 14.3. HRMS (ESI): calcd for
C16H19O4, [M+H] +, 275.1278; found, 275.1280.
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(E)-ethyl 3-(5-fluoro-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a18. White solid. 641 mg. Yield
49%. 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 15.8 Hz, 1H), 7.80 (d, J = 16.0 Hz, 1H), 7.59 (dd,
J = 8.7, 5.6 Hz, 1H), 7.31 – 7.22 (m, 1H), 7.12 (td, J = 8.3, 2.6 Hz, 1H), 6.58 (d, J = 16.0 Hz, 1H),
6.35 (d, J = 15.8 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 2.40 (s, 3H), 1.36 (t, J = 7.1 Hz, 3H). 13C
NMR (150 MHz, CDCl3) δ 197.7, 166.0, 163.56 (d, J = 251.3 Hz), 139.9, 138.6, 136.70 (d, J =
7.9 Hz), 130.46 (d, J = 3.2 Hz), 130.1, 129.7 (d, J = 8.7 Hz), 123.1, 117.43 (d, J = 22.0 Hz),
114.21 (d, J = 22.8 Hz), 60.9, 27.9, 14.2. HRMS (ESI): calcd for C15H16O3F, [M+H]+, 263.1078;
found, 263.1079.
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(E)-ethyl 3-(5-chloro-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a19. White solid. 583 mg. Yield
42%. Mp. 100ꢀ101 oC. 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 15.8 Hz, 1H), 7.78 (d, J = 16.1
Hz, 1H), 7.54 (dd, J = 8.3, 5.1 Hz, 2H), 7.37 (dd, J = 8.4, 1.7 Hz, 1H), 6.61 (d, J = 16.0 Hz, 1H),
6.36 (d, J = 15.8 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 2.40 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H). 13C
NMR (150 MHz, CDCl3) δ 197.6, 166.0, 139.7, 138.5, 136.2, 136.0, 132.6, 130.5, 130.0, 128.9,
127.6, 123.2, 60.9, 27.9, 14.2. HRMS (ESI): calcd for C15H16ClO3, [M+H] +, 279.0782; found,
279.0784.
(E)-ethyl 3-(5-methyl-2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylate a20. White solid. 670 mg. Yield
52%. 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 15.8 Hz, 1H), 7.84 (d, J = 16.1 Hz, 1H), 7.50 (d,
J = 8.0 Hz, 1H), 7.38 (s, 1H), 7.22 (d, J = 8.0 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.34 (d, J = 15.8
Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 2.40 (s, 3H), 2.39 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H). 13C NMR
(150 MHz, CDCl3) δ 198.0, 166.4, 141.2, 140.6, 139.8, 134.4, 131.4, 131.1, 129.4, 128.3, 127.5,
+
121.8, 60.7, 27.7, 21.3, 14.3. HRMS (ESI): calcd for C16H19O3, [M+H] , 259.1329; found,
259.1330.
(E)-ethyl 3-(2-((E)-3-oxobut-1-en-1-yl)naphthalen-1-yl)acrylate a21. White solid. 588 mg. Yield
40%. 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 16.1 Hz, 1H), 8.13 – 8.01 (m, 1H), 7.92 (d, J = 16.2
Hz, 1H), 7.85 (dd, J = 9.2, 3.8 Hz, 2H), 7.71 (d, J = 8.7 Hz, 1H), 7.56 (dd, J = 6.3, 3.3 Hz, 2H), 6.76 (d,
J = 16.2 Hz, 1H), 6.15 (d, J = 16.1 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 2.40 (s, 3H), 1.39 (t, J = 7.1 Hz,
3H). 13C NMR (151 MHz, CDCl3) δ 198.2, 165.8, 141.6, 140.7, 134.2, 133.8, 131.4, 130.5, 129.4,
129.3, 128.5, 128.4, 127.4, 127.3, 125.4, 123.6, 61.0, 27.6, 14.3. HRMS (ESI): calcd for C19H19O3,
[M+H] +, 295.1329; found, 295.1325.
(E)-3-(2-((E)-3-oxobut-1-en-1-yl)phenyl)acrylonitrile a22. White solid. 364 mg. Yield 37%. Mp.
o
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149ꢀ150 C. H NMR (400 MHz, CDCl3) δ 7.77 (dd, J = 16.2, 4.2 Hz, 2H), 7.60 (d, J = 7.3 Hz,
1H), 7.54 – 7.34 (m, 3H), 6.63 (d, J = 16.0 Hz, 1H), 5.85 (d, J = 16.5 Hz, 1H), 2.42 (s, 3H). 13C
NMR (150 MHz, CDCl3) δ 197.5, 147.4, 138.7, 134.8, 134.1, 133.3, 131.1, 130.9, 130.4, 127.9,
126.9, 99.9, 28.2. HRMS (ESI): calcd for C13H12NO, [M+H] +, 198.0913; found, 198.0914.
(E)-Methyl 3-(2-((E)-3-oxoprop-1-enyl)phenyl)acrylate. a23.19 Yellow solid. 367 mg. Yield 34%.
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Mp. 82ꢀ84 oC. 1H NMR (400 MHz, CDCl3) δ 9.80 (d, J = 7.6 Hz, 1H), 8.09 (d, J = 15.8 Hz, 1H),
7.90 (d, J = 15.8 Hz, 1H), 7.72 – 7.58 (m, 2H), 7.55 – 7.43 (m, 2H), 6.69 (dd, J = 15.8, 7.7 Hz,
1H), 6.41 (d, J = 15.8 Hz, 1H), 3.86 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 193.5, 166.8, 148.8,
141.0, 134.5, 133.5, 131.4, 131.0, 130.3, 127.9, 127.7, 122.1, 52.0. LRMS (EI): 216[M+], 201,
184, 157, 143, 128, 115, 102, 89. HRMS (ESI): calcd for C13H13O3, [M+H] +, 217.0859; found,
217.0866.
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(E)-ethyl 3-(2-((E)-3-oxoprop-1-enyl)phenyl)acrylate. a24.20 Yellow solid. 414 mg. Yield 36%. 1H
NMR (400 MHz, CDCl3) δ 9.78 (d, J = 7.7 Hz, 1H), 8.06 (d, J = 15.8 Hz, 1H), 7.88 (d, J = 15.8
Hz, 1H), 7.69 – 7.57 (m, 2H), 7.55 – 7.38 (m, 2H), 6.67 (dd, J = 15.8, 7.7 Hz, 1H), 6.39 (d, J =
15.8 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
193.4, 166.3, 148.8, 140.7, 134.7, 133.5, 131.4, 131.0, 130.2, 127.9, 127.6, 122.6, 60.9, 14.3.
(E)-isopropyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a25. Colorless oil. 402 mg. Yield
33%. 1H NMR (400 MHz, CDCl3) δ 9.80 (d, J = 7.7 Hz, 1H), 8.06 (d, J = 15.8 Hz, 1H), 7.91 (d, J
= 15.8 Hz, 1H), 7.74 – 7.59 (m, 2H), 7.55 – 7.35 (m, 2H), 6.69 (dd, J = 15.8, 7.7 Hz, 1H), 6.38 (d,
J = 15.8 Hz, 1H), 5.48 – 4.96 (m, 1H), 1.35 (d, J = 6.3 Hz, 6H). 13C NMR (150 MHz, CDCl3) δ
193.5, 165.9, 148.9, 140.4, 134.7, 133.4, 131.3, 131.0, 130.1, 127.8, 127.6, 123.0, 68.3, 21.9.
LRMS (EI): 244[M+], 215, 202, 184, 173, 157, 129, 115, 102, 89. HRMS (ESI): calcd for
C15H17O3, [M+H] +, 245.1172; found, 245.1170.
(E)-butyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a26. White solid. 516 mg. Yield 40%. 1H
NMR (400 MHz, CDCl3) δ 9.80 (d, J = 7.7 Hz, 1H), 8.08 (d, J = 15.8 Hz, 1H), 7.90 (d, J = 15.8
Hz, 1H), 7.74 – 7.58 (m, 2H), 7.55 – 7.41 (m, 2H), 6.69 (dd, J = 15.8, 7.7 Hz, 1H), 6.41 (d, J =
15.8 Hz, 1H), 4.27 (t, J = 6.7 Hz, 2H), 1.72 (dd, J = 14.7, 6.7 Hz, 2H), 1.47 (dd, J = 14.7, 7.4 Hz,
2H), 1.00 (t, J = 7.4 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 193.5, 166.5, 148.8, 140.7, 134.6,
133.4, 131.4, 131.0, 130.2, 127.8, 127.6, 122.5, 64.8, 30.7, 19.22, 13.7. LRMS (EI): 258[M+], 229,
201, 184, 173, 157, 129, 115, 102, 89. HRMS (ESI): calcd for C16H19O3, [M+H] +, 259.1329;
found, 259.1328.
(E)-tert-butyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a27. White solid. 464 mg. Yield 36%.
1H NMR (400 MHz, CDCl3) δ 9.79 (d, J = 7.7 Hz, 1H), 8.00 (d, J = 15.7 Hz, 1H), 7.91 (d, J =
15.8 Hz, 1H), 7.69 – 7.58 (m, 2H), 7.56 – 7.41 (m, 2H), 6.69 (dd, J = 15.8, 7.7 Hz, 1H), 6.34 (d, J
= 15.7 Hz, 1H), 1.58 (s, 9H). 13C NMR (150 MHz, CDCl3) δ 193.5, 165.7, 149.0, 139.6, 134.8,
133.3, 131.2, 131.0, 130.0, 127.8, 127.5, 124.3, 81.1, 28.2. LRMS (EI): 258[M+], 202, 184, 173,
+
157, 145, 129, 115, 102, 89. HRMS (ESI): calcd for C16H19O3, [M+H] , 259.1329; found,
259.1334.
(E)-cyclopentyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a28. Colorless oil. 513 mg. Yield
38%. 1H NMR (400 MHz, CDCl3) δ 9.77 (d, J = 7.7 Hz, 1H), 8.04 (d, J = 15.8 Hz, 1H), 7.88 (d, J =
15.8 Hz, 1H), 7.73 – 7.52 (m, 2H), 7.45 (dd, J = 6.3, 2.7 Hz, 2H), 6.67 (dd, J = 15.8, 7.7 Hz, 1H), 6.36
(d, J = 15.8 Hz, 1H), 5.32 (ddd, J = 8.6, 6.1, 2.7 Hz, 1H), 2.03 – 1.88 (m, 2H), 1.85 – 1.50 (m, 6H). 13C
NMR (150 MHz, CDCl3) δ 193.5, 166.2, 148.9, 140.4, 134.7, 133.4, 131.3, 131.0, 130.1, 127.8, 127.6,
123.0, 77.6, 32.7, 23.8. LRMS (EI): 270[M+], 202, 184, 173, 157, 129, 115. HRMS (ESI): calcd
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(E)-cyclohexyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a29. White solid. 482 mg. Yield
34%. 1H NMR (400 MHz, CDCl3) δ 9.79 (d, J = 7.7 Hz, 1H), 8.06 (d, J = 15.8 Hz, 1H), 7.90 (d, J
= 15.8 Hz, 1H), 7.71 – 7.61 (m, 2H), 7.51 – 7.43 (m, 2H), 6.68 (dd, J = 15.8, 7.7 Hz, 1H), 6.40 (d,
J = 15.8 Hz, 1H), 4.99 – 4.88 (m, 1H), 2.01 – 1.91 (m, 2H), 1.83 – 1.75 (m, 2H), 1.61 – 1.27 (m,
6H). 13C NMR (150 MHz, CDCl3) δ 193.5, 165.8, 148.9, 140.4, 134.7, 133.3, 131.3, 131.0, 130.1,
127.8, 127.6, 123.1, 73.2, 31.7, 25.3, 23.8. LRMS (EI): 284[M+], 202, 184, 157, 129, 115, 102, 83.
HRMS (ESI): calcd for C18H21O3, [M+H] +, 285.1485; found, 285.1489.
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(E)-benzyl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a30. White solid. 613 mg. Yield 42%.
1H NMR (400 MHz, CDCl3) δ 9.79 (d, J = 7.6 Hz, 1H), 8.13 (d, J = 15.8 Hz, 1H), 7.89 (d, J =
15.8 Hz, 1H), 7.67 – 7.62 (m, 2H), 7.49 – 7.38 (m, 7H), 6.69 (dd, J = 15.8, 7.6 Hz, 1H), 6.46 (d, J
= 15.8 Hz, 1H), 5.31 (s, 2H). 13C NMR (150 MHz, CDCl3) δ 193.4, 166.2, 148.7, 141.3, 135.7,
134.4, 133.5, 131.4, 131.0, 130.3, 128.6, 128.4, 128.4, 127.8, 127.6, 122.1, 66.7. LRMS (EI):
292[M+], 201, 186, 157, 141, 128, 115, 91. HRMS (ESI): calcd for C19H17O3, [M+H]+, 293.1172;
found, 293.1180.
(E)-pent-4-en-1-yl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a31. Colorless oil. 405 mg.
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Yield 30%. H NMR (400 MHz, CDCl3) δ 9.78 (d, J = 7.7 Hz, 1H), 8.07 (d, J = 15.8 Hz, 1H),
7.88 (d, J = 15.8 Hz, 1H), 7.74 – 7.56 (m, 2H), 7.46 (dd, J = 8.9, 5.3 Hz, 2H), 6.67 (dd, J = 15.8,
7.6 Hz, 1H), 6.39 (d, J = 15.8 Hz, 1H), 6.02 – 5.64 (m, 1H), 5.07 (dd, J = 17.1, 1.5 Hz, 1H), 5.02
(d, J = 10.2 Hz, 1H), 4.26 (t, J = 6.6 Hz, 2H), 2.19 (dd, J = 14.3, 7.2 Hz, 2H), 1.89 – 1.70 (m, 2H).
13C NMR (150 MHz, CDCl3) δ 193.4, 166.4, 148.8, 140.8, 137.4, 134.5, 133.4, 131.4, 131.0,
130.2, 127.8, 127.6, 122.4, 115.4, 64.3, 30.0, 27.8. LRMS (EI): 270[M+], 201, 184, 157, 129, 28.
HRMS (ESI): calcd for C17H19O3, [M+H] +, 271.1329; found, 271.1330.
(E)-hex-5-en-1-yl 3-(2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a32. Colorless oil. 498 mg. Yield
35%. 1H NMR (400 MHz, CDCl3) δ 9.77 (d, J = 7.7 Hz, 1H), 8.06 (d, J = 15.8 Hz, 1H), 7.88 (d, J =
15.8 Hz, 1H), 7.63 (dd, J = 10.4, 7.0 Hz, 2H), 7.46 (dd, J = 8.9, 5.3 Hz, 2H), 6.67 (dd, J = 15.8, 7.7 Hz,
1H), 6.39 (d, J = 15.7 Hz, 1H), 5.82 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.04 (dd, J = 17.1, 1.6 Hz, 1H),
4.99 (d, J = 10.2 Hz, 1H), 4.25 (t, J = 6.6 Hz, 2H), 2.13 (q, J = 7.1 Hz, 2H), 1.81 – 1.68 (m, 2H), 1.62 –
1.40 (m, 2H). 13C NMR (150 MHz, CDCl3) δ 193.4, 166.4, 148.8, 140.7, 138.3, 134.6, 133.4, 131.4,
131.0, 130.2, 127.8, 127.6, 122.4, 114.9, 64.8, 33.3, 28.1, 25.2. LRMS (EI): 284[M+], 172, 157, 128,
115. HRMS (ESI): calcd for C18H21O3, [M+H] +, 285.1485; found, 285.1487.
(E)-methyl 3-(4 or 5-methyl-2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate. a33. White solid. 369
mg. Yield 32%. 1H NMR (400 MHz, CDCl3) δ 9.76 (t, J = 7.1 Hz, 1H), 8.05 (dd, J = 15.8, 7.2 Hz,
1H), 7.86 (dd, J = 15.7, 10.7 Hz, 1H), 7.69 – 7.49 (m, 1H), 7.43 (d, J = 9.8 Hz, 1H), 7.35 – 7.14
(m, 1H), 6.80 – 6.55 (m, 1H), 6.38 (dd, J = 15.8, 7.6 Hz, 1H), 3.84 (d, J = 2.7 Hz, 3H), 2.41 (d, J =
9.7 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 193.5, 193.5, 166.9, 166.8, 148.9, 148.8, 141.6, 141.1,
140.8, 140.6, 134.5, 133.4, 132.0, 131.7, 131.2, 130.7, 130.4, 128.3, 128.1, 127.7, 127.6, 121.8,
120.9, 51.97, 51.93, 21.49, 21.38. LRMS (EI): 230[M+], 215, 198, 185, 171, 157, 142, 128, 115,
102, 89. HRMS (ESI): calcd for C14H15O3, [M+H] +, 231.1016; found, 231.1017.
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(E)-methyl 3-(4 or 5-chloro-2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a34. White solid. 375 mg.
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Yield 30%. H NMR (400 MHz, CDCl3) δ 9.91 – 9.73 (d, J =7.0 Hz, 1H), 8.00 (d, J = 15.8 Hz,
1H), 7.80 (d, J = 15.8 Hz, 1H), 7.59 (m, 2H), 7.44 (d, J = 8.4 Hz, 1H), 6.66 (dd, J = 15.8, 7.5 Hz,
1H), 6.40 (dd, J = 15.8, 7.0 Hz, 1H), 3.86 (d, J = 1.9 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ
193.1, 192.9, 166.5, 166.4, 147.2, 147.0, 139.7, 139.64, 137.1, 136.4, 136.03, 135.0, 132.7, 132.2,
131.8, 131.6, 130.9, 130.3, 129.12 128.9, 127.7, 127.5, 123.2, 122.4, 52.1, 52.0. LRMS (EI):
250[M+], 235, 221, 207, 191, 183, 162, 151, 142, 127, 115, 101, 87. HRMS (ESI): calcd for
C13H11O3ClNa, [M+Na] +, 273.0289; found, 273.0296.
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(E)-methyl 3-(4 or 5-fluoro-2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a35. White solid. 387 mg.
Yield 33%. 1H NMR (400 MHz, CDCl3) δ 9.78 (dd, J = 12.2, 7.6 Hz, 1H), 8.01 (dd, J = 15.7, 5.5
Hz, 1H), 7.82 (dd, J = 15.8, 9.1 Hz, 1H), 7.71 – 7.51 (m, 1H), 7.32 (dd, J = 14.4, 5.8 Hz, 1H), 7.18
(dd, J = 10.5, 5.9 Hz, 1H), 6.64 (dt, J = 15.8, 7.9 Hz, 1H), 6.38 (t, J = 16.3 Hz, 1H), 3.85 (d, J =
3.9 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 193.2, 193.0, 166.6, 166.4, 164.0 (d, J = 253.1 Hz),
163.5 (d, J = 252.0 Hz), 147.4, 147.1, 139.7 (d, J = 11.0 Hz), 136.8 (d, J = 8.4 Hz), 135.5, 132.1,
131.17 (d, J = 1.4 Hz), 130.71 (d, J = 3.3 Hz), 129.9, 129.9, 129.8, 129.75 (d, J = 3.1 Hz), 123.1,
121.8, 118.38 (d, J = 22.0 Hz), 117.70 (d, J = 22.1 Hz), 114.40 (d, J = 22.3 Hz), 114.10 (d, J =
22.3 Hz), 52.1, 52.0. HRMS (ESI): calcd for C13H12O3F, [M+H] +, 235.0765; found, 235.0766.
(E)-ethyl 3-(4 or 5-chloro-2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a36. Colorless oil. 463 mg.
Yield 35%. 1H NMR (400 MHz, CDCl3) δ 9.79 (d, J = 7.6, 1H), 7.99 (d, J = 15.8, 1H), 7.81 (d, J
= 15.8, 1H), 7.64 – 7.54 (m, 2H), 7.47 – 7.40 (m, 1H), 6.66 (dd, J = 15.8, 7.6 Hz, 1H), 6.40 (d, J =
15.7, 1H), 4.36 – 4.29 (m, 2H), 1.37 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 193.2,
193.0, 166.2, 166.0, 147.3, 147.1, 139.5, 139.3, 137.1, 136.3, 136.1, 134.9, 132.9, 132.2, 131.8,
131.5, 130.9, 130.2, 129.1, 128.9, 127.7, 127.4, 123.7, 122.9, 61.10 61.0, 14.30, 14.31. LRMS
(EI): 264[M+], 235, 218, 207, 191, 163, 155, 128, 115, 101, 87. HRMS (ESI): calcd for
C14H14O3Cl, [M+H] +, 265.0626; found, 265.0628.
(E)-ethyl 3-(4 or 5-fluoro-2-((E)-3-oxoprop-1-en-1-yl)phenyl)acrylate a37. Colorless oil. 396 mg.
Yield 32%. 1H NMR (400 MHz, CDCl3) δ 9.78 (dd, J = 12.2, 7.6 Hz, 1H), 8.01 (dd, J = 15.7, 5.5
Hz, 1H), 7.83 (dd, J = 15.8, 9.0 Hz, 1H), 7.73 – 7.57 (m, 1H), 7.44 – 7.25 (m, 1H), 7.24 – 7.10 (m,
1H), 6.64 (dt, J = 15.7, 7.8 Hz, 1H), 6.37 (t, J = 16.5 Hz, 1H), 4.72 – 3.79 (m, 2H), 1.37 (t, J = 7.1
Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 193.27 (s), 193.0, 166.2, 166.0, 164.01 (d, J = 253.1 Hz),
163.46 (d, J = 251.5 Hz), 147.5, 147.2, 139.5, 139.4, 136.9 (d, J = 8.1 Hz), 135.5 (d, J = 8.0 Hz),
132.1, 131.1, 129.96 (d, J = 9.0 Hz), 129.9, 129.8, 129.71 (d, J = 2.9 Hz), 123.6, 122.3, 118.38 (d,
J = 22.0 Hz), 117.63 (d, J = 22.1 Hz), 114.4 (d, J = 22.7 Hz), 114.07 (d, J = 22.5 Hz), 61.0, 60.9,
14.2. HRMS (ESI): calcd for C14H14O3F, [M+H] +, 249.0921; found, 249.0923.
(E)-3-[2-{(E)-2-Methoxycarbonylvinyl}phenyl]acrylic acid methyl ester a3816. White solid. 984
mg. Yield 80%. Mp. 64ꢀ65 oC. 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 15.8 Hz, 2H), 7.57 (dd,
J = 5.7, 3.5 Hz, 2H), 7.40 (dd, J = 5.8, 3.4 Hz, 2H), 6.36 (d, J = 15.8 Hz, 2H), 3.83 (s, 6H). 13C
NMR (150 MHz, CDCl3) δ 166.84, 141.46, 134.23, 130.11, 127.62, 121.45, 51.83. LRMS (EI):
246[M+], 231, 215, 199, 186, 171, 155, 143, 128, 115, 102, 92, 77. HRMS (ESI): calcd for
C14H15O4, [M+H] +, 247.0965; found, 247.0967.
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Compound b1’. White solid. 61 mg. Yield 57%. Mp. 79ꢀ80 oC. 1H NMR (400 MHz, CDCl3) δ 7.32
(d, J = 7.4 Hz, 1H), 7.27 (td, J = 7.4, 1.3 Hz, 1H), 7.16 (td, J = 7.3, 1.3 Hz, 1H), 7.10 (d, J = 7.0 Hz,
1H), 5.24 (d, J = 6.2 Hz, 1H), 3.38 (dd, J = 6.2, 2.8 Hz, 1H), 2.34 (d, J = 7.8 Hz, 1H), 1.95 (dd, J = 7.8,
2.7 Hz, 1H), 1.82 (s, 3H), 1.69 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 205.6, 133.6, 131.0, 128.4,
126.5, 125.0, 123.5, 75.7, 61.7, 52.8, 29.4, 23.9, 20.2, 16.8. HRMS (ESI): calcd for C14H15O2, [M+H]
+, 215.1067; found, 215.1069.
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Compound b1’’. Colorless oil. 29 mg. Yield 27%. 1H NMR (400 MHz, CDCl3) δ 7.33 (m, 2H), 7.22
(t, J = 6.9 Hz, 1H), 7.18 (d, J = 7.3 Hz, 1H), 5.17 (s, 1H), 2.34 (d, J = 9.3 Hz, 4H), 2.27 (s, 1H), 1.94 (d,
J = 8.0 Hz, 1H), 1.79 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 208.1, 134.5, 132.5, 128.2, 126.6, 125.0,
122.2, 77.5, 60.4, 53.9, 28.5, 25.0, 20.8, 16.5. HRMS (ESI): calcd for C14H15O2, [M+H]+, 215.1067;
found, 215.1074.
Compound b2’. White solid. 61 mg. Yield 51%. Mp. 86ꢀ87 oC. 1H NMR (400 MHz, CDCl3) δ 7.31
(d, J = 7.4 Hz, 1H), 7.27 – 7.20 (m, 1H), 7.14 (t, J = 7.3 Hz, 1H), 7.07 (d, J = 7.3 Hz, 1H), 5.26 (d, J =
6.2 Hz, 1H), 3.35 (dd, J = 6.2, 2.6 Hz, 1H), 2.21 (dq, J = 17.7, 7.2 Hz, 1H), 2.12 – 1.91 (m, 4H), 1.05 (t,
J = 7.4 Hz, 3H), 0.73 (t, J = 7.2 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 208.2, 133.7, 131.4, 128.2,
126.3, 124.9, 123.5, 75.7, 66.4, 52.0, 35.2, 23.9, 22.6, 18.7, 10.4, 7.1. HRMS (ESI): calcd for
C16H19O2, [M+H] +, 243.1380; found, 243.1381.
Compound b2’’. Colorless oil. 36 mg. Yield 30%. 1H NMR (400 MHz, CDCl3) δ 7.30 (t, J = 7.6 Hz,
2H), 7.18 (t, J = 7.2 Hz, 1H), 7.14 (d, J = 7.1 Hz, 1H), 5.16 (s, 1H), 2.83 – 2.49 (m, 2H), 2.34 (d, J =
8.1 Hz, 1H), 2.26 (s, 1H), 2.19 – 1.98 (m, 2H), 1.93 (d, J = 8.1 Hz, 1H), 1.11 (t, J = 7.3 Hz, 3H), 1.06 (t,
J = 7.6 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 210.0, 134.9, 132.7, 128.1, 126.5, 124.9, 122.1, 77.4,
65.2, 52.7, 34.3, 23.6, 23.5, 19.6, 10.5, 7.6. HRMS (ESI): calcd for C16H19O2, [M+H] +, 243.1380;
found, 243.1383
Compound b3. Colorless oil. 77 mg. Yield 52%. 1H NMR (400 MHz, CDCl3) δ 7.52 – 6.85 (m, 4H),
5.02 (s, 1H), 2.64 (s, 1H), 2.48 (d, J = 8.2 Hz, 1H), 1.88 (d, J = 8.2 Hz, 1H), 1.18 (s, 9H), 1.09 (s, 9H).
13C NMR (150 MHz, CDCl3) δ 213.8, 135.8, 133.2, 127.9, 126.6, 124.7, 121.6, 78.0, 72.4, 46.4, 44.8,
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31.1, 27.4, 26.5, 21.4, 20.1. H NMR (400 MHz, CDCl3) δ 7.29 – 6.74 (m, 4H), 5.30 (d, J = 5.9 Hz,
1H), 3.64 (dd, J = 5.8, 2.2 Hz, 1H), 2.56 (d, J = 8.2 Hz, 1H), 1.88 (d, J = 8.2 Hz, 1H), 1.05 (s, 9H), 1.02
(s, 9H). 13C NMR (150 MHz, CDCl3) δ 211.7, 134.8, 131.3, 128.1, 125.8, 124.5, 122.6, 76.1, 71.0, 46.7,
44.22, 31.1, 27.0, 26.55, 20.37, 20.1. HRMS (ESI): calcd for C20H27O2, [M+H] +, 299.2006; found,
299.2007.
Compound b4. Yellow oil. 76 mg. Yield 45%. 1H NMR (400 MHz, CDCl3) δ 8.04 – 7.92 (m, 2H),
7.58 (t, J = 7.4 Hz, 1H), 7.55 – 7.51 (m, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.41 (d, J = 7.4 Hz, 1H), 7.38 –
7.32 (m, 3H), 7.27 (t, J = 5.8 Hz, 3H), 5.42 (s, 1H), 3.34 (s, 1H), 2.89 (d, J = 8.1 Hz, 1H), 2.53 (d, J =
8.1 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 197.4, 136.4, 135.8, 135.0, 133.4, 132.5, 128.8, 128.4,
128.4, 128.3, 127.5, 127.0, 126.6, 125.4, 122.3, 78.1, 65.8, 48.4, 27.3, 23.2. HRMS (ESI): calcd for
C24H19O2, [M+H] +, 339.1380; found, 339.1384.
Compound b5’. White solid. 57 mg. Yield 50%. Mp. 95ꢀ96 oC. 1H NMR (400 MHz, CDCl3) δ
7.31 (d, J = 7.4 Hz, 1H), 7.26 (td, J = 7.4, 1.4 Hz, 1H), 7.14 (td, J = 7.3, 1.3 Hz, 1H), 7.09 (d, J =
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7.0 Hz, 1H), 5.20 (d, J = 6.2 Hz, 1H), 3.43 (dd, J = 6.2, 2.9 Hz, 1H), 3.32 (s, 3H), 2.30 (d, J = 7.9
Hz, 1H), 1.94 (dd, J = 7.9, 2.9 Hz, 1H), 1.68 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 165.1, 128.0,
126.2, 122.9, 121.1, 119.5, 118.2, 70.4, 56.2, 46.2, 39.4, 18.5, 14.4, 11.5. HRMS (ESI): calcd for
C14H15O3, [M+H] +, 231.1016; found, 231.1018.
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Compound b5’’. Colorless oil. 32 mg. Yield 27%. H NMR (400 MHz, CDCl3) δ 7.42 – 7.23 (m,
2H), 7.23 – 6.98 (m, 2H), 5.25 (s, 1H), 3.78 (s, 3H), 2.29 (s, 1H), 2.27 (d, J = 8.1 Hz, 1H), 1.99 (d, J =
8.0 Hz, 1H), 1.74 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 167.4, 129.0, 127.3, 122.9, 121.2, 119.6,
117.1, 72.8, 55.1, 46.9, 40.7, 19.3, 14.9, 11.2. HRMS (ESI): calcd for C14H15O3, [M+H]+, 231.1016;
found, 231.1014.
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Compound b6’. White solid. 61 mg. Yield 50%
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Mp. 109ꢀ110 C. 1H NMR (400 MHz, CDCl3) δ
7.32 (d, J = 7.4 Hz, 1H), 7.29 – 7.21 (m, 1H), 7.14 (td, J = 7.3, 1.2 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H),
5.20 (d, J = 6.3 Hz, 1H), 3.96 – 3.57 (m, 2H), 3.41 (dd, J = 6.2, 2.9 Hz, 1H), 2.31 (d, J = 7.9 Hz, 1H),
1.94 (dd, J = 7.9, 2.9 Hz, 1H), 1.68 (s, 3H), 0.89 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ
170.0, 133.5, 131.4, 128.2, 126.3, 124.6, 123.7, 75.8, 61.5, 60.3, 44.8, 23.8, 19.8, 16.8, 13.8. HRMS
(ESI): calcd for C15H17O3, [M+H] +, 245.1172; found, 245.1173.
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Compound b6’’. Colorless oil. 27 mg. Yield 23%. H NMR (400 MHz, CDCl3) δ 7.44 – 7.23 (m,
2H), 7.23 – 6.94 (m, 2H), 5.24 (s, 1H), 4.23 (qd, J = 7.1, 1.1 Hz, 2H), 2.36 – 2.12 (m, 2H), 1.99 (d, J =
8.0 Hz, 1H), 1.74 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 172.3, 134.3, 132.7,
128.1, 126.5, 124.9, 122.4, 78.2, 61.1, 60.4, 46.2, 24.7, 20.3, 16.5, 14.2. HRMS (ESI): calcd for
C15H17O3, [M+H] +, 245.1172; found, 245.1174.
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Compound b7’. White solid. 66 mg. Yield 49%. H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 7.2 Hz,
1H), 7.29 – 7.23 (m, 1H), 7.14 (td, J = 7.3, 1.2 Hz, 1H), 7.09 (d, J = 6.6 Hz, 1H), 5.20 (d, J = 6.2 Hz,
1H), 3.72 (qt, J = 10.8, 6.5 Hz, 2H), 3.42 (dd, J = 6.2, 2.9 Hz, 1H), 2.30 (d, J = 7.9 Hz, 1H), 1.94 (dd, J
= 7.9, 2.9 Hz, 1H), 1.68 (s, 3H), 1.38 – 1.20 (m, 2H), 1.20 – 1.07 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H).13C
NMR (150 MHz, CDCl3) δ 170.1, 133.4, 131.4, 128.1, 126.4, 124.7, 123.7, 75.7, 64.2, 61.4, 44.8, 30.4,
23.8, 19.8, 18.9, 16.8, 13.6. HRMS (ESI): calcd for C17H21O3, [M+H] +, 273.1485; found, 273.1489.
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Compound b7’’. Colorless oil. 31 mg. Yield 23%. H NMR (400 MHz, CDCl3) δ 7.35 – 7.19 (m,
2H), 7.22 – 6.81 (m, 2H), 5.23 (s, 1H), 4.47 – 3.77 (m, 2H), 2.27 (d, J = 8.0 Hz, 2H), 1.99 (d, J = 8.0
Hz, 1H), 1.73 (s, 3H), 1.70 – 1.59 (m, 2H), 1.54 – 1.31 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H). 13C NMR
(150 MHz, CDCl3) δ 172.3, 134.4, 132.7, 128.1, 126.5, 124.9, 122.4, 78.2, 64.9, 60.3, 46.2, 30.6, 24.7,
20.3, 19.1, 16.5, 13.7. HRMS (ESI): calcd for C17H21O3, [M+H] +, 273.1485; found, 273.1486.
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Compound b8’. White solid. 64 mg. Yield 48%
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Mp. 105ꢀ106 C. 1H NMR (400 MHz, CDCl3) δ
7.32 (d, J = 7.4 Hz, 1H), 7.28 – 7.21 (m, 1H), 7.15 (td, J = 7.2, 1.2 Hz, 1H), 7.12 (d, J = 7.3 Hz, 1H),
5.13 (d, J = 6.3 Hz, 1H), 3.35 (dd, J = 6.3, 2.9 Hz, 1H), 2.27 (d, J = 7.9 Hz, 1H), 1.90 (dd, J = 7.9, 2.9
Hz, 1H), 1.67 (s, 3H), 1.08 (s, 9H). 13C NMR (150 MHz, CDCl3) δ 169.3, 133.7, 131.6, 128.1, 126.4,
124.5, 124.1, 80.7, 75.9, 61.5, 45.7, 27.5, 23.8, 20.0, 16.8. HRMS (ESI): calcd for C17H21O3, [M+H]+,
273.1485; found, 273.1483.
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Compound b8’’. Colorless oil. 28 mg. Yield 21%. H NMR (400 MHz, CDCl3) δ 7.37 – 7.24 (m,
2H), 7.16 (dd, J = 4.5, 2.1 Hz, 2H), 5.19 (s, 1H), 2.24 (d, J = 8.0 Hz, 1H), 2.17 (s, 1H), 1.93 (d, J = 8.0
Hz, 1H), 1.73 (s, 3H), 1.51 (s, 9H). 13C NMR (150 MHz, CDCl3) δ 171.5, 134.6, 132.8, 128.0, 126.4,
124.8, 122.4, 81.2, 78.4, 60.3, 47.1, 28.1, 24.7, 20.5, 16.6. HRMS (ESI): calcd for C17H21O3, [M+H]+,
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Compound b9’. Colorless oil. 61 mg. Yield 42%.1H NMR (400 MHz, CDCl3) δ 7.40 – 7.29 (m, 2H),
7.24 – 7.16 (m, 4H), 7.13 – 7.06 (m, 1H), 6.45 (dd, J = 5.5, 3.7 Hz, 2H), 5.36 (d, J = 6.3 Hz, 1H), 3.67
(dd, J = 6.3, 2.9 Hz, 1H), 2.37 (d, J = 7.9 Hz, 1H), 2.05 (dd, J = 7.9, 2.9 Hz, 1H), 1.71 (s, 3H). 13C
NMR (150 MHz, CDCl3) δ 168.7, 150.2, 133.6, 131.4, 129.2, 128.5, 126.7, 125.8, 124.9, 124.0, 121.2,
75.9, 61.9, 45.0, 24.1, 19.8, 16.8. HRMS (ESI): calcd for C19H17O3, [M+H] +, 293.1172; found,
293.1179.
Compound b9’’. Colorless oil. 29 mg. Yield 20%.1H NMR (400 MHz, CDCl3) δ 7.44 – 7.36 (m,
2H), 7.35 – 7.27 (m, 2H), 7.27 – 7.18 (m, 3H), 7.18 – 7.12 (m, 2H), 5.41 (s, 1H), 2.52 (s, 1H), 2.33 (d,
J = 8.0 Hz, 1H), 2.11 (d, J = 8.0 Hz, 1H), 1.77 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 170.9, 150.7,
134.2, 132.6, 129.5, 128.3, 126.6, 126.0, 125.1, 122.6, 121.5, 78.3, 60.6, 46.5, 24.8, 20.3, 16.5. HRMS
(ESI): calcd for C19H17O3, [M+H] +, 293.1172; found, 293.1176.
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Compound b10’. White solid. 81 mg. Yield 55%. 1H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 7.4 Hz,
1H), 7.29 – 7.22 (m, 1H), 7.14 (td, J = 7.3, 1.2 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H), 5.19 (d, J = 6.3 Hz,
1H), 4.77 – 4.23 (m, 1H), 3.40 (dd, J = 6.2, 2.9 Hz, 1H), 2.30 (d, J = 7.9 Hz, 1H), 1.94 (dd, J = 7.9, 2.9
Hz, 1H), 1.68 (s, 3H), 1.61 – 1.52 (m, 2H), 1.49 – 1.34 (m, 3H), 1.26 – 0.85 (m, 5H). 13C NMR (150
MHz, CDCl3) δ 169.4, 133.5, 131.4, 128.1, 126.3, 124.6, 123.9, 75.8, 72.5, 61.4, 45.0, 31.29, 31.20,
25.2, 23.8, 23.6, 19.8, 16.8. HRMS (ESI): calcd for C19H23O3, [M+H] +, 299.1642; found, 299.1643.
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Compound b10’’. Colorless oil. 31 mg. Yield 21%. H NMR (400 MHz, CDCl3) δ 7.46 – 7.23 (m,
2H), 7.23 – 6.95 (m, 2H), 5.22 (s, 1H), 5.02 – 4.45 (m, 1H), 2.26 (d, J = 7.8 Hz, 2H), 1.98 (d, J = 8.0
Hz, 1H), 1.93 – 1.82 (m, 2H), 1.81 – 1.70 (m, 5H), 1.57 – 1.21 (m, 6H). 13C NMR (150 MHz, CDCl3) δ
171.7, 134.4, 132.8, 128.1, 126.4, 124.8, 122.4, 78.3, 73.2, 60.3, 46.4, 31.59, 31.54, 25.4, 24.7, 23.6,
20.3, 16.5. HRMS (ESI): calcd for C19H23O3, [M+H] +, 299.1642; found, 299.1644.
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Compound b11’. White solid. 80 mg. Yield 49%. H NMR (400 MHz, CDCl3) δ 7.37 – 7.22 (m,
5H), 7.12 – 6.76 (m, 4H), 5.20 (d, J = 6.2 Hz, 1H), 4.74 (q, J = 12.3 Hz, 2H), 3.46 (dd, J = 6.2, 2.9 Hz,
1H), 2.30 (d, J = 7.9 Hz, 1H), 1.96 (dd, J = 7.9, 2.9 Hz, 1H), 1.67 (s, 3H). 13C NMR (150 MHz, CDCl3)
δ 169.9, 135.4, 133.4, 131.3, 128.4, 128.3, 128.2, 128.1, 126.4, 124.8, 123.7, 75.7, 66.3, 61.5, 44.8,
23.9, 19.8, 16.8. HRMS (ESI): calcd for C20H18O3Na, [M+Na] +, 329.1148; found, 329.1143.
Compound b11’’. Colorless oil. 44 mg. Yield 27%. 1H NMR (400 MHz, CDCl3) δ 7.42 – 7.31 (m,
5H), 7.30 – 7.23 (m, 2H), 7.20 – 7.11 (m, 2H), 5.27 (s, 1H), 5.22 (q, J = 12.4 Hz, 2H), 2.33 (s, 1H),
2.27 (d, J = 8.1 Hz, 1H), 2.01 (d, J = 8.0 Hz, 1H), 1.72 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 172.1,
135.8, 134.2, 132.6, 128.6, 128.3, 128.2, 128.1, 126.5, 124.9, 122.5, 78.1, 66.8, 60.4, 46.2, 24.7, 20.3,
16.5. HRMS (ESI): calcd for C20H18O3Na, [M+Na] +, 329.1148; found, 329.1146.
Compound b12’. White solid. 77 mg. Yield 48%. 1H NMR (400 MHz, CDCl3) δ 7.29 (d, J = 7.3 Hz,
1H), 7.24 (td, J = 7.4, 1.1 Hz, 1H), 7.06 (td, J = 7.4, 1.2 Hz, 1H), 7.02 – 6.87 (m, 5H), 5.19 (d, J = 6.2
Hz, 1H), 4.72 (s, 2H), 3.45 (dd, J = 6.2, 2.9 Hz, 1H), 2.30 (d, J = 7.9 Hz, 1H), 1.96 (dd, J = 7.9, 2.9 Hz,
1H), 1.67 (s, 3H). 13C NMR (150 MHz, CDCl3) 169.8, 162.58 (d, J = 246.7 Hz), 133.3, 131.32 (d, J =
3.2 Hz), 131.2, 130.3, 130.3, 128.2, 126.4, 124.8, 123.7, 115.34 (d, J = 21.4 Hz), 75.6, 65.5, 61.5, 44.8,
23.8, 19.8, 16.7. HRMS (ESI): calcd for C20H18FO3, [M+H] +, 325.1234; found, 325.1233.
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Compound b12’’. Colorless oil. 38 mg. Yield 24%. H NMR (400 MHz, CDCl3) δ 7.41 – 7.33 (m,
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2H), 7.31 – 7.25 (m, 2H), 7.20 – 7.14 (m, 2H), 7.10 – 7.03 (m, 2H), 5.25 (s, 1H), 5.18 (q, J = 12.3 Hz,
2H), 2.32 (s, 1H), 2.27 (d, J = 8.1 Hz, 1H), 1.99 (d, J = 8.1 Hz, 1H), 1.71 (s, 3H). 13C NMR (150 MHz,
CDCl3) δ 172.1, 162.71 (d, J = 247.4 Hz), 134.2, 132.6, 131.67 (d, J = 3.2 Hz), 130.2, 130.1, 128.2,
126.5, 125.0, 122.4, 115.59 (d, J = 21.9 Hz), 78.1, 66.1, 60.4, 46.2, 24.7, 20.3, 16.4. HRMS (ESI):
calcd for C20H18FO3, [M+H] +, 325.1234; found, 325.1232.
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Compound b13’. White solid. 90 mg. Yield 48%. H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.1 Hz,
2H), 7.29 (d, J = 7.3 Hz, 1H), 7.26 – 7.19 (m, 1H), 7.07 (d, J = 8.1 Hz, 2H), 7.06 – 7.00 (m, 1H), 6.95
(d, J = 7.3 Hz, 1H), 5.21 (d, J = 6.2 Hz, 1H), 4.93 – 4.47 (m, 2H), 3.49 (dd, J = 6.2, 2.9 Hz, 1H), 2.31
(d, J = 7.8 Hz, 1H), 1.98 (dd, J = 7.9, 2.9 Hz, 1H), 1.68 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 169.8,
139.3, 133.3, 131.1, 130.2 (q, J = 32.2 Hz), 128.3, 126.4, 125.3 (q, J = 3.6 Hz), 125.38, 124.8, 124.04
(q, J = 280.5 Hz), 123.7, 75.6, 65.3, 61.5, 44.7, 23.8, 19.7, 16.7. HRMS (ESI): calcd for C21H18O3F3,
[M+H] +, 375.1203; found, 375.1210.
Compound b13’’. White solid. 41 mg. Yield 22%1H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.2 Hz,
2H), 7.54 (d, J = 8.1 Hz, 2H), 7.37 – 7.29 (m, 2H), 7.26 – 6.91 (m, 2H), 5.30 (m, 3H), 2.39 (s, 1H),
2.33 (d, J = 8.1 Hz, 1H), 2.05 (d, J = 8.1 Hz, 1H), 1.76 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 172.0,
139.8, 134.1, 132.5, 130.4 (q, J = 32.2 Hz), 128.3, 128.0, 126.5, 125.6 (q, J = 3.6 Hz), 125.0, 124.0 (q,
J = 272.0 Hz), 122.4, 78.15, 65.8, 60.4, 46.2, 24.7, 20.3, 16.5. HRMS (ESI): calcd for C21H18O3F3,
[M+H] +, 375.1203; found, 375.1206.
Compound b14. Colorless oil. 114 mg. Yield 68%. 1H NMR (400 MHz, CDCl3) δ 7.32 (d, J = 8.6
Hz, 2H), 7.18 – 7.11 (m, 2H), 7.07 (t, J = 7.3 Hz, 1H), 6.97 (t, J = 7.0 Hz, 3H), 5.24 (s, 1H), 5.14 (m,
2H), 3.78 (s, 3H), 2.29 (s, 1H), 2.28 (d, J = 6.5 Hz, 1H), 1.98 (d, J = 8.1 Hz, 1H), 1.72 (s, 3H). 13C
NMR (151 MHz, CDCl3) δ 172.2, 159.7, 134.3, 132.7, 130.2, 128.1, 127.9, 126.4, 124.9, 122.5, 114.0,
78.2, 66.7, 60.4, 55.3, 46.2, 24.7, 20.3, 16.5.1H NMR (400 MHz, CDCl3) δ 7.30 – 7.21 (m, 4H), 6.89 (d,
J = 8.5 Hz, 2H), 6.79 (d, J = 8.5 Hz, 2H), 5.17 (d, J = 6.4 Hz, 1H), 4.67 (s, 2H), 3.79 (s, 3H), 3.43 (dd,
J = 6.2, 2.8 Hz, 1H), 2.25 (d, J = 8.1 Hz, 1H), 1.94 (dd, J = 7.8, 2.8 Hz, 1H), 1.65 (s, 3H). 13C NMR
(151 MHz, CDCl3) δ 169.9, 159.6, 133.4, 131.3, 130.1, 128.1, 127.6, 126.5, 124.8, 123.7, 113.8, 75.7,
66.1, 60.4, 55.3, 44.8, 23.9, 19.9, 16.8. HRMS (ESI): calcd for C21H20NaO4, [M+Na]+, 359.1254;
found, 359.1261.
Compound b15’. White solid. 62 mg. Yield 48%. Mp. 130ꢀ131 oC. 1H NMR (400 MHz, CDCl3) δ
7.20 – 6.96 (m, 2H), 6.83 (td, J = 9.2, 2.4 Hz, 1H), 5.19 (d, J = 6.2 Hz, 1H), 4.10 – 3.63 (m, 2H), 3.42
(dd, J = 6.2, 2.8 Hz, 1H), 2.29 (d, J = 7.9 Hz, 1H), 1.98 (dd, J = 7.9, 2.8 Hz, 1H), 1.68 (s, 3H), 0.93 (t, J
= 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.76, 162.7 (d, J = 245.0 Hz), 135.8 (d, J = 8.9 Hz),
127.3, 125.3 (d, J = 8.9 Hz), 113.4 (d, J = 22.7 Hz), 111.5 (d, J = 22.1 Hz), 75.1, 61.6, 60.4, 44.8, 24.1
(d, J = 1.6 Hz), 20.1, 16.7, 13.9. HRMS (ESI): calcd for C15H16FO3, [M+H] +, 263.1078; found,
263.1072.
Compound b15’’. Colorless oil. 27 mg. Yield 20%. 1H NMR (400 MHz, CDCl3) δ 7.13 (dd, J = 8.1,
5.5 Hz, 1H), 7.01 (dd, J = 9.1, 2.2 Hz, 1H), 6.94 – 6.85 (m, 1H), 5.23 (s, 1H), 4.23 (q, J = 7.0 Hz, 2H),
2.25 (d, J = 8.3 Hz, 2H), 2.02 (d, J = 8.0 Hz, 1H), 1.74 (d, J = 4.4 Hz, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13
C
NMR (150 MHz, CDCl3) δ 171.9, 162.7 (d, J = 244.5 Hz), 135.0 (d, J = 8.8 Hz), 130.2 (d, J = 2.2 Hz),
124.0 (d, J = 8.8 Hz), 113.5 (d, J = 22.4 Hz), 111.5 (d, J = 22.0 Hz), 77.6, 61.1, 60.4, 46.3, 24.9, 20.5,
16.4, 14.2. HRMS (ESI): calcd for C15H16FO3, [M+H] +, 263.1078; found, 263.1077.
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Compound b16’. White solid. 59 mg. Yield 43%. Mp. 118ꢀ119 oC. 1H NMR (400 MHz, CDCl3) δ
7.31 (d, J = 1.4 Hz, 1H), 7.13 (dd, J = 7.9, 1.8 Hz, 1H), 7.04 (d, J = 7.9 Hz, 1H), 5.19 (d, J = 6.2 Hz,
1H), 3.99 – 3.68 (m, 2H), 3.42 (dd, J = 6.2, 2.9 Hz, 1H), 2.27 (d, J = 7.9 Hz, 1H), 1.99 (dd, J = 7.9, 2.8
Hz, 1H), 1.67 (s, 3H), 0.94 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.6, 135.4, 133.7,
129.8, 126.4, 125.0, 124.8, 75.1, 61.7, 60.5, 44.7, 23.8, 20.1, 16.6, 13.9. HRMS (ESI): calcd for
C15H16ClO3, [M+H] +, 279.0782; found, 279.0780.
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Compound b16’’. Colorless oil. 29 mg. Yield 21%. 1H NMR (400 MHz, CDCl3) δ 7.27 (d, J = 10.4
Hz, 1H), 7.16 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 7.9 Hz, 1H), 5.23 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H), 2.24
(d, J = 10.8 Hz, 2H), 2.03 (d, J = 8.0 Hz, 1H), 1.73 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13C NMR (150
MHz, CDCl3) δ 171.8, 134.7, 133.7, 132.7, 126.5, 124.9, 123.7, 77.5, 61.2, 60.6, 46.1, 24.5, 20.5, 16.3,
14.2. HRMS (ESI): calcd for C15H16ClO3, [M+H] +, 279.0782; found, 279.0781.
Compound b17’. White solid. 47 mg. Yield 34%. 1H NMR (400 MHz, CDCl3) δ 7.01 (d, J = 8.2
Hz, 1H), 6.87 (d, J = 2.4 Hz, 1H), 6.67 (dd, J = 8.2, 2.5 Hz, 1H), 5.16 (d, J = 6.2 Hz, 1H), 3.89 –
3.66 (m, 5H), 3.39 (dd, J = 6.2, 2.9 Hz, 1H), 2.26 (d, J = 7.9 Hz, 1H), 1.93 (dd, J = 7.9, 2.9 Hz,
1H), 1.67 (s, 3H), 0.94 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 170.0, 159.6, 134.9,
124.8, 124.2, 111.6, 110.4, 75.3, 61.4, 60.3, 55.2, 45.1, 24.3, 20.1, 16.8, 14.0. HRMS (ESI): calcd
for C16H19O4, [M+H] +, 275.1278; found, 275.1274.
Compound b17’’. Colorless oil. 21 mg. Yield 16%. 1H NMR (400 MHz, CDCl3) δ 7.09 (d, J =
8.2 Hz, 1H), 6.85 (d, J = 2.4 Hz, 1H), 6.70 (dd, J = 8.2, 2.5 Hz, 1H), 5.20 (s, 1H), 4.22 (qd, J = 7.1,
1.1 Hz, 2H), 3.80 (s, 3H), 2.28 (s, 1H), 2.22 (d, J = 8.0 Hz, 1H), 1.98 (d, J = 8.0 Hz, 1H), 1.73 (s,
3H), 1.31 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 172.3, 159.7, 134.2, 127.2, 123.5,
112.2, 110.1, 77.8, 61.0, 60.2, 55.3, 46.6, 25.1, 20.6, 16.5, 14.2. HRMS (ESI): calcd for C16H19O4,
[M+H] +, 275.1278; found, 275.1274.
Compound b18’. White solid. 47 mg. Yield 36%. 1H NMR (400 MHz, CDCl3) δ 7.26 (t, J = 6.6 Hz,
1H), 6.97 (t, J = 8.9 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 5.17 (d, J = 6.2 Hz, 1H), 3.83 (q, J = 6.9 Hz,
2H), 3.55 – 3.15 (m, 1H), 2.30 (d, J = 7.9 Hz, 1H), 1.94 (dd, J = 7.8, 2.4 Hz, 1H), 1.67 (s, 3H), 0.94 (t,
J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.7, 160.70 (d, J = 243.3 Hz), 132.91 (d, J = 7.5 Hz),
129.1, 127.67 (d, J = 7.7 Hz), 114.99 (d, J = 21.8 Hz), 111.13 (d, J = 22.6 Hz), 75.2, 61.4, 60.5, 44.7,
23.1, 19.6, 16.6, 13.9. HRMS (ESI): calcd for C15H16FO3, [M+H] +, 263.1078; found, 263.1080.
Compound b18’’. Colorless oil. 26 mg. Yield 20%. 1H NMR (400 MHz, CDCl3) δ 7.30 – 7.17 (m,
1H), 6.98 (td, J = 8.9, 2.5 Hz, 1H), 6.92 (dd, J = 8.2, 2.4 Hz, 1H), 5.20 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H),
2.35 – 2.18 (m, 2H), 1.98 (d, J = 8.1 Hz, 1H), 1.73 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13C NMR (150
MHz, CDCl3) δ 171.9, 160.73 (d, J = 243.9 Hz), 135.71 (d, J = 7.3 Hz), 128.34 (d, J = 2.8 Hz), 127.74
(d, J = 7.8 Hz), 114.81 (d, J = 21.5 Hz), 110.00 (d, J = 22.6 Hz), 77.69 (d, J = 1.8 Hz), 61.2, 60.3, 46.0,
24.0, 20.0, 16.3, 14.2. HRMS (ESI): calcd for C15H16FO3, [M+H] +, 263.1078; found, 263.1076.
Compound b19’. White solid.49 mg. Yield 35%. Mp. 123ꢀ124 oC. 1H NMR (400 MHz, CDCl3) δ
7.25 (d, J = 7.3 Hz, 2H), 7.11 (s, 1H), 5.16 (d, J = 6.3 Hz, 1H), 4.13 – 3.74 (m, 2H), 3.42 (dd, J =
6.2, 2.9 Hz, 1H), 2.29 (d, J = 7.9 Hz, 1H), 1.97 (dd, J = 7.9, 2.8 Hz, 1H), 1.67 (s, 3H), 0.94 (t, J =
7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.6, 132.8, 132.0, 130.5, 128.1, 127.7, 124.0, 75.1,
61.8, 60.5, 44.6, 23.4, 19.9, 16.6, 13.9. HRMS (ESI): calcd for C15H16ClO3, [M+H] +, 279.0782;
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Compound b19’’. Yellow solid. 34 mg. Yield 25%. Mp. 75ꢀ76 oC. 1H NMR (400 MHz, CDCl3) δ
7.26 (dd, J = 8.1, 1.9 Hz, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.19 (d, J = 1.5 Hz, 1H), 5.21 (s, 1H), 4.25
(q, J = 7.1 Hz, 2H), 2.32 – 2.22 (m, 2H), 2.03 (d, J = 8.1 Hz, 1H), 1.74 (s, 3H), 1.33 (t, J = 7.1 Hz,
3H). 13C NMR (150 MHz, CDCl3) δ 171.8, 135.6, 131.3, 130.6, 128.1, 127.8, 122.8, 77.6, 61.2,
60.6, 45.9, 24.2, 20.3, 16.3, 14.2. HRMS (ESI): calcd for C15H16ClO3, [M+H] +, 279.0782; found,
279.0784.
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Compound b20’. White solid. 44 mg. Yield 35%. Mp. 85ꢀ86oC. 1H NMR (400 MHz, CDCl3) δ 7.19
(d, J = 7.6 Hz, 1H), 7.07 (d, J = 7.5 Hz, 1H), 6.92 (s, 1H), 5.15 (d, J = 6.2 Hz, 1H), 3.81 (q, J = 7.1 Hz,
2H), 3.39 (dd, J = 6.2, 2.9 Hz, 1H), 2.30 (s, 3H), 2.26 (d, J = 7.9 Hz, 1H), 1.90 (dd, J = 7.9, 2.8 Hz, 1H),
1.66 (s, 3H), 0.89 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 170.1, 134.1, 131.3, 130.3, 128.8,
126.1, 124.5, 75.8, 61.4, 60.2, 44.9, 23.5, 21.1, 19.7, 16.8, 13.8. HRMS (ESI): calcd for C16H19O3,
[M+H] +, 259.1329; found, 259.1330.
Compound b20’’. Colorless oil. 26 mg. Yield 20%. 1H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 7.6
Hz, 1H), 7.08 (d, J = 7.7 Hz, 1H), 6.99 (s, 1H), 5.18 (s, 1H), 4.22 (q, J = 7.1 Hz, 2H), 2.33 (s, 3H),
2.26 (s, 1H), 2.22 (d, J = 8.0 Hz, 1H), 1.95 (d, J = 8.0 Hz, 1H), 1.72 (s, 3H), 1.31 (t, J = 7.1 Hz,
3H). 13C NMR (150 MHz, CDCl3) δ 172.3, 134.5, 134.3, 129.6, 128.7, 126.3, 123.2, 78.3, 61.0,
60.3, 46.3, 24.3, 21.1, 20.2, 16.5, 14.2. HRMS (ESI): calcd for C16H19O3, [M+H] +, 259.1329;
found, 259.1332.
Compound b21. Colorless oil. 67 mg. Yield 53%. 1H NMR (600 MHz, CDCl3) δ 8.04 (d, J = 8.3 Hz,
1H), 7.83 (d, J = 8.2 Hz, 1H), 7.77 (d, J = 8.2 Hz, 1H), 7.52 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 7.5 Hz,
1H), 7.38 (d, J = 8.3 Hz, 1H), 6.12 (s, 1H), 4.99 (d, J = 6.6 Hz, 1H), 4.41 – 4.15 (m, 2H), 3.86 – 3.56
(m, 1H), 3.38 (s, 1H), 1.51 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.7,
148.4, 148.2, 132.6, 131.6, 129.6, 129.2, 128.7, 126.9, 124.9, 123.7, 119.4, 99.6, 76.4, 60.6, 51.6, 39.2,
19.8, 14.3. HRMS (ESI): calcd for C19H19O3, [M+H] +, 295.1329; found, 295.1321.
Compound b22’. White solid. 55 mg. Yield 56%. Mp. 147ꢀ148 oC. 1H NMR (400 MHz, CDCl3) δ
7.37 (d, J = 4.0 Hz, 2H), 7.32 – 7.02 (m, 2H), 5.22 (d, J = 5.6 Hz, 1H), 3.30 (dd, J = 5.5, 2.9 Hz, 1H),
2.37 (d, J = 7.8 Hz, 1H), 2.06 (dd, J = 7.7, 2.8 Hz, 1H), 1.67 (s, 3H). 13C NMR (150 MHz, CDCl3) δ
131.5, 130.9, 129.1, 126.9, 125.7, 123.9, 117.3, 75.7, 61.2, 29.7, 23.7, 20.9, 16.3. HRMS (ESI): calcd
for C13H12NO, [M+H] +, 198.0913; found, 198.0916.
Compound b22’’. Colorless oil. 22 mg. Yield 22%. 1H NMR (400 MHz, CDCl3) δ 7.33 (m, 2H),
7.25 – 7.20 (m, 1H), 7.16 (d, J = 7.4 Hz, 1H), 5.25 (s, 1H), 2.34 (d, J = 6.1 Hz, 2H), 2.08 (d, J = 8.1 Hz,
1H), 1.78 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 132.5, 131.3, 129.0, 126.8, 125.6, 122.7, 119.5, 77.6,
+
60.5, 31.9, 24.5, 21.1, 16.3. HRMS (ESI): calcd for C13H12NO, [M+H] , 198.0913; found,
198.0915.
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Compound b23. White solid. 67 mg. Yield 62%. H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.3
Hz, 1H), 7.34 – 7.27 (m, 1H), 7.20 (t, J = 7.3 Hz, 1H), 7.13 (d, J = 7.2 Hz, 1H), 5.24 (d, J = 5.9 Hz,
1H), 4.22 (m, 1H), 3.37 (s, 4H), 2.43 (m, 1H), 2.18 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 170.3,
132.4, 131.7, 128.3, 126.5, 124.9, 123.6, 74.6, 54.5, 51.6, 43.9, 17.72, 14.4. LRMS (EI): 216[M+],
201, 187, 172, 155, 143, 129, 115, 102. HRMS (ESI): calcd for C13H13O3, [M+H] +, 217.0859;
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Compound b24. White solid. 69 mg. Yield 60%. 1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 7.4 Hz,
1H), 7.28 (dd, J = 7.4, 1.3 Hz, 1H), 7.16 (td, J = 7.4, 1.1 Hz, 1H), 7.10 (d, J = 7.2 Hz, 1H), 5.21 (d, J =
6.3 Hz, 1H), 4.51 – 4.08 (m, 1H), 3.92 – 3.67 (m, 2H), 3.33 (dd, J = 6.3, 3.0 Hz, 1H), 2.40 (dd, J = 8.0,
5.2 Hz, 1H), 2.26 – 2.00 (m, 1H), 0.90 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 169.8, 132.5,
131.7, 128.2, 126.5, 124.8, 123.7, 74.7, 60.4, 54.5, 44.0, 17.7, 14.4, 13.8. HRMS (ESI): calcd for
C14H15O3, [M+H] +, 231.1016; found, 231.1018
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Compound b25. White solid. 70 mg. Yield 58%. H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.4
Hz, 1H), 7.27 (t, J = 6.5 Hz, 1H), 7.15 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H), 5.20 (d, J =
6.2 Hz, 1H), 4.63 (dt, J = 12.5, 6.2 Hz, 1H), 4.17 (t, J = 4.1 Hz, 1H), 3.43 – 3.25 (m, 1H), 2.47 –
2.29 (m, 1H), 2.21 – 2.06 (m, 1H), 0.90 (d, J = 6.2 Hz, 6H). 13C NMR (151 MHz, CDCl3) δ 169.4,
132.6, 131.6, 128.3, 126.5, 124.7, 124.0, 74.7, 67.8, 54.6, 44.1, 21.4, 17.7, 14.4. LRMS (EI):
244[M+], 215, 201, 186, 173, 157, 129, 102. HRMS (ESI): calcd for C15H17O3, [M+H] +, 245.1172,
found, 245.1178.
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Compound b26. White solid. 82 mg. Yield 64%. H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.5
Hz, 1H), 7.28 (d, J = 7.4 Hz, 1H), 7.16 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H), 5.21 (d, J =
6.2 Hz, 1H), 4.18 (t, J = 4.5 Hz, 1H), 3.74 (dtd, J = 17.4, 11.1, 6.3 Hz, 2H), 3.43 – 3.24 (m, 1H),
2.50 – 2.30 (m, 1H), 2.20 – 2.06 (m, 1H), 1.34 – 1.25 (m, 2H), 1.17 (dt, J = 20.9, 7.1 Hz, 2H),
0.82 (t, J = 7.2 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 169.9, 132.5, 131.7, 128.3, 126.5, 124.8,
123.7, 74.7, 64.3, 54.5, 44.0, 30.4, 18.9, 17.7, 14.5, 13.6. LRMS (EI): 258[M+], 242, 229, 205,
184, 173, 157, 129, 102. HRMS (ESI): calcd for C16H19O3, [M+H] +, 259.1329; found, 259.1330.
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Compound b27. White solid. 67 mg. Yield 52%. H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 7.6
Hz, 1H), 7.29 (d, J = 7.3 Hz, 1H), 7.17 (t, J = 7.3 Hz, 1H), 7.12 (d, J = 7.3 Hz, 1H), 5.14 (d, J =
6.2 Hz, 1H), 4.16 (s, 1H), 3.45 – 3.09 (m, 1H), 2.55 – 2.28 (m, 1H), 2.11 (s, 1H), 1.09 (s, 9H). 13
C
NMR (150 MHz, CDCl3) δ 169.1, 132.7, 131.9, 128.2, 126.5, 124.6, 124.1, 80.8, 74.8, 54.5, 44.8,
27.5, 17.6, 14.6. LRMS (EI): 258[M+], 228, 214, 202, 185, 173, 157, 129, 102. HRMS (ESI):
calcd for C16H19O3, [M+H] +, 259.1329; found, 259.1332.
Compound b28. White solid. 74 mg. Yield 55%. 1H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.4 Hz,
1H), 7.28 (dd, J = 7.4, 6.6 Hz, 1H), 7.17 (t, J = 7.4 Hz, 1H), 7.10 (d, J = 7.2 Hz, 1H), 5.18 (d, J = 6.3
Hz, 1H), 4.80 (dt, J = 8.3, 2.9 Hz, 1H), 4.17 (t, J = 4.6 Hz, 1H), 3.30 (dd, J = 6.3, 3.0 Hz, 1H), 2.38 (dd,
J = 8.0, 5.2 Hz, 1H), 2.20 – 2.07 (m, 1H), 1.63 – 1.09 (m, 8H). 13C NMR (150 MHz, CDCl3) δ 169.68 ,
132.66 , 131.73 , 128.32 , 126.54 , 124.76 , 123.82 , 77.30 ,74.75 , 54.55 , 44.12 , 32.34 , 32.23 , 23.76 ,
23.70 , 17.69 , 14.52 . LRMS (EI): 270[M+], 199, 173, 155, 129. HRMS (ESI): calcd for C17H19O3,
[M+H] +, 271.1329; found, 271.1330.
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Compound b29. White solid. 79 mg. Yield 56%. H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.4
Hz, 1H), 7.27 (t, J = 5.9 Hz, 1H), 7.15 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H), 5.20 (d, J =
6.2 Hz, 1H), 4.48 – 4.35 (m, 1H), 4.17 (t, J = 4.5 Hz, 1H), 3.46 – 3.19 (m, 1H), 2.49 – 2.32 (m,
1H), 2.24 – 2.08 (m, 1H), 1.56 (d, J = 12.8 Hz, 2H), 1.44 (d, J = 5.0 Hz, 3H), 1.25 – 1.03 (m, 5H).
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13C NMR (150 MHz, CDCl3) δ 169.3, 132.6, 131.6, 128.3, 126.5, 124.7, 123.9, 74.7, 72.6, 54.5,
44.2, 31.2, 25.2, 23.6, 17.7, 14.5. LRMS (EI): 284[M+], 255, 202, 173, 157, 129, 102. HRMS
(ESI): calcd for C18H21O3, [M+H] +, 285.1485; found, 285.1490.
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Compound b30. White solid. 93 mg. Yield 64%. H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.4
Hz, 1H), 7.28 (dd, J = 6.4, 2.6 Hz, 4H), 7.11 (t, J = 7.4 Hz, 1H), 7.05 (dd, J = 6.3, 2.7 Hz, 2H),
7.00 (d, J = 7.3 Hz, 1H), 5.21 (d, J = 6.2 Hz, 1H), 4.77 (q, J = 12.2 Hz, 2H), 4.18 (t, J = 4.6 Hz,
1H), 3.38 (dd, J = 6.2, 2.9 Hz, 1H), 2.40 (dd, J = 7.9, 5.2 Hz, 1H), 2.22 – 2.11 (m, 1H). 13C NMR
(150 MHz, CDCl3) δ 169.7, 135.4, 132.4, 131.6, 128.4, 128.3, 128.3, 128.1, 126.5, 125.0, 123.7,
74.6, 66.4, 54.5, 44.07, 17.7, 14.5. LRMS (EI): 292[M+], 262, 244, 217, 199, 173, 155, 129, 91.
HRMS (ESI): calcd for C19H17O3, [M+H] +, 293.1172; found, 293.1176.
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Compound b31. White solid. 72 mg. Yield 53%. 1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 7.4 Hz,
1H), 7.30 – 7.23 (m, 1H), 7.16 (td, J = 7.4, 0.9 Hz, 1H), 7.10 (d, J = 7.2 Hz, 1H), 5.69 (ddt, J = 16.3,
9.7, 6.6 Hz, 1H), 5.22 (d, J = 6.3 Hz, 1H), 4.97 (dd, J = 3.2, 1.4 Hz, 1H), 4.93 (d, J = 0.9 Hz, 1H), 4.30
– 4.02 (m, 1H), 3.75 (qt, J = 10.9, 6.6 Hz, 2H), 3.34 (dd, J = 6.2, 2.9 Hz, 1H), 2.40 (dd, J = 8.0, 5.2 Hz,
1H), 2.26 – 2.07 (m, 1H), 2.01 – 1.80 (m, 2H), 1.48 13C NMR (151 MHz, CDCl3) δ 169.9, 137.4, 132.5,
131.7, 128.3, 126.5, 124.9, 123.7, 115.1, 74.7, 63.9, 54.5, 44.0, 29.8, 27.5, 17.7, 14.5. LRMS (EI):
+
270[M+], 241, 193, 155, 129. HRMS (ESI): calcd for C17H19O3, [M+H] , 271.1329; found,
271.1334.
Compound b32. White solid. 76 mg. Yield 54%. 1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 7.5 Hz,
1H), 7.31 – 7.24 (m, 1H), 7.16 (t, J = 7.4 Hz, 1H), 7.10 (d, J = 7.3 Hz, 1H), 5.75 (ddt, J = 16.9, 10.2,
6.7 Hz, 1H), 5.21 (d, J = 6.3 Hz, 1H), 5.05 – 4.92 (m, 2H), 4.18 (t, J = 4.6 Hz, 1H), 3.90 – 3.54 (m, 2H),
3.34 (dd, J = 6.2, 2.9 Hz, 1H), 2.40 (dd, J = 7.9, 5.2 Hz, 1H), 2.27 – 2.08 (m, 1H), 1.96 (q, J = 6.8 Hz,
2H), 1.39 – 1.12 (m, 4H). 13C NMR (150 MHz, CDCl3) δ 169.9, 138.3, 132.5, 131.7, 128.3, 126.5,
124.8, 123.7, 114.8, 74.7, 64.4, 54.5, 44.0, 33.2, 27.8, 24.9, 17.7, 14.5. LRMS (EI): 284[M+], 199,
184, 172, 155, 129. HRMS (ESI): calcd for C18H20O3Na, [M+Na] +, 307.1305; found, 307.1308.
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Compound b33. White solid. 55 mg. Yield 48%. H NMR (400 MHz, CDCl3) δ 7.25 – 6.90 (m,
3H), 5.17 (t, J = 6.6 Hz, 1H), 4.16 (s, 1H), 3.37 (s, 3H), 3.34 – 3.23 (m, 1H), 2.44 – 2.28 (m, 4H),
2.18 – 2.03 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 170.4, 138.0, 132.2, 129.1, 127.1, 125.7,
123.4, 74.4, 54.5, 51.6, 44.1, 21.2, 17.4, 14.5. LRMS (EI): 230[M+], 213, 201, 186, 169, 157, 142,
128, 115, 102. HRMS (ESI): calcd for C14H15O3, [M+H] +, 231.1016; found, 231.1019.
Compound b34. White solid. 68 mg. Yield 55%. 1H NMR (400 MHz, CDCl3) δ 7.35 (s, 1H), 7.14
(t, J = 8.2 Hz, 1H), 7.04 (d, J = 7.9 Hz, 1H), 5.20 (d, J = 6.0 Hz, 1H), 4.29 – 4.12 (m, 1H), 3.58 –
3.29 (m, 4H), 2.38 (m, 1H), 2.24 – 2.10 (m, 1H). 13C NMR (150 MHz, CDCl3) major: δ 170.0,
134.3, 131.0, 130.1, 127.9, 125.1, 123.8, 74.0, 54.6, 51.8, 43.8, 17.6, 14.8, minor: δ 170.0, 133.9,
130.8, 128.4, 127.9, 126.6, 124.9, 74.0, 54.6, 51.8, 43.8, 17.6, 14.8. LRMS (EI): 250[M+], 235,
221, 207, 191, 177, 162, 142, 127, 101. HRMS (ESI): calcd for C13H12ClO3, [M+H] +, 251.0469;
found, 251.0470.
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Compound b35.White solid. 60 mg. Yield 52%. H NMR (400 MHz, CDCl3) δ 7.07 (d, J = 7.6
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Hz, 2H), 6.86 (t, J = 8.6 Hz, 1H), 5.21 (d, J = 6.0 Hz, 1H), 4.19 (s, 1H), 3.54 – 3.19 (m, 4H), 2.47
– 2.32 (m, 1H), 2.28 – 2.06 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 170.1, 162.77 (d, J = 245.0
Hz), 134.74 (d, J = 8.9 Hz), 134.74 (d, J = 8.9 Hz), 127.7, 125.22 (d, J = 8.8 Hz), 113.62 (d, J =
22.7 Hz), 111.94 (d, J = 22.1 Hz), 74.0, 54.5, 51.7, 44.0, 18.0, 14.8. LRMS (EI): 234[M+], 219,
205, 190, 175, 161, 146, 135, 127, 115. HRMS (ESI): calcd for C13H12O3F, [M+H] +, 235.0765;
found, 235.0769.
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Compound b36. White solid. 70 mg. Yield 54%. 1H NMR (400 MHz, CDCl3) δ 7.35 (s, 1H), 7.10
(m, 2H), 5.20 (d, J = 6.1 Hz, 1H), 4.20 (m, 1H), 3.99 – 3.65 (m, 2H), 3.34 (m, 1H), 2.52 – 2.28 (m,
1H), 2.25 – 2.04 (m, 1H), 0.95 (t, J = 6.8 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.5, 134.5,
133.8, 130.1, 126.6, 125.1, 125.0, 74.1, 60.6, 54.6, 43.9, 17.6, 14.8, 13.9. LRMS (EI): 264[M+],
+
248, 235, 218, 207, 191, 163, 127, 115, 101. HRMS (ESI): calcd for C14H14O3Cl, [M+H] ,
265.0626; found, 265.0628.
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Compound b37. White solid. 65 mg. Yield 53%. H NMR (400 MHz, CDCl3) δ 7.32 – 7.27 (m,
1H), 7.07 (d, J = 8.5 Hz, 2H), 6.85 (t, J = 8.6 Hz, 1H), 5.20 (d, J = 6.2 Hz, 1H), 4.36 – 4.08 (m,
1H), 3.90 – 3.67 (m, 2H), 3.50 – 3.11 (m, 1H), 2.52 – 2.31 (m, 1H), 2.21 – 2.06 (m, 1H), 0.94 (t, J
= 6.9 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 169.6 (s), 162.79 (d, J = 245.1 Hz), 134.91 (d, J =
8.8 Hz), 127.68 (d, J = 3.0 Hz), 125.39 (d, J = 9.0 Hz), 113.58 (d, J = 22.6 Hz), 111.76 (d, J =
22.0 Hz), 74.1, 60.5, 54.5, 44.0, 18.0, 14.8, 13.9. LRMS (EI): 248[M+], 229, 219, 202, 191, 175,
159, 147, 127, 115. HRMS (ESI): calcd for C14H14O3F, [M+H] +, 249.0921; found, 249.0923.
Compound b38. Colorless oil. 56 mg. Yield 46%. 1H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 7.4 Hz,
1H), 7.26 (t, J = 7.3 Hz, 1H), 7.16 (t, J = 7.3 Hz, 1H), 7.09 (d, J = 7.3 Hz, 1H), 5.27 (d, J = 6.1 Hz, 1H),
3.55 (s, 4H), 3.32 (s, 3H), 2.80 (d, J = 8.4 Hz, 1H), 2.36 (dd, J = 8.3, 2.4 Hz, 1H). 13C NMR (100 MHz,
CDCl3) δ 169.9, 132.8, 131.5, 128.4, 126.1, 125.3, 123.7, 95.5, 75.7, 57.0, 51.5, 43.8, 24.9, 19.4.
HRMS (ESI): calcd for C14H15O4, [M+H] +, 247.0965; found, 247.0967.
Compound c1. White solid. 244 mg. Yield 78%. 1H NMR (600 MHz, CDCl3) δ 7.34 – 7.24 (m, 3H),
7.16 (d, J = 7.1 Hz, 1H), 4.07 (s, 1H), 3.91 (s, 1H), 3.54 (dd, J = 9.3, 2.0 Hz, 1H), 3.43 (s, 1H), 3.39 (d,
J = 5.1 Hz, 1H), 3.32 (dd, J = 9.3, 2.0 Hz, 1H), 2.38 (s, 3H), 2.21 (s, 3H). 13C NMR (150 MHz, CDCl3)
δ 207.5, 204.5, 171.3, 171.0, 136.0, 133.6, 129.1, 128.9, 126.1, 125.4, 50.6, 49.6, 45.0, 41.4, 38.5, 38.0,
29.4, 28.0. HRMS (ESI): calcd for C18H17O5, [M+H] +, 313.1071; found, 313.1078.
Compound c5. Colorless oil. 256 mg. Yield 75%. 1H NMR (400 MHz, CDCl3) δ 7.25 – 7.14 (m,
3H), 7.12 – 6.94 (m, 1H), 4.09 – 4.00 (m, 1H), 3.97 (t, J = 3.1 Hz, 1H), 3.81 (s, 3H), 3.44 (dd, J = 5.4,
2.2 Hz, 1H), 3.33 (dd, J = 5.4, 2.9 Hz, 1H), 3.29 (dd, J = 8.5, 3.2 Hz, 1H), 3.15 (dd, J = 8.5, 3.3 Hz,
1H), 2.49 (s, 3H), 2.23 (s, 3H).13C NMR (150 MHz, CDCl3) δ 204.6, 177.3, 177.0, 173.5, 136.3, 133.8,
128.4, 128.2, 125.7, 125.3, 52.7, 52.5, 44.4, 42.4, 41.0, 38.7, 38.6, 28.1, 24.3. HRMS (ESI): calcd for
C19H20O5N, [M+H] +, 342.1336; found, 342.1339.
Compound d10. Colorless oil. 63 mg. Yield 90%. 1H NMR (400 MHz, CDCl3) δ 7.23 – 7.16 (m,
1H), 7.15 – 7.10 (m, 2H), 7.07 (d, J = 7.4 Hz, 1H), 4.97 (d, J = 4.9 Hz, 1H), 4.66 – 4.45 (m, 1H), 4.08
(q, J = 6.3 Hz, 1H), 3.39 (t, J = 5.0 Hz, 1H), 3.34 (dd, J = 17.5, 4.1 Hz, 1H), 2.78 (d, J = 17.4 Hz, 1H),
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2.62 (s, 1H), 1.72 – 1.51 (m, 2H), 1.44 – 1.31 (m, 4H), 1.27 (d, J = 6.3 Hz, 4H), 1.20 – 1.07 (m, 2H),
1.05 – 0.83 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 169.6, 138.0, 133.5, 129.1, 128.3, 127.9, 126.1,
80.7, 77.7, 72.5, 47.3, 41.3, 33.5, 31.3, 30.8, 25.2, 23.4, 23.2, 21.8. HRMS (ESI): calcd for C19H25O3,
[M+H] +, 301.1798; found, 301.1794.
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ASSOCIATED CONTENT
Supporting Information
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The Supporting Information is available free of charge on the ACS Publications website at DOI:
1H and 13C NMR spectra, NOE spectra, and 2D spectra of starting materials and products (PDF).
Xꢀray crystal structure data for b6’ and b22’ (CIF).
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: xyyang@hit.edu.cn
*Eꢀmail: xiawj@hit.edu.cn
ORCID
Qiang Liu: 0000ꢀ0001ꢀ8342ꢀ712X
Wujiong Xia: 0000ꢀ0001ꢀ9396ꢀ9520
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful for the financial supports from China NSFC (Nos. 21372055, 21472030 and
21672047), SKLUWRE (No. 2017DX03) and the Fundamental Research Funds for the Central
Universities (Grant No. HIT.BRETIV.201310).
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