Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation

Article abstract of DOI:10.1021/acs.joc.5b00775

A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

Full text of DOI:10.1021/acs.joc.5b00775

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The Journal of Organic Chemistry
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PalladiumꢀCatalyzed orthoꢀOlefination of Phenyl Acetic and Phenyl
Propylacetic Esters via C–H Bond Activation
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Jundie Hu, Mingyu Guan, Jian Han, ZhiꢀBin Huang, DaꢀQing Shi,* and Yingsheng Zhao*
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Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical
Engineering and Materials Science, Soochow University, Suzhou 215123, China
Email: yszhao@suda.edu.cn; dqshi@suda.edu.cn
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ABSTRACT: A highly regioselective palladiumꢀcatalyzed esterꢀdirected orthoꢀolefination
of phenyl acetic and propionic esters with olefins via C
developed. A wide variety of phenyl aceticꢀ and propionic esters were tolerated in this
transformation, affording the corresponding olefinated aromatic compounds. The ortho
–H bond activation has been
ꢀ
olefination of heterocyclic acetic and propionic esters also took place smoothly giving the
products in good yields, thus proving the potential utility of this protocol in synthetic
chemistry.
INTRODUCTION
Directing groupꢀassisted C–H functionalization has emerged as a powerful method of
synthesis in organic chemistry, with wide application in total synthesis, medicinal
chemistry, and material chemistry.1 From literature, highly regioselective Pdꢀcatalyzed C–
H transformation has been accomplished via cyclopalladation using amides,2 acids,3
oximes,4 and hydroxyls5 as directing groups. Although a variety of directing groups have
been developed,6ꢀ9 the esterꢀassisted oxidative Heck reaction is not well explored (Scheme
1A).10 In a groundꢀbreaking research, Chang and coꢀworkers first reported that the ester
unit can be employed as directing group in the Rh (III)ꢀcatalyzed olefination of
benzoates.11 In 2012, Ackermann and coꢀworkers also reported a ruthenium (II) complex
catalyzed oxidative olefination of arenes using weakly coordinated esters as directing
groups.12 Very recently, Yu and coꢀworkers13 described the use of Weinreb amides/esters
as effective directing groups and monoprotected amino acid as ligand in the Pdꢀcatalyzed
directed orthoꢀC–H olefination of phenylacetic acids derivatives. In spite of these
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significant progresses, developing an ester as directing group in assisted orthoꢀC–H
transformation of phenylpropionic acid is still desirable. As functional group/directing
group, esters are widely available and can be readily converted to amides, alcohols, or
carbonyl compounds.14ꢀ15 These advantages make them better than other reported amide
types of directing group which usually need to go through introduction and removal
processes.16ꢀ17 Herein, we report a palladiumꢀcatalyzed esterꢀdirected C–H olefination
reaction of synthetically useful phenyl acetic18 and propionic19 acid derivatives employing
1,10ꢀphenanthroline as ligand (Scheme 1B). Notably, heterocyclic acetic and propionic
acids reacted well under mild conditions giving corresponding products in good yields.
Scheme 1. Weakly Coordinated Directing Groupꢀassisted C−H Transformation
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RESULTS AND DISCUSSION
We commenced our studies by exploring the effects of solvents (for detailed
information see supporting information), ligands, oxidants, and additives on the palladiumꢀ
catalyzed regioselective oxidative olefination of phenylacetic ester 1a with acrylate 2a
.
Initially, starting materials 1a and 2a were reacted in the presence of Pd(OAc)2 (10 mol %)
o
and Ag2CO3 (2 equiv) in hexafluoroisopropanol (HFIP) at 100 C for 24 h. The isolated
yield of the desired orthoꢀolefinated product 3a was 11%. The addition of different
additives, such as PivOH, 1ꢀAdOH (1ꢀAdamantane carboxylic acid), PPh3, pyridine, all
gave unsatisfactory yields (Table 1, entries 1ꢀ5). Expectedly, the addition of AcꢀGlyꢀOH,
which is well known to improve the reactivity of the palladium center in weakly
coordinated functional group20 assisted C–H functionalization, greatly improved the yield
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of product (entry 6). Other bidentate ligands were also screened, and 1,10ꢀphenanthroline
exhibited the best promoting effect, thus affording the highly regioselective product 3a in
73% yield (entry 7). Also, oxidants such as AgOAc, Ag2O, O2/Cu(OAc)2, O2/BQ, K2S2O8
were all tested, but still silver carbonate turned out to be the best (entries 8ꢀ12).
Interestingly, further improvement could be observed when 1ꢀAdOH and 1,10ꢀ
phenanthroline were both employed in the reaction (entries 13ꢀ15). Experiment also
showed that no reaction could take place in the absence of palladium catalyst. It is worthy
to note that a variety of phenylacetic esters, such as methyl (1b), ethyl (1c), isopropyl
esters (1d) and ethyl acrylate 2a were tested under the optimal reaction condition with all
affording the corresponding oxidative Heckꢀtype products (Scheme 2). However, the yields
of olefinated compounds obtained from these esters are lower compared with that of
substrate 1a. In addition, better regioselectivity was achieved with ester 1a as against
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Table 1. Optimization Reaction Conditionsa
entry
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oxidant
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
AgOAc
Ag2O
additive
ꢀ
PivOH
1ꢀAdOH
Ph3P
yieldb (%)
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pyridine
AcꢀGlyꢀOH
1,10ꢀphenanthroline
1,10ꢀphenanthroline
1,10ꢀphenanthroline
1,10ꢀphenanthroline
1,10ꢀphenanthroline
1,10ꢀphenanthroline
1,10ꢀphenanthroline
PivOH
1,10ꢀphenanthroline
1ꢀAdOH
1,10ꢀphenanthroline
AcOH
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13c
O2/BQ
O2/Cu(OAc)2
K2S2O8
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79
Ag2CO3
14c
Ag2CO3
Ag2CO3
Ag2CO3
86 (82)d
15c
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0
16c,e
1,10ꢀphenanthroline
1ꢀAdOH
aReaction conditions: 1a (0.1 mmol), 2a (0.2 mmol), Pd(OAc)2 (10 mol %), ligand (10 mol %), oxidant (0.2
mmol), HFIP (0.3 mL), 100 °C, 24 h. bLC yield determined using acetophenone as internal standard. cwith ligands
(10 mol %) respectively. dIsolated yield. eWithout Pd(OAc)2. Ac = acetyl, Gly = glycine, BQ = 1,4ꢀbenzoquinone.
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Scheme 2. Directing Group Optimization Studies
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substrates 1bꢀc, which were identified by proton NMR spectrum (for detailed information,
see supporting information). We speculated that the coordinating ability of the carbonyl
group was enhanced by electron rich 1,3ꢀdimethoxypropanꢀ2ꢀol. Thus, the palladium
intermediate could be trapped in the coordination center thereby avoiding the competitive
poorly regioselective oxidative Heck reaction.
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With an optimized catalytic system in hand, we next explored the scope of palladiumꢀ
catalyzed esterꢀdirected orthoꢀolefination of phenylacetic esters (Table 2). Various
phenylacetic acid esters substituted with electron withdrawingꢀ or donating functional
groups were tolerated under slightly modified reaction conditions, giving products in good
yield (3a and 3fꢀl). Interestingly, the substrate bearing sterically hindered 3,4,5ꢀtrimethoxy
group 1m underwent the reaction, affording monoꢀolefinated product 3m in good yield.
Also the presence of strong electronꢀwithdrawing group of trifluoromethyl (3k) and
bromide (3i) reduced reactivity; acceptable yields could be obtained by increasing reaction
temperature and time to 110oC and 48 hours respectively. Delightfully, heterocyclic acetic
esters also gave monoꢀolefinated products (3n, 3o) in acceptable synthetic yields. The ester
of cyclohexeneacetic acid (1p) required a longer period of time to furnish the olefinated
product in good yield. To further expand the substrate scope, the unsubstituted ester of
phenylacetic acid was tested, and rather disappointingly a mixture of oxidative Heck type
monoꢀolefinated products 3q (ortho/others: 3:2) were generated, thereby limiting the
substrate scope of this protocol. We speculated that the optimal reaction condition is
propitious to an undirected palladiumꢀcatalyzed oxidative olefination, resulting in mixture
of olefinated products (see supporting information). However, the presence of a para
ꢀ
substituent in arene would inhibit oxidative olefination reaction, thereby favouring the
highly regioselective orthoꢀolefination reaction via the assistance of weakly coordinated
directing group of ester.21
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Table 2. Scope of Phenylacetyl Estersa
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aReaction conditions:
1 (0.2 mmol), 2a (0.3 mmol), Pd(OAc)2 (10 mol %), Ag2CO3 (0.4 mmol), 1,10ꢀ
phenanthroline (10 mol %), 1ꢀAdOH (10 mol %), HFIP (0.5 mL), 100 oC, 24 h. b110 oC. c48 h.
A series of olefins were also tested and representative data are listed in Table 3. For example,
acrylic esters, acrylic amides, acrylic ketone, all afforded the corresponding Heckꢀtype olefinated
products, and the yields were in the range of 56 to 77%. When acrylonitrile was used as a
Table 3. Scope of Olefinsa
aReaction conditions: 1a (0.2 mmol),
2 (0.3 mmol), Pd(OAc)2 (10 mol %), Ag2CO3 (0.4 mmol), 1,10ꢀ
phenanthroline (10 mol %), 1ꢀAdOH (10 mol %), HFIP (0.5 mL), 100 oC, 24 h. b80 oC.
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counterpart, the orthoꢀolefinated product (3w) was obtained in 66% yield, proving its
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potential utilization in the construction of useful synthon.
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To our delight, our newly developed protocol was also applicable to phenylpropionic
acid derivatives (Table 4). Under modified reaction conditions, several paraꢀsubstituted
phenylpropionic acids were tested, affording the products in good to excellent yields (5aꢀ
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d
). It is worth noting that the diolefinated products were observed in less than 5% yields.
We reasoned that the olefinated products would stabilize the palladium catalyst, inhibiting
further C–H transformation. The olefination reaction of 3ꢀ(2ꢀfuryl) propionic acid and 2ꢀ
thiophenepropionic acid occurred regioselectively at the 3ꢀposition, giving monoꢀ
olefinated products in 72% and 69% yields respectively (5eꢀf).
Table 4. Scope of Phenylpropionic Acid Derivativesa
aReaction conditions:
4 (0.2 mmol), 2a (0.3 mmol), Pd(OAc)2 (10 mol %), Ag2CO3 (0.4 mmol), 1,10ꢀ
phenanthroline (10 mol %), 1ꢀAdOH (10 mol %), HFIP (0.5 mL), 100 C, 24 h. b110 C. 48 h. Dark
o
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d
operation.
The substrate scope of ester directed orthoꢀolefination reaction could be further extended to
benzoic acid derivates.22 For example, substrate 6a and 6b was transformed into the corresponding
monoꢀolefinated products in good yield under standard reaction conditon (Scheme 3).
To fulfil synthetic requirements, the newly developed protocol should be easily scaled up in
the lab. Indeed, the gramꢀscale reaction was carried out with 5 mol % Pd(OAc)2 under an extended
period of time (48 hours) to give the product in 74% yield (Scheme 4).
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Scheme 3. Scope of Benzoates
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Scheme 4. Gram Scale of Reaction
In an attempt to gain a deep understanding of the role of phenanthroline in this ester
directed C–H transformation, 1a and 20 equivalents of AcOD were treated with and
without 1,10ꢀphenanthroline (10 mol %) in the presence of Pd(OAc)2 (10 mol %) at 100 oC
for 30 h. It turned out that 77% (Scheme 5B) deuteration incorporation occurred with
phenanthroline compared with 11% deuteration incorporation (Scheme 5A) without
phenanthroline. We hypothesized that phenanthroline could increase the rate of C–H
activation or stabilize the palladium intermediate during the catalytic cycle. Although the
mechanistic details are still unclear, a plausible mechanism for this reaction based on
above data and pioneering reports23is proposed in Scheme 6. It is postulated that palladium
intermediate
pathway. The subsequent migratory insertion of olefin
which undergoes ꢀhydride elimination to give olefin products
Scheme 5. Deuterium Experiments
A
is possibly formed through a concerted metalation−deprotonation (CMD)
2
might generate intermediate B,
β
3.
CONCLUSION
In conclusion, we have developed a regioselective palladium–catalyzed ester directed
orthoꢀolefination of phenyl acetic and propionic esters with olefins. The new method
provides an efficient, economical and practical way to modify aromaticꢀcontaining alipatic
acids under mild condition. Olefinated heterocyclic acetic and propionic acid esters were
also obtained in good yields. The use of ester directing group could find potential
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application in other C–H transformations and the study is being undertaken presently in our
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laboratory.
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Scheme 6. Plausible Mechanism
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EXPERIMENTAL SECTION
Preparation of directing group (1bꢀ1e). To a solution of 2ꢀ(4ꢀmethoxyphenyl) acetic acid (1.7 g,
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10 mmol, 1.0 equiv) in DCM (50 mL) at 0 C was added SOCl2 (2.4 g, 20 mmol, 2.0 equiv)
dropwise and stirred for 15 min. To the mixture was added slowly the alcohol (30 mmol, 3.0 equiv)
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and further stirred for 2 hrs at 0 C. Et3N (4.4 g, 40 mmol, 4.0 equiv) was then added to the
resulting suspension and allowed to stir whilst slowly warming to room temperature over 8 hrs.24
The resultant was concentrated, washed with ether, and filtered through celite, washed again with
aqueous NaOH (50 mL), and saturated aqueous NH4Cl (50 mL), dried over sodium sulfate, and
concentrated in vacuo. The resulting residue was purified by column chromatography on silica gel
to give the oily products.
Methyl-2-(4-methoxyphenyl)acetate (1b): Colorless oil, 3.02 g, yield 84%, PE/EA= 10:1 (PE =
1
petroleum ether, EA = ethyl acetate). H NMR (400 MHz, CDCl3) δ: 7.20 (d, J = 8.8 Hz, 2H),
6.87 (d, J = 8.8 Hz, 2H), 3.78 (s, 3H), 3.68 (s, 3H), 3.57 (s, 2H); 13C NMR (101 MHz, CDCl3) δ:
171.9, 158.3, 129.8, 125.6, 113.5, 54.7, 51.5, 39.8; HRMS (ESIꢀTOF) m/z Calcd for C10H13O3
[M+H]+: 181.0865; Found: 181.0866.
Ethyl-2-(4-methoxyphenyl)acetate (1c): Colorless oil, 3.34 g, yield 86%, PE/EA= 10:1. 1H NMR
(400 MHz, CDCl3) δ: 7.20 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 4.14 (q, J = 7.2 Hz, 2H),
3.79 (s, 3H), 3.55 (s, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 172.1, 158.8,
130.4, 126.4, 114.1, 60.9, 55.4, 40.6, 14.3; HRMS (ESIꢀTOF) m/z Calcd for C11H14O3Na[M+Na]+:
217.0841; Found: 217.0841.
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Isopropyl 2-(4-methoxyphenyl)acetate (1d): Colorless oil, 3.33 g, yield 80%, PE/EA= 10:1. H
NMR (400 MHz, CDCl3) δ: 7.20 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 5.04ꢀ4.97 (m, 1H),
3.79 (s, 3H), 3.52 (s, 2H), 1.22 (d, J = 6.4 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ: 171.0, 158.1,
129.7, 125.9, 113.5, 67.6, 54.8, 40.3, 21.3; HRMS (ESIꢀTOF) m/z Calcd for C12H16O3Na[M+Na]+:
231.0997; Found: 231.0986.
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2-methoxyethyl 2-(4-methoxyphenyl)acetate (1e): Colorless oil, 3.72 g, yield 83%, PE/EA= 10:1.
1H NMR (400 MHz, CDCl3) δ: 7.19 (d, J = 8.8 Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 4.23ꢀ4.21 (m,
2H), 3.76 (s, 3H), 3.58 (s, 2H), 3.57ꢀ3.55 (m, 2H), 3.34 (s, 3H); 13C NMR (101 MHz, CDCl3) δ:
172.0, 158.8, 130.4, 126.1, 114.0, 70.4, 63.9, 59.0, 55.3, 40.2; HRMS (ESIꢀTOF) m/z Calcd for
C12H16O4Na[M+Na]+: 247.0946; Found: 247.0940.
Preparation of substrates (1a, 1fꢀ1p, 4aꢀ4f, 6a and 6b).25ꢀ26 To a solution of DCC (2.1 g, 10
o
mmol, 1.0 equiv) in DCM (50 mL) at 0 C was added DMAP (1.5 g, 12 mmol, 1.2 equiv) and 2ꢀ
(4ꢀmethoxyphenyl) acetic acid (1.7 g, 10 mmol, 1.0 equiv). To the resulting suspension was then
added 1,3ꢀdimethoxyꢀ2ꢀpropanol (1.8 g, 15 mmol, 1.5 equiv). The reaction mixture was allowed
to stir whilst slowly warming to room temperature over 15 hrs. The reaction was concentrated in
vacuo, washed with ether, filtered through celite, washed again with NaOH (aq, 50 mL), washed
with saturated NH4Cl (aq, 50 mL), dried over sodium sulfate, and concentrated in vacuo. The
crude mixture was purified by column chromatography on silica gel to give the corresponding
products.
1,3-dimethoxypropan-2-yl 2-(4-methoxyphenyl)acetate (1a): Colorless oil, 2.09 g, yield 83%,
1
PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.19 (d, J = 8.8 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H),
5.16ꢀ5.11 (m, 1H), 3.77 (s, 3H), 3.59 (s, 2H), 3.51 (d, J = 5.2 Hz, 4H), 3.31 (s, 6H); 13C NMR
(101 MHz, CDCl3) δ: 171.5, 158.7, 130.3, 126.0, 113.9, 71.6, 71.1, 59.2, 55.2, 40.4; HRMS (ESIꢀ
TOF) m/z Calcd for C14H20O5Na[M+Na]+: 291.1208; Found: 291.1208.
1,3-dimethoxypropan-2-yl 2-(4-fluorophenyl)acetate (1f): Colorless oil, 2.11 g, yield 88%,
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PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.30ꢀ7.25 (m, 2H), 7.02 (t, J = 8.8 Hz, 2H), 5.19ꢀ
5.14 (m, 1H), 3.66 (s, 2H), 3.54 (d, J = 4.8 Hz, 4H), 3.34 (s, 6H); 13C NMR (101 MHz, CDCl3) δ:
171.0, 162.0 (d, JCꢀF = 244 Hz), 130.8 (d, JCꢀF = 8.0 Hz), 129.7 (d, JCꢀF = 3.3 Hz), 115.3 (d, JCꢀF
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21 Hz), 71.8, 71.1, 59.2, 40.4; HRMS (ESIꢀTOF) m/z Calcd for C13H17FO4Na[M+Na]+: 279.1009;
Found: 279.1009.
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1,3-dimethoxypropan-2-yl 2-(4-chlorophenyl)acetate (1g): Colorless oil, 1.99 g, yield 78%,
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PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.30ꢀ7.27 (m, 2H), 7.23 (d, J = 8.8 Hz, 2H), 5.18ꢀ
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5.13 (m, 1H), 3.64 (s, 2H), 3.52 (d, J = 5.2 Hz, 4H), 3.33 (s, 6H); 13C NMR (101 MHz, CDCl3) δ:
170.8, 133.0, 132.4, 130.6, 128.6, 71.8, 71.1, 59.2, 40.6; HRMS (ESIꢀTOF) m/z Calcd for
C13H17ClO4Na[M+Na]+: 295.0713; Found: 295.0707.
1,3-dimethoxypropan-2-yl 1-(4-chlorophenyl)cyclobutanecarboxylate (1h): Colorless oil, 2.53 g,
yield 81%, PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.24 (s, 4H), 5.12ꢀ5.07 (m, 1H), 3.41 (d, J
= 5.2 Hz, 4H), 3.21 (s, 6H), 2.86ꢀ2.80 (m, 2H), 2.48ꢀ2.41 (m, 2H), 2.07ꢀ2.00 (m, 1H), 1.89ꢀ1.82
(m, 1H); 13C NMR (101 MHz, CDCl3) δ: 174.8, 142.1, 132.3, 128.2, 127.8, 71.8, 71.1, 59.1, 52.1,
32.2, 16.5; HRMS (ESIꢀTOF) m/z Calcd for C16H21ClO4Na[M+Na]+: 335.1026; Found: 335.1025.
1,3-dimethoxypropan-2-yl 2-(4-bromophenyl)acetate (1i): Colorless oil, 2.49 g, yield 83%,
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PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.48 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H),
5.23ꢀ5.18 (m, 1H), 3.67 (s, 2H), 3.57 (d, J = 5.2 Hz, 4H), 3.37 (s, 6H); 13C NMR (101 MHz,
CDCl3) δ: 170.6, 132.9, 131.6, 131.0, 121.1, 71.8, 71.1, 59.2, 40.6; HRMS (ESIꢀTOF) m/z Calcd
for C13H17BrO4Na[M+Na] +: 339.0208; Found: 339.0215.
1,3-dimethoxypropan-2-yl 2-(4-bromo-2-methoxyphenyl)acetate (1j): Colorless oil, 2.51 g, yield
76%, PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.00ꢀ6.93 (m, 2H), 6.93 (s, 1H), 5.12ꢀ5.07 (m,
1H), 3.72 (s, 3H), 3.55 (s, 2H), 3.47 (d, J = 5.2 Hz, 4H), 3.28 (s, 6H); 13C NMR (101 MHz, CDCl3)
δ: 170.8, 158.1, 131.9, 123.4, 122.2, 121.6, 114.0, 71.6, 71.1, 59.1, 55.6, 35.5; HRMS (ESIꢀTOF)
m/z Calcd for C14H19BrO5Na[M+Na]+: 369.0314; Found: 369.0323.
1,3-dimethoxypropan-2-yl 2-(4-(trifluoromethyl)phenyl)acetate (1k): Colorless oil, 2.29 g, yield
79%, PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.55 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.0 Hz,
2H), 5.18ꢀ5.13 (m, 1H), 3.71 (s, 2H), 3.50 (d, J = 5.2 Hz, 4H), 3.30 (s, 6H); 13C NMR (101 MHz,
CDCl3) δ: 169.9, 137.5, 129.2, 125.0, 124.9, 124.9, 122.3, 71.5, 70.6, 58.6, 40.5; HRMS (ESIꢀ
TOF) m/z Calcd for C14H17F3O4Na[M+Na]+: 329.0977; Found: 329.0980.
1,3-dimethoxypropan-2-yl 1-(4-methoxyphenyl)cyclopropanecarboxylate (1l): Colorless oil, 2.53
1
g, yield 86%, PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.26 (d, J = 8.8 Hz, 2H), 6.82 (d, J =
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8.4 Hz, 2H), 5.09ꢀ5.04 (m, 1H), 3.79 (s, 3H), 3.45 (d, J = 5.2 Hz, 4H), 3.29 (s, 6H), 1.60 (q, J =
4.0 Hz, 2H), 1.16 (q, J = 4.0 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 174.3, 158.6, 131.7, 131.5,
113.4, 71.9, 71.2, 59.2, 55.3, 28.4, 16.6; HRMS (ESIꢀTOF) m/z Calcd for C16H22O5Na[M+Na]+:
317.1365; Found: 317.1360.
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1,3-dimethoxypropan-2-yl 2-(3,4,5-trimethoxyphenyl)acetate (1m): Colorless oil, 2.43 g, yield
74%, PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 6.51 (s, 2H), 5.18ꢀ5.13 (m, 1H), 3.84 (s, 6H),
3.81 (s, 3H), 3.59 (s, 2H), 3.53 (d, J = 5.6 Hz, 4H), 3.32 (s, 6H); 13C NMR (101 MHz, CDCl3) δ:
170.6, 152.7, 136.6, 129.0, 105.8, 73.3, 71.3, 70.6, 60.3, 58.7, 55.6, 41.1; HRMS (ESIꢀTOF) m/z
Calcd for C16H24O7Na[M+Na] +: 351.1420; Found: 351.1414.
1,3-dimethoxypropan-2-yl 2-(1-methyl-1H-indol-2-yl)acetate (1n): Colorless oil, 2.44 g, yield
84%, PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.67 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.0 Hz,
1H), 7.29ꢀ7.25 (m, 1H), 7.17 (t, J = 8.0 Hz, 1H), 7.09 (s, 1H), 5.27ꢀ5.22 (m, 1H), 3.87 (s, 2H),
3.74 (s, 3H), 3.60 (d, J = 5.6 Hz, 4H), 3.38 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 171.7, 137.0,
127.9, 127.8, 121.7, 119.1, 119.0, 109.3, 106.7, 71.6, 71.2, 59.2, 32.6, 31.3; HRMS (ESIꢀTOF)
m/z Calcd for C16H21NO4Na[M+Na]+: 314.1368; Found: 314.1360.
1,3-dimethoxypropan-2-yl 2-(thiophen-2-yl)acetate (1o): Colorless oil, 1.78 g, yield 73%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.20ꢀ7.19 (m, 1H), 6.94 (s, 2H), 5.19ꢀ5.13 (m, 1H),
3.87 (s, 2H), 3.53 (d, J = 5.2 Hz, 4H), 3.33 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 169.5, 134.5,
126.4, 126.3, 124.5, 71.6, 70.5, 58.7, 34.9; HRMS (ESIꢀTOF) m/z Calcd for
C11H16SO4Na[M+Na]+: 267.0667; Found: 267.0667.
1,3-dimethoxypropan-2-yl 2-(cyclohex-1-en-1-yl)acetate (1p): Colorless oil, 2.15 g, yield 89%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 5.55 (s, 1H), 5.14ꢀ5.09 (m, 1H), 3.51 (d, J = 4.8 Hz,
4H), 3.33 (s, 6H), 2.96 (s, 2H), 1.98 (s, 4H), 1.62ꢀ1.60 (m, 2H), 1.55ꢀ1.51 (m, 2H); 13C NMR (101
MHz, CDCl3) δ: 171.5, 131.0, 125.7, 71.2, 71.2, 59.2, 43.6, 28.3, 25.3, 22.7, 22.0; HRMS (ESIꢀ
TOF) m/z Calcd for C13H22O4Na[M+Na]+: 265.1416; Found: 265.1408.
1,3-dimethoxypropan-2-yl 3-(4-fluorophenyl)propanoate (4a): Colorless oil, 4.06 g, yield 80%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.12ꢀ7.08 (m, 2H), 6.91ꢀ6.87 (m, 2H), 5.12ꢀ5.07 (m,
1H), 3.43 (d, J = 4.8 Hz, 4H), 3.27 (s, 6H), 2.87 (t, J = 7.6 Hz, 2H), 2.59 (t, J = 7.6 Hz, 2H); 13
C
NMR (101 MHz, CDCl3) δ: 172.1, 161.4 (d, JCꢀF = 243 Hz), 136.1 (d, JCꢀF = 3.2 Hz), 129.7 (d, JCꢀ
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F = 7.8 Hz), 115.1 (d, JCꢀF = 21 Hz), 71.2 (d, JCꢀF = 12.6 Hz), 59.0, 35.9, 30.0; HRMS (ESIꢀTOF)
m/z Calcd for C14H19FO4Na[M+Na] +: 293.1165; Found: 293.1158.
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1,3-dimethoxypropan-2-yl 2-(4-fluorophenoxy)acetate (4b): Colorless oil, 4.45 g, yield 87%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 6.96ꢀ6.91 (m, 2H), 6.85ꢀ6.81 (m, 2H), 5.26ꢀ5.23 (m,
1H), 4.60 (d, J = 4.0 Hz, 2H), 3.52 (d, J = 3.6 Hz, 4H), 3.31 (s, 6H); 13C NMR (101 MHz, CDCl3)
δ: 168.0, 157.3 (d, JCꢀF = 238 Hz), 153.5 (d, JCꢀF = 2.2 Hz), 115.5 (d, JCꢀF = 2.0 Hz), 115.3 (d, JCꢀF
= 13.0 Hz), 71.7, 70.5, 65.4, 58.7; HRMS (ESIꢀTOF) m/z Calcd for C13H17FO5Na[M+Na]+:
295.0958; Found: 295.0963.
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1,3-dimethoxypropan-2-yl 3-(4-bromophenyl)propanoate (4c): Colorless oil, 4.96 g, yield 79%,
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PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.34 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H),
5.12ꢀ5.07 (m, 1H), 3.44 (d, J = 5.6 Hz, 4H), 3.28 (s, 6H), 2.86 (t, J = 7.6 Hz, 2H), 2.60 (t, J = 7.6
Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 172.0, 139.4, 131.4, 130.1, 120.0, 71.3, 71.1, 59.1, 35.5,
30.3; HRMS (ESIꢀTOF) m/z Calcd for C14H19BrO4Na [M+Na]+: 353.0364; Found: 353.0352.
1,3-dimethoxypropan-2-yl 3-(4-methoxyphenyl)propanoate (4d): Colorless oil, 4.31 g, yield 81%,
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PE/EA= 8:1. H NMR (400 MHz, CDCl3) δ: 7.12 (d, J = 8.8 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H),
5.16ꢀ5.11 (m 1H), 3.78 (s, 3H), 3.50 (d, J = 5.2 Hz, 4H), 3.34 (s, 6H), 2.90 (t, J = 7.6 Hz, 2H),
2.64 (t, J = 7.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 172.5, 158.1, 132.5, 129.3, 113.9, 71.2,
59.2, 55.3, 36.2, 30.1; HRMS (ESIꢀTOF) m/z Calcd for C15H22O5Na[M+Na]+: 305.1365; Found:
305.1362.
1,3-dimethoxypropan-2-yl 3-(furan-2-yl)propanoate (4e): Colorless oil, 3.96 g, yield 82%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.30 (s, 1H), 6.28ꢀ6.26 (m, 1H), 6.03 (d, J = 3.2 Hz,
1H), 5.19ꢀ5.14 (m, 1H), 3.53 (d, J = 4.8 Hz, 4H), 3.35 (s, 6H), 2.98 (t, J = 7.6 Hz, 2H), 2.71 (t, J =
7.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 172.0, 154.1, 141.2, 110.2, 105.3, 71.3, 71.1, 59.2,
32.7, 23.4; HRMS (ESIꢀTOF) m/z Calcd for C12H18O5Na[M+Na]+: 265.1052; Found: 265.1043.
1,3-dimethoxypropan-2-yl 3-(thiophen-2-yl)propanoate (4f): Colorless oil, 4.39 g, yield 85%,
PE/EA= 8:1. 1H NMR (400 MHz, CDCl3) δ: 7.09 (d, J = 5.2 Hz, 1H), 6.89ꢀ6.87 (m, 1H), 6.80 (d,
J = 3.2 Hz, 1H), 5.17ꢀ5.12(m, 1H), 3.50 (d, J = 5.2 Hz, 4H), 3.32 (s, 6H), 3.15 (t, J = 7.6 Hz, 2H),
2.71 (t, J = 7.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 171.9, 143.0, 126.8, 124.7, 123.5, 71.4,
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71.1, 59.2, 36.1, 25.2; HRMS (ESIꢀTOF) m/z Calcd for C12H18SO4Na[M+Na]+: 281.0823; Found:
281.0832.
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1,3-dimethoxypropan-2-yl 4-methoxybenzoate (6a): Colorless oil, 4.00 g, yield 84%, PE/EA= 8:1.
1H NMR (400 MHz, CDCl3) δ: 7.98 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 5.34ꢀ5.29 (m,
1H), 3.80 (s, 3H), 3.62 (d, J = 5.2 Hz, 4H), 3.35 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 165.8,
163.4, 131.8, 122.5, 113.5, 71.6, 71.3, 59.2, 55.4; HRMS (ESIꢀTOF) m/z Calcd for
C13H18O5Na[M+Na] +: 277.1052; Found: 277.1045.
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1,3-dimethoxypropan-2-yl 4-fluorobenzoate (6b): Colorless oil, 3.75 g, yield 83%, PE/EA= 8:1.
1H NMR (400 MHz, CDCl3) δ: 8.01ꢀ8.05 (m, 2H), 7.09 (t, J = 8.8 Hz, 2H), 5.38ꢀ3.33 (m, 1H),
3.65 (d, J = 5.6 Hz, 4H), 3.38 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 165.8 (d, JCꢀF = 252 Hz),
165.1, 132.4 (d, JCꢀF = 9.3 Hz), 132.1 (d, JCꢀF = 9.3 Hz), 126.4 (d, JCꢀF = 3.0 Hz), 115.5 (d, JCꢀF
=
22.0 Hz), 72.1, 71.3, 59.3; HRMS (ESIꢀTOF) m/z Calcd for C12H15FO4Na[M+Na]+: 265.0852;
Found: 265.0835.
General procedure for the synthesis of products (3aꢀ3w, 5aꢀ5f, 7a and 7b). A mixture of
phenylacetate (0.2 mmol, 1.0 equiv), 2a (0.3 mmol, 1.5 equiv), Pd(OAc)2 (4.4 mg, 0.1 equiv),
Ag2CO3 (547.6 mg, 2.0 equiv), 1,10ꢀphenanthroline (3.6 mg, 0.1 equiv), adamantine carboxylic
acid (3.6 mg, 0.1 equiv) and HFIP (0.5 mL) in a 15 mL glass vial (sealed with PTFE cap) was
o
heated at 100 C for 24 hours. The reaction mixture was cooled to rt, and concentrated in vacuo.
The resulting residue was purified by column chromatography on silica gel to give the
corresponding products. Reactions involving 3i, 3k, 5d and 5e were heated at 110 oC, while 3k, 3o,
5d were reacted for 48 h, 5f took place under dark.
Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-5-methoxyphenyl)acrylate
(3a):
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Colorless oil, 60.0 mg, yield 82%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.92 (d, J = 16.0
Hz, 1H), 7.41 (s, 1H), 7.23 (d, J = 8.4 Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 6.49 (d, J = 16.4 Hz, 1H),
5.15ꢀ5.10 (m, 1H), 4.22 (q, J = 6.8 Hz, 2H), 3.83 (s, 3H), 3.58 (s, 2H), 3.50 (d, J = 4.8 Hz, 4H),
3.30 (s, 6H), 1.29 (t, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.2, 167.4, 157.4, 139.7,
132.2, 129.7, 126.1, 123.4, 119.0, 111.3, 71.8, 71.1, 60.3, 59.2, 55.6, 40.3, 14.3; HRMS (ESIꢀTOF)
m/z Calcd for C19H26O7Na[M+Na]+: 389.1576; Found: 389.1577.
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Ethyl-3-(5-methoxy-2-(2-methoxy-2-oxoethyl)phenyl)acrylate (3b): Colorless oil, 40.6 mg, yield
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73%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.99 (d, J = 16.4 Hz, 1H), 7.45 (d, J = 2.0 Hz,
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1H), 7.31ꢀ7.28 (m, 1H), 6.91 (d, J = 7.6 Hz, 1H), 6.57 (d, J = 16.0 Hz, 1H), 6.40 (d, J = 15.6 Hz,
0.07H), 4.30 (q, J = 7.2 Hz, 2H), 3.91 (s, 3H), 3.73 (s, 3H), 3.61 (s, 2H), 1.37 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, CDCl3) δ: 171.6, 167.0, 157.0, 139.2, 131.7, 129.3, 125.7, 123.0, 118.6,
110.8, 76.9, 76.6, 76.3, 59.9, 55.1, 51.6, 39.6, 38.1, 35.9, 27.4, 13.9; HRMS (ESIꢀTOF) m/z Calcd
for C15H18O5Na[M+Na]+: 301.1052; Found: 301.1050.
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Ethyl-3-(2-(2-ethoxy-2-oxoethyl)-5-methoxyphenyl)acrylate (3c): Colorless oil, 43.2 mg, yield
74%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.99 (d, J = 16.0 Hz, 1H), 7.45 (d, J = 2.4 Hz,
1H), 7.31ꢀ7.29 (m, 1H), 6.91 (d, J = 8.8 Hz, 1H), 6.57 (d, J = 16.0 Hz, 1H), 6.40 (d, J = 15.6 Hz,
0.11H), 4.30 (q, J = 7.2 Hz, 2H), 4.19 (q, J = 7.2 Hz, 2H), 3.91 (s, 3H), 3.59 (s, 2H), 1.37 (t, J =
7.2 Hz, 3H), 1.29 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.1, 167.0, 157.0, 139.3,
131.7, 129.2, 125.8, 123.0, 118.6, 110.8, 60.4, 59.9, 55.1, 39.9, 13.8, 13.7; HRMS (ESIꢀTOF) m/z
Calcd for C16H20O5Na[M+Na]+: 315.1208; Found: 315.1213.
Ethyl-3-(2-(2-isopropoxy-2-oxoethyl)-5-methoxyphenyl)acrylate (3d): Colorless oil, 41.6 mg,
yield 68%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.00 (d, J = 16.4 Hz, 1H), 7.46 (d, J = 2.4
Hz, 1H), 7.32ꢀ7.29 (m, 1H), 6.91 (d, J = 8.6 Hz, 1H), 6.57 (d, J = 16.4 Hz, 1H), 6.40 (d, J = 16.0
Hz, 0.1H), 5.08ꢀ5.02 (m, 1H), 4.30 (q, J = 7.2 Hz, 2H), 3.92 (s, 3H), 3.56 (s, 2H), 1.38 (t, J = 7.2
Hz, 3H), 1.27 (d, J = 6.4 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ: 170.7, 167.0, 156.9, 139.3,
131.6, 129.2, 126.0, 122.9, 118.5, 110.8, 67.8, 59.9, 55.1, 40.2, 21.3, 13.9; HRMS (ESIꢀTOF) m/z
Calcd for C17H22O5Na[M+Na]+: 329.1365; Found: 329.1359.
Ethyl-3-(5-methoxy-2-(2-(2-methoxyethoxy)-2-oxoethyl)phenyl)acrylate (3e): Colorless oil, 36.7
mg, yield 57%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.95 (d, J = 16.0 Hz, 1H), 7.43 (d, J
= 2.0 Hz, 1H), 7.27ꢀ7.25 (m, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.52 (d, J = 16.4 Hz, 1H), 6.35 (d, J =
15.6 Hz, 0.05H), 4.28ꢀ4.22 (m, 4H), 3.87 (s, 3H), 3.60ꢀ3.58 (m, 4H), 3.37 (s, 3H), 1.33 (t, J = 7.2
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.2, 167.0, 157.0, 139.2, 131.7, 129.3, 125.6, 123.0,
118.6, 110.8, 69.9, 63.5, 59.9, 58.5, 55.1, 39.6, 13.9; HRMS (ESIꢀTOF) m/z Calcd for
C17H22O6Na[M+Na]+: 345.1314; Found: 345.1314.
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Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-5-fluorophenyl)acrylate
(3f):
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Colorless oil, 57.3 mg, yield 81%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.76 (d, J = 16.0
Hz, 1H), 7.47 (d, J = 7.2 Hz, 1H), 7.27 (s, 1H), 7.05 (d, J = 8.4 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H),
5.18ꢀ5.13 (m, 1H), 4.25 (q, J = 7.2 Hz, 2H), 3.64 (s, 2H), 3.52 (d, J = 5.2 Hz, 4H), 3.32 (s, 6H),
1.32 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.2, 166.3, 160 (d, JCꢀF = 252 Hz),
136.5 (d, JCꢀF = 2.6 Hz), 132.0 (d, JCꢀF = 8.8 Hz), 129.7 (d, JCꢀF = 3.7 Hz), 129.3 (d, JCꢀF = 3.1 Hz),
122.0 (d, JCꢀF = 12.1 Hz), 120.6 (d, JCꢀF = 6.5 Hz), 115.8 (d, JCꢀF = 22.0 Hz), 71.5, 70.6, 60.1, 58.7,
39.9, 13.8; HRMS (ESIꢀTOF) m/z Calcd for C18H23FO6Na[M+Na]+: 377.1376; Found: 377.1375.
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Ethyl-3-(5-chloro-2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)phenyl)acrylate
(3g):
Colorless oil, 51.1 mg, yield 69%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.05 (d, J = 16.0
Hz, 1H), 7.56 (s, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7.24 (d, J = 6.0 Hz, 1H), 6.45 (d, J = 16.0 Hz, 1H),
5.19ꢀ5.14 (m, 1H), 4.27 (q, J = 7.2 Hz, 2H), 3.66 (s, 2H), 3.53 (d, J = 5.6 Hz, 4H), 3.33 (s, 6H),
1.34 (t, J = 7.2 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 170.5, 166.5, 140.1, 133.7, 133.1, 132.8,
131.9, 130.2 , 128.5, 121.2, 72.0, 71.1, 60.7, 59.2, 40.6, 14.3; HRMS (ESIꢀTOF) m/z Calcd for
C18H23ClO6Na[M+Na]+: 393.1081; Found: 393.1082.
1,3-dimethoxypropan-2-yl 1-(4-chloro-2-(3-ethoxy-3-oxoprop-1-en-1-yl)phenyl)cyclobutanecar-
boxylate (3h): Compound 3h, colorless oil, 58.2 mg, yield 71%, PE/EA= 5:1. 1H NMR (400 MHz,
CDCl3) δ: 8.06 (d, J = 16.0 Hz, 1H), 7.55 (d, J = 2.4 Hz, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7.27 (d, J
= 2.4 Hz, 1H), 6.46 (d, J = 16.0 Hz, 1H), 5.14ꢀ5.09 (m, 1H), 4.28 (q, J = 7.2 Hz, 2H), 3.43 (d, J =
5.2 Hz, 4H), 3.24 (s, 6H), 2.89ꢀ2.83 (m, 2H), 2.51ꢀ2.44 (m, 2H), 2.11ꢀ2.02 (m,1H), 1.93ꢀ1.85 (m,
1H), 1.35 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 174.7, 166.5, 142.8, 140.4, 133.1,
132.4, 129.8, 129.1, 125.7, 121.1, 72.0, 71.2, 60.7, 59.2, 52.1, 32.3, 16.6, 14.3; HRMS (ESIꢀTOF)
m/z Calcd for C21H27ClO6Na[M+Na] +: 433.1394; Found: 433.1393.
Ethyl-3-(5-bromo-2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)phenyl)acrylate
(3i):
Colorless oil, 55.5 mg, yield 67%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.01 (d, J = 16.0
Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.4 Hz, 1H), 6.40 (d, J = 16.0 Hz, 1H), 5.19ꢀ5.14
(m, 1H), 4.27 (q, J = 7.2 Hz, 2H), 3.64 (s, 2H), 3.53 (d, J = 4.8 Hz, 4H), 3.33 (s, 6H), 1.33 (t, J =
7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.3, 166.4, 142.7, 134.6, 133.8, 133.4, 132.1,
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128.6, 123.9, 121.4, 72.0, 71.1, 60.7, 59.2, 40.6, 14.3; HRMS (ESIꢀTOF) m/z Calcd for
C18H23BrO6Na[M+Na]+: 439.0555; Found: 439.0557.
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Ethyl-3-(5-bromo-2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-3-methoxyphenyl)acrylate
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(3j): Colorless oil, 57.7 mg, yield 65%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.95 (d, J =
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16.0 Hz, 1H), 7.47 (s, 1H), 7.05 (s, 1H), 6.29 (d, J = 16.0 Hz, 1H), 5.18ꢀ5.13 (m, 1H), 4.24 (q, J =
7.2 Hz, 2H), 3.81 (s, 3H), 3.61 (s, 2H), 3.52 (d, J = 5.1 Hz, 4H), 3.33 (s, 6H), 1.31 (t, J = 7.2 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ: 170.5, 166.7, 159.2, 142.3, 129.5, 126.5, 125.3, 123.3, 118.8,
115.1, 71.8, 71.1, 60.5, 59.2, 55.9, 35.5, 14.3; HRMS (ESIꢀTOF) m/z Calcd for
C19H25BrO7Na[M+Na]+: 469.0658; Found: 469.0657.
Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-5-(trifluoromethyl)phenyl)acrylate
(3k): Colorless oil, 54.9 mg, yield 68%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.91 (d, J =
15.6 Hz, 1H), 7.81 (s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 6.43 (d, J = 15.6 Hz,
1H), 5.20ꢀ5.15 (m, 1H), 4.27 (q, J = 7.2 Hz, 2H), 3.87 (s, 2H), 3.52 (d, J = 5.2 Hz, 4H), 3.32 (s,
6H), 1.34 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 207.0, 168.0 (d, JCꢀF = 358 Hz),
140.2, 137.1, 135.0, 131.6, 128.9, 126.3, 123.8 (d, JCꢀF = 4 Hz), 122.5, 72.2, 71.0, 60.8, 59.2, 30.9,
14.3; HRMS (ESIꢀTOF) m/z Calcd for C19H23F3O6Na [M+Na]+: 427.1344; Found: 427.1344.
1,3-dimethoxypropan-2-yl 1-(2-(3-ethoxy-3-oxoprop-1-en-1-yl)-4-methoxyphenyl)cyclopropane-
carboxylate (3l): Colorless oil, 61.9 mg, yield 79%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ:
7.93 (d, J = 16.4 Hz, 1H), 7.48 (d, J = 2.0 Hz, 1H), 7.31ꢀ7.29 (m, 1H), 6.82 (d, J = 8.4 Hz, 1H),
6.51 (d, J = 16.0 Hz, 1H), 5.08ꢀ5.03 (m, 1H), 4.23 (q, J = 7.2 Hz, 2H), 3.85 (s, 3H), 3.43 (d, J =
5.2 Hz, 4H), 3.28 (s, 6H), 1.61 (q, J = 4.0 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H), 1.15 (q, J = 4.0 Hz,
2H); 13C NMR (101 MHz, CDCl3) δ: 173.9, 167.4, 157.3, 139.9, 133.3, 131.7, 131.0, 123.0, 118.8,
110.8, 72.0, 71.1, 60.3, 59.2, 55.6, 28.3, 16.6, 14.3; HRMS (ESIꢀTOF) m/z Calcd for
C21H28O7Na[M+Na]+: 415.1733; Found: 415.1732.
Ethyl-3-(6-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-2,3,4-trimethoxyphenyl)acrylate
(3m): Colorless oil, 62.2 mg, yield 73%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.67 (d, J =
16.4 Hz, 1H), 6.58 (s, 1H), 6.46 (d, J = 16.0 Hz, 1H), 5.14ꢀ5.09 (m, 1H), 4.19 (q, J = 7.2 Hz, 2H),
3.81 (s, 3H), 3.80 (s, 6H), 3.70 (s, 2H), 3.48 (d, J = 4.8 Hz, 4H), 3.27 (s, 6H), 1.27 (t, J = 7.2 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ: 170.1, 167.0, 153.5, 153.0, 141.1, 137.7, 129.3, 121.4, 120.8,
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109.6, 71.4, 70.5, 60.3, 60.1, 59.7, 58.6, 55.4, 38.9, 13.8; HRMS (ESIꢀTOF) m/z Calcd for
C21H30O9Na[M+Na]+: 449.1788; Found: 449.1782.
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Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-1-methyl-1H-indol-3-yl)acrylate
(3n): Colorless oil, 46.3 mg, yield 62%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J =
16.0 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.30ꢀ7.29 (m, 2H), 7.16ꢀ7.12 (m, 1H), 6.48 (d, J = 16.0 Hz,
1H), 5.18ꢀ5.13 (m, 1H), 4.29 (q, J = 7.2 Hz, 2H), 3.95 (s, 2H), 3.82 (s, 3H), 3.53 (d, J = 4.8 Hz,
4H), 3.31 (s, 6H), 1.36 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.8, 167.0, 138.3,
132.7, 132.2, 127.6, 124.1, 120.2, 120.2, 119.8, 111.2, 109.5, 71.9, 71.1, 60.7, 59.2, 31.4, 30.9,
14.4; HRMS (ESIꢀTOF) m/z Calcd for C21H27NO6Na[M+Na]+: 412.1736; Found: 412.1744.
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Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)thiophen-3-yl)acrylate
(3o):
Colorless oil, 41.0 mg, yield 60%, PE/EA= 5:1.1H NMR (400 MHz, CDCl3) δ: 7.70 (d, J = 15.6
Hz, 1H), 7.09 (d, J = 3.6 Hz, 1H), 6.90 (d, J = 3.6 Hz, 1H), 6.16 (d, J = 15.6 Hz, 1H), 5.21ꢀ5.16
(m, 1H), 4.24 (q, J = 7.2 Hz, 2H), 3.87 (s, 2H), 3.55 (d, J = 5.2 Hz, 4H), 3.35 (s, 6H), 1.32 (t, J =
7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 169.4, 166.9, 139.3, 138.5, 137.1, 130.9, 128.0,
116.6, 72.4, 71.0, 60.5, 59.3, 35.9, 14.3; HRMS (ESIꢀTOF) m/z Calcd for C16H22SO6Na[M+Na]+:
365.1035; Found: 365.1036.
Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)cyclohex-1-en-1-yl)acrylate
(3p):
1
Colorless oil, 53.0 mg, yield 78%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.72 (d, J = 15.6
Hz, 1H), 5.84 (d, J = 15.6 Hz, 1H), 5.14ꢀ5.09 (m, 1H), 4.18 (q, J = 7.2 Hz, 2H), 3.50 (d, J = 5.2
Hz, 4H), 3.32 (s, 6H), 2.23 (s, 2H), 2.18 (s, 2H), 1.89ꢀ1.88 (m, 1H), 1.69 (s, 2H), 1.65ꢀ1.61 (m,
3H), 1.27 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.3, 167.6, 141.8, 138.6, 130.6,
116.6, 71.7, 71.1, 60.2, 59.2, 39.0, 38.6, 36.4, 31.9, 27.8, 25.5, 22.3, 14.3; HRMS (ESIꢀTOF) m/z
Calcd for C18H28O6Na[M+Na]+: 363.1784; Found: 363.1783.
1,3-dimethoxypropan-2-yl 2-(4-methoxy-2-(3-oxopent-1-en-1-yl)phenyl)acetate (3r): Colorless
1
oil, 51.1 mg, yield 73%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.87 (d, J = 16.4 Hz, 1H),
7.47 (d, J = 2.0 Hz, 1H), 7.28ꢀ7.26 (m, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.77 (d, J = 16.4 Hz, 1H),
5.17ꢀ5.12 (m, 1H), 3.87 (s, 3H), 3.61 (s, 2H), 3.53 (d, J = 5.2 Hz, 4H), 3.33 (s, 6H), 2.70 (q, J =
7.2 Hz, 2H), 1.15 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 201.5, 171.2, 157.5, 137.2,
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132.4, 129.2, 126.9, 126.2, 123.6, 111.3, 71.8, 71.1, 59.2, 55.6, 40.3, 33.6, 8.3; HRMS (ESIꢀTOF)
m/z Calcd for C19H26O6Na[M+Na]+: 373.1627; Found: 373.1627.
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Benzyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethyl)-5-methoxyphenyl)acrylate
(3s):
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Colorless oil, 60.8 mg, yield 71%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.00 (d, J = 16.4
Hz, 1H), 7.44ꢀ7.24 (m, 2H), 7.41ꢀ7.39 (m, 2H), 7.38ꢀ7.37(m, 1H), 7.35ꢀ7.33 (m, 1H), 7.28ꢀ7.25
(m, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.59 (d, J = 16.4 Hz, 1H), 5.25 (s, 2H), 5.18ꢀ5.13 (m, 1H), 3.86
(s, 3H), 3.61 (s, 2H), 3.53 (d, J = 5.2 Hz, 4H), 3.32 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 171.2,
167.3, 157.5, 140.4, 136.3, 132.4, 129.9, 128.6, 128.2, 128.1, 126.2, 123.4, 118.6, 111.3, 71.8,
71.1, 66.2, 59.2, 55.6, 40.3; HRMS (ESIꢀTOF) m/z Calcd for C24H28O7Na[M+Na]+: 451.1733;
Found: 451.1739.
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2ꢀhydroxyethyl 3ꢀ(2ꢀ(2ꢀ((1,3ꢀdimethoxypropanꢀ2ꢀyl)oxy)ꢀ2ꢀoxoethyl)ꢀ5ꢀmethoxyphenyl)ꢀ
acrylate (3t): Colorless oil, 42.8 mg, yield 56%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.97
(d, J = 16.0 Hz, 1H), 7.43 (d, J = 2.4 Hz, 1H), 7.28ꢀ7.25 (m, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.56 (d,
J = 16.0 Hz, 1H), 5.17ꢀ5.12 (m, 1H), 4.4ꢀ 4.32 (m, 2H), 3.93ꢀ3.88 (m, 2H), 3.86 (s, 3H), 3.61 (s,
2H), 3.52 (d, J = 5.2Hz, 4H), 3.32 (s, 6H), 2.26 (s, 1H); 13C NMR (101 MHz, CDCl3) δ: 171.2,
167.8, 157.6, 140.7, 132.5, 129.9, 126.2, 123.2, 118.3, 111.3, 71.8, 71.1, 66.2, 61.4, 59.2, 55.6,
40.2; HRMS (ESIꢀTOF) m/z Calcd for C19H26O8Na[M+Na]+: 405.1525; Found: 405.1524.
1,3-dimethoxypropan-2-yl 2-(2-(3-(tert-butylamino)-3-oxoprop-1-en-1-yl)-4-methoxyphenyl)-
acetate (3u): Colorless oil, 56.6 mg, yield 72%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.78
(d, J = 16.0 Hz, 1H), 7.36 (s, 1H), 7.20 (d, J = 8.8 Hz, 1H), 6.82 (d, J = 8.4 Hz, 1H), 6.44 (d, J =
15.6 Hz, 1H), 5.62 (s, 1H), 5.16ꢀ5.11 (m, 1H), 3.82 (s, 3H), 3.58 (s, 2H), 3.51 (d, J = 5.2 Hz, 4H),
3.31 (s, 6H), 1.41 (s, 9H); 13C NMR (101 MHz, CDCl3) δ: 171.3, 165.8, 157.3, 135.3, 131.3,
129.5, 125.9, 124.0, 123.1, 111.2, 71.7, 71.1, 59.2, 55.5, 51.4, 40.3, 28.9; HRMS (ESIꢀTOF) m/z
Calcd for C21H31NO6Na[M+Na]+: 416.2049; Found: 416.2037.
1,3-dimethoxypropan-2-yl 2-(2-(3-(dimethylamino)-3-oxoprop-1-en-1-yl)-4-methoxyphenyl)-
acetate (3v): Colorless oil, 49.6 mg, yield 68%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.89
(d, J = 15.6 Hz, 1H), 7.42 (s, 1H), 7.25ꢀ7.22 (m, 1H), 6.98 (d, J = 15.6 Hz, 1H), 6.86 (d, J = 8.8
Hz, 1H), 5.18ꢀ5.13 (m, 1H), 3.86 (s, 2H), 3.62 (s, 2H), 3.53 (d, J = 5.2 Hz, 4H), 3.33 (s, 6H), 3.11
(s, 6H); 13C NMR (101 MHz, CDCl3) δ: 207.0, 171.3, 157.3, 137.7, 131.4, 129.7, 126.0, 124.4,
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118.4, 111.3, 71.7, 71.1, 59.2, 55.6, 40.4, 30.9, 29.3; HRMS (ESIꢀTOF) m/z Calcd for
C19H27NO6Na[M+Na]+: 388.1736; Found: 388.1726.
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1,3-dimethoxypropan-2-yl 2-(2-(2-cyanovinyl)-4-methoxyphenyl)acetate (3w): Colorless oil, 42.1
mg, yield 66%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.60 (d, J = 16.8 Hz, 1H), 7.33ꢀ7.26
(m, 2H), 6.88 (d, J = 8.4 Hz, 1H), 6.06 (d, J = 16.8 Hz, 1H), 5.18ꢀ5.13 (m, 1H), 3.88 (s, 3H), 3.62
(s, 2H), 3.53 (d, J = 4.4 Hz, 4H), 3.34 (s, 6H); 13C NMR (101 MHz, CDCl3) δ: 171.0, 157.3, 146.2,
133.1, 129.6, 126.4, 122.6, 118.9, 111.4, 97.2, 71.8, 71.1, 59.2, 55.7, 40.1; HRMS (ESIꢀTOF) m/z
Calcd for C17H21NO5Na[M+Na]+: 342.1317; Found: 342.1312.
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Ethyl-03-(2-(3-((1,3-dimethoxypropan-2-yl)oxy)-3-oxopropyl)-5-fluorophenyl)acrylate
(5a):
Colorless oil, 54.5 mg, yield 74%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.78 (d, J = 16.4
Hz, 1H), 7.39ꢀ7.37 (m, 1H), 7.23ꢀ7.19 (m, 1H), 7.05ꢀ7.00 (m, 1H), 6.54 (d, J = 16.4 Hz, 1H),
5.18ꢀ5.13 (m, 1H), 4.28 (q, J = 7.2 Hz, 2H), 3.51 (d, J = 5.2 Hz, 4H), 3.35 (s, 6H), 2.96 (t, J = 7.6
Hz, 2H), 2.69 (t, J = 7.6 Hz, 2H), 1.35 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 172.0,
166.8, 160 (d, JCꢀF = 251 Hz), 137.2 (d, JCꢀF = 2.5 Hz), 136.6 (d, JCꢀF = 3.6 Hz), 131.6 (d, JCꢀF
=
8.6 Hz), 128.8 (d, JCꢀF = 3.0 Hz), 122.3 (d, JCꢀF = 11.9 Hz), 120.8 (d, JCꢀF = 6.7 Hz), 116.1 (d, JCꢀF
= 22.0 Hz), 71.4, 71.2, 60.6, 59.2, 38.7, 36.4, 35.8, 30.0, 27.8, 14.3; HRMS (ESIꢀTOF) m/z Calcd
for C19H25FO6Na[M+Na]+: 391.1533; Found: 391.1537.
Ethyl-3-(2-(2-((1,3-dimethoxypropan-2-yl)oxy)-2-oxoethoxy)-5-fluorophenyl)acrylate
(5b):
Colorless oil, 66.6 mg, yield 90%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.74 (d, J = 16.0
Hz, 1H), 7.04ꢀ7.00 (m, 2H), 6.93 – 6.89 (m, 1H), 6.49 (d, J = 16.0 Hz, 1H), 5.33ꢀ5.27 (m, 1H),
4.66 (s, 2H), 4.26 (q, J = 7.2 Hz, 2H), 3.55 (d, J = 5.6 Hz, 4H), 3.35 (s, 6H), 1.33 (t, J = 7.2 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ: 167.8, 166.2, 156.0 (d, JCꢀF = 247 Hz), 153.5 (d, JCꢀF = 2.2
Hz), 136.4 (d, JCꢀF = 2.5 Hz), 122.5 (d, JCꢀF = 3.0 Hz), 120.7 (d, JCꢀF = 6.4 Hz), 117.7 (d, JCꢀF = 8.5
Hz), 116.5 (d, JCꢀF = 24.0 Hz), 113.5 (d, JCꢀF = 3.0 Hz), 71.8, 70.6, 65.5, 60.2, 58.7, 30.4, 13.8;
HRMS (ESIꢀTOF) m/z Calcd for C18H23FO7Na[M+Na]+: 393.1326; Found: 393.1326.
Ethyl-3-(5-bromo-2-(3-((1,3-dimethoxypropan-2-yl)oxy)-3-oxopropyl)phenyl)acrylate
(5c):
Colorless oil, 71.0 mg, yield 83%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.00 (d, J = 16.0
Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.45ꢀ7.43 (m, 1H), 7.22 (d, J = 8.0 Hz, 1H), 6.38 (d, J = 16.0
Hz, 1H), 5.19ꢀ5.11(m, 1H), 4.26 (q, J = 7.2 Hz, 2H), 3.48 (d, J = 2.4 Hz, 4H), 3.32 (s, 6H), 2.93(t,
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J = 7.6 Hz, 2H), 2.67 (t, J = 7.6 Hz, 2H), 1.34 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ:
171.9, 166.4, 144.3, 142.8, 140.2, 133.4, 128.9, 128.2, 127.8, 117.7, 71.2, 60.7, 59.2, 35.4, 30.7,
30.3, 14.3; HRMS (ESIꢀTOF) m/z Calcd for C19H25BrO6Na[M+Na]+: 451.0732; Found: 451.0728.
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Ethyl-3-(2-(3-((1,3-dimethoxypropan-2-yl)oxy)-3-oxopropyl)-5-methoxyphenyl)acrylate
(5d):
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Colorless oil, 47.9 mg, yield 63%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.93 (d, J = 16.4
Hz, 1H), 7.33 (d, J = 2.0 Hz, 1H), 7.19ꢀ7.16 (m, 1H), 6.82 (d, J = 8.4 Hz, 1H), 6.51 (d, J = 16.4
Hz, 1H), 5.15ꢀ5.10 (m, 1H), 4.24 (q, J = 7.2 Hz, 2H), 3.85 (s, 3H), 3.49 (d, J = 5.2 Hz, 4H), 3.32
(s, 6H), 2.90 (t, J = 7.2 Hz, 2H), 2.65(t, J = 8.0 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H); 13C NMR (101
MHz, CDCl3) δ: 172.3, 167.5, 156.9, 140.0, 132.5, 131.3, 128.8, 123.3, 118.8, 111.3, 71.2, 71.2,
60.3, 59.2, 55.6, 36.0, 30.0, 14.4; HRMS (ESIꢀTOF) m/z Calcd for C20H28O7Na[M+Na]+:
403.1733; Found: 403.1722.
Ethyl-3-(2-(3-((1,3-dimethoxypropan-2-yl)oxy)-3-oxopropyl)furan-3-yl)acrylate (5e): Colorless
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oil, 49.0 mg, yield 70%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 7.33 (d, J = 15.6 Hz, 1H),
6.48 (d, J = 3.2 Hz, 1H), 6.21 (d, J = 16.0 Hz, 1H), 6.12 (d, J = 3.6 Hz, 1H), 5.18ꢀ5.13 (m, 1H),
4.21 (q, J = 7.2 Hz, 2H), 3.51 (d, J = 5.2 Hz, 4H), 3.33 (s, 6H), 2.99 (t, J = 7.6 Hz, 2H), 2.72 (t, J
= 7.2 Hz, 2H), 1.29 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.7, 167.2, 157.1, 149.8,
130.9, 116.0, 114.7, 108.5, 71.2, 59.2, 38.6, 32.3, 27.8, 23.7, 14.3; HRMS (ESIꢀTOF) m/z Calcd
for C17H25O7 [M+H]+: 341.1600; Found: 341.1600.
Ethyl-3-(2-(3-((1,3-dimethoxypropan-2-yl)oxy)-3-oxopropyl)thiophen-3-yl)acrylate
(5f):
Colorless oil, 49.1 mg, yield 69%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 7.66 (d, J = 15.6
Hz, 1H), 7.02 (d, J = 3.6 Hz, 1H), 6.74 (d, J = 3.6 Hz,, 1H), 6.08 (d, J = 15.6 Hz, 1H), 5.16ꢀ5.11
(M, 1H), 4.20 (q, J = 7.2 Hz, 2H), 3.49 (d, J = 5.2 Hz, 4H), 3.31 (s, 6H), 3.12(t, J = 7.6 Hz, 2H),
2.71 (t, J = 7.6 Hz, 2H), 1.28 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 171.6, 166.9,
146.9, 137.9, 137.2, 131.3, 126.0, 116.0, 71.5, 71.1, 60.4, 59.2, 35.6, 25.6, 14.3; HRMS (ESIꢀTOF)
m/z Calcd for C17H24SO6Na[M+Na]+: 379.1191; Found: 379.1205.
1,3-dimethoxypropan-2-yl 2-(3-ethoxy-3-oxoprop-1-en-1-yl)-4-methoxybenzoate (7a): Colorless
oil, 57.0 mg, yield 81%, PE/EA= 5:1. 1H NMR (400 MHz, CDCl3) δ: 8.21 (s, 1H), 8.08ꢀ8.05 (m,
1H), 7.95 (d, J = 16.4 Hz, 1H), 6.93 (d, J = 8.8 Hz, 1H), 6.58 (d, J = 16.0 Hz, 1H), 5.40ꢀ5.35 (m,
1H), 4.27 (q, J = 7.2 Hz, 2H), 3.94 (s, 3H), 3.67 (d, J = 5.2 Hz, 4H), 3.39 (s, 6H), 1.34 (t, J = 7.2
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Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 167.2, 165.4, 161.7, 139.0, 133.3, 130.7, 123.4, 122.7,
120.0, 110.7, 71.9, 71.4, 60.5, 59.3, 55.9, 14.4; HRMS (ESIꢀTOF) m/z Calcd for
C18H24O7Na[M+Na]+: 375.1420; Found: 375.1412.
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1,3-dimethoxypropan-2-yl 2-(3-ethoxy-3-oxoprop-1-en-1-yl)-4-fluorobenzoate (7b): Colorless oil,
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50.3 mg, yield 74%, PE/EA= 5:1. H NMR (400 MHz, CDCl3) δ: 8.27 (d, J = 7.2 Hz, 1H), 8.09ꢀ
8.06 (m, 1H), 7.80 (d, J = 16.4 Hz, 1H), 7.18ꢀ7.10 (m, 1H), 6.61 (d, J = 16.4 Hz, 1H), 5.42ꢀ5.37
(m, 1H), 4.28 (q, J = 7.2 Hz, 2H), 3.66 (d, J = 4.8 Hz, 4H), 3.39 (s, 6H), 1.35 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, CDCl3) δ: 166.0, 164.2, 163.4 (d, JCꢀF = 259 Hz), 135.6 (d, JCꢀF = 2.4 Hz),
132.8 (d, JCꢀF = 10.0 Hz), 130.6 (d, JCꢀF = 4.4 Hz), 126.4 (d, JCꢀF = 3.2 Hz), 121.7 (d, JCꢀF = 6.4
Hz), 116.0, 115.8, 71.9, 70.8 (d, JCꢀF = 8.0 Hz), 60.3, 58.8 (d, JCꢀF = 6.4 Hz), 38.2, 35.9, 27.3, 13.8;
HRMS (ESIꢀTOF) m/z Calcd for C17H21FO6Na[M+Na]+: 363.1220; Found: 363.1225.
General procedure for the deuterium experiments are represented as follows (Scheme 5A
and 5B). A mixture of phenylacetate 1a (134.0 mg, 0.5 mmol, 1.0 equiv), AcOD (610.0 mg, 10
mmol, 20 equiv), Pd(OAc)2 (11.2 mg, 0.05 mmol, 0.1 equiv) with and without 1,10ꢀ
phenanthroline (9.0 mg, 0.05 mmol, 0.1 equiv) in a 25 mL glass vial (purged with Ar, sealed with
PTFE cap) were heated at 100 oC for 30 h respectively. The reaction mixture was cooled to room
temperature, and concentrated in vacuo. The resulting residue was purified by column
chromatography on silica gel to give the corresponding products.
Scheme 5A: Colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.20 (d, J = 8.4 Hz, 2H), 6.84 (d, J =
8.8 Hz, 1.77H), 5.16ꢀ5.11 (m, 2H), 3.78 (s, 3H), 3.60 (s, 2H), 3.52 (d, J = 5.0 Hz, 4H), 3.32 (s,
6H).
Scheme 5B: Colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.21ꢀ7.20 (m, 2H), 6.86ꢀ6.84 (m,
0.46H), 5.16ꢀ5.11 (m, 2H), 3.78 (s, 3H), 3.60 (s, 2H), 3.52 (d, J = 9.2 Hz, 4H), 3.33 (s, 6H).
General procedure for synthesis of 3q.
A mixture of 1q (0.2 mmol, 1.0 equiv), 2a (0.3 mmol, 1.5 equiv), Pd(OAc)2 (4.4 mg, 0.1 equiv),
Ag2CO3 (547.6 mg, 2.0 equiv), 1,10ꢀphenanthroline (3.6 mg, 0.1 equiv), adamantane carboxylic
acid (3.6 mg, 0.1 equiv) and HFIP (0.5 mL) in a 15 mL glass vial (sealed with PTFE cap) was
o
heated at 100 C for 24 hours. The reaction mixture was cooled to rt, and concentrated in vacuo.
The resulting residue was purified by column chromatography on silica gel to give the
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corresponding product and the isolated yield is 77% yield. The regioselective is 2:3. When the
temperature of this reaction is 60 oC, the isolated yield is 71% yield. The ortho/others is 3:2.
General procedure for ortho olefination of ethyl 2ꢀphenylacetate
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A mixture of ethyl 2ꢀphenylacetate (0.2 mmol, 1.0 equiv), 2a (0.3 mmol, 1.5 equiv), Pd(OAc)2
(4.4 mg, 0.1 equiv), Ag2CO3 (547.6 mg, 2.0 equiv), 1,10ꢀphenanthroline (3.6 mg, 0.1 equiv),
adamantane carboxylic acid (3.6 mg, 0.1 equiv) and HFIP (0.5 mL) in a 15 mL glass vial (sealed
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with PTFE cap) was heated at 100 C for 24 hours. The reaction mixture was cooled to rt, and
concentrated in vacuo. The resulting residue was purified by column chromatography on silica gel
to give the corresponding product and the isolated yield is 62%. The ortho/others is 1:1.
General procedure for palladiumꢀcatalyzed oxidative olefination
A mixture of toluene (1.0 mmol, 5.0 equiv), 2a (0.2 mmol, 1.0 equiv), Pd(OAc)2 (4.4 mg, 0.1
equiv), Ag2CO3 (547.6 mg, 2.0 equiv), 1,10ꢀphenanthroline (3.6 mg, 0.1 equiv), adamantane
carboxylic acid (3.6 mg, 0.1 equiv) and HFIP (0.5 mL) in a 15 mL glass vial (sealed with PTFE
cap) was heated at 60 oC for 24 hours. The reaction mixture was cooled to rt, and concentrated in
vacuo. The resulting residue was purified by column chromatography on silica gel to give the
corresponding product and the isolated yield is 78%. The ortho/others is 1:1.
General procedure for the synthesis of 3a use HOAc as solvent.
A mixture of 1a (0.2 mmol, 1.0 equiv), 2a (0.3 mmol, 1.5 equiv), Pd(OAc)2 (4.4 mg, 0.1 equiv),
Ag2CO3 (547.6 mg, 2.0 equiv), 1,10ꢀphenanthroline (3.6 mg, 0.1 equiv), HOAc (0.5 mL) in a 15
mL glass vial (sealed with PTFE cap) was heated at 100 oC for 24 hours. The reaction mixture was
cooled to rt, and concentrated in vacuo. The resulting residue was purified by column
chromatography on silica gel to give the corresponding product and the isolated yield is 55%.
ASSOCIATED CONTENT
Supporting Information
1
Optimization of reaction conditions, and H and 13C NMR spectra for new compounds. This
material is available free of charge via the Internet at http://pubs.acs.org.
ACKNOWLEDGMENT
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We sincerely acknowledge the Natural Science Foundation of Jiangsu Province of China
(BK20130294), the Young National Natural Science Foundation of China (No. 21402133), and
PAPD for their financial support.
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ACS Paragon Plus Environment