Transition-Metal-Free Synthesis of Ynones via Decarboxylative Alkynylation of α-Keto Acids under Mild Conditions

Article abstract of DOI:10.1021/acs.joc.5b01387

A transition-metal-free synthetic method of various ynones via decarboxylative alkynylation of α-keto acids is described. The reaction is carried out under mild conditions and exhibits remarkable tolerance of functional groups. The mechanism of a radical

Full text of DOI:10.1021/acs.joc.5b01387

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Note
Transition-Metal-free Synthesis of Ynones via Decarboxylative
Alkynylation of #-Keto Acids under Mild Conditions
Peng-Fei Wang, Yi-Si Feng, Zhi-Fei Cheng, Qiu-Min Wu, Guang-
Yu Wang, Liang-Liang Liu, Jian-Jun Dai, Jun Xu, and Hua-Jian Xu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01387 • Publication Date (Web): 24 Aug 2015
Downloaded from http://pubs.acs.org on August 25, 2015
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TransitionꢀMetalꢀfree Synthesis of Ynones via Decarboxylative
Alkynylation of αꢀKeto Acids under Mild Conditions
PengꢀFei Wang,† YiꢀSi Feng,*†,‡ ZhiꢀFei Cheng,† QiuꢀMin Wu,† GuangꢀYu Wang,†
LiangꢀLiang Liu,† JianꢀJun Dai,§ Jun Xu,§ and HuaꢀJian Xu*‡,§
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†School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009,
P. R. China
‡Anhui Key Laboratory of Controllable Chemical Reaction & Material Chemical Engineering,
Hefei 230009, P. R. China
§School of Medical Engineering, Hefei University of Technology, Hefei 230009, P. R. China
ABSTRACT: A transitionꢀmetalꢀfree synthetic method of various ynones via decarboxylative
alkynylation of αꢀketo acids is described. The reaction is carried out under mild conditions and
exhibits remarkable tolerance of functional groups. The mechanism of a radical process is
proposed in the reaction.
Ynones are highly valuable and amusing compounds that are widely employed as
fascinating precursors of heterocyclic compounds in organic synthesis.1 Typical approaches for
the synthesis of ynones involve Sonogashira couplings reactions of terminal alkynes with acyl
chlorides utilizing Pd/Cu as catalysts2 or carbonylative couplings reactions between terminal
alkynes and aryl or alkyl halides,3 aryl triflates,4 aryl amines5 with CO insertion. Recently, other
methods have also emerged as new strategies for the synthesis of ynones. For example, Hashmi
et al reported a goldꢀcatalyzed dehydrogenative MeyerꢀSchusterꢀlike rearrangement to produce
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ynones (Scheme 1, eq 1).6 Huang et al reported a general synthesis of ynones from aldehydes via
oxidative C−C bond cleavage under aerobic conditions (Scheme 1, eq 2).7 More recently, direct
alkynylation of aldehydes to synthesize ynones via nucleophilic addition/Oppenauer oxidation
and CꢀH activation have also been reported.8 When our study work is accomplished, Chen et al
reported that dual hypervalent iodine(III) reagents and photoredox catalysis enabled
decarboxylative ynonylation (Scheme 1, eq 3).9 Almost meanwhile, Wang et al reported a
sunlightꢀdriven decarboxylative alkynylation of aꢀketo acids with bromoacetylenes by
hypervalent iodine reagent catalysis (Scheme 1, eq 4).10 Although considerable efforts and
significant progress have been made to prepare ynones, most synthetic methods have some
shortcomings, such as the usage of toxic CO, harsh reaction conditions, limited substrate scope
and expensive catalysts. Therefore, further development of preparing ynones is of great demand
to enable mild reaction conditions as well as available raw materials. In order to achieve this goal,
it is greatly important to explore new approaches for the efficient synthesis of ynones.
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Transitionꢀmetalꢀcatalyzed decarboxylative crossꢀcoupling reactions of carboxylic acids
represent one of most important methods for the construction of CꢀC and Cꢀheteroatom
bonds.11ꢀ16 These reactions don’t require expensive organometallic reagents and produce nontoxic
CO2. In 2002, Myers first reported a palladiumꢀcatalyzed Heckꢀtype olefination of arene
carboxylates,11 subsequently considerable studies on the decarboxylative coupling reactions are
conducted by Forgione,12 Goossen,13 Liu14 and others.15ꢀ16 These reactions reveal that
decarboxylative couplings provide an alternative method for catalytic synthesis purpose.
Although many significant contributions are achieved in this field, decarboxylation of αꢀketo
acids receives relatively less attention. Decarboxylation of aꢀketo acids can afford acyl donors
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which it is crucial for the preparation of carbonyl compounds. We are interested in developing
new strategies to prepare ynones from αꢀketo acids under mild conditions. In particular, the
reactions that are conducted under transitionꢀmetalꢀfree condition are highly desirable to enable
potential application because of the significance of ynones. Herein, we reported a general and
efficient synthesis of ynones via K2S2O8ꢀpromoted decarboxylative alkynylation of αꢀketo acids
under mild conditions (Scheme 1 eq 5).17
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Scheme 1. The Synthetic methods of Ynones.
Previous work:
O
O
R2
O
PhI(OAc)2
Ph3PAuCl
AgNTf2
(1)
R1
R1
R2
R'
I
O
O
O
O
O
AuCl3
(2)
(3)
H
R
R
pyrrolidine, O2
R
R'
R'
R'
I
O
O
[Ru(bpy)3](PF6)2
blue LED, BI-OAc
OH
OH
O
R
R
O
O
O
sunlight
BI-OH
(4)
R'
Br
R
O
R'
This work:
R'
I
O
O
O
K2S2O8
OH
(5)
O
R
R
O
R'
We initiated optimization of the reaction conditions by selecting benzoylformic acid (1a) with
1ꢀ[(triisopropylsilyl)ethynyl]ꢀ1,2ꢀbenziodoxolꢀ3(1H)ꢀone (2a) as model substrates (Table 1). With
AgNO3 (20 mol %) as a catalyst and K2S2O8 (3 equiv) as an oxidant, it was delighted to find that
CH3CN was used as a solvent to give the desired product 3a in 12% yield at 50 oC under an argon
atmosphere (entry 1). Next, other solvents such as H2O, acetone/H2O (V:V = 1:1), CH2Cl2/H2O
(V:V = 1:1) and CH3CN/H2O (V:V = 1:1) were examined (entries 2ꢀ5). It was found that
CH3CN/H2O was the optimal medium for the transformation, which brought about an obviously
increasing yield of 88%. Then the use of other silver salts such as AgBF4, Ag2CO3, Ag2SO4 also
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showed the similar yields (entries 6ꢀ8). Furthermore, the use of Na2S2O8 and (NH4)2S2O8 as
oxidants led to the reduction of yield (entries 9ꢀ10). Reducing or increasing the reaction
temperature didn’t improve the yield of 3a (entries 11ꢀ13). The control experiment proved that
K2S2O8 was essential, and the reaction still could be conducted to give the desired product 3a in
high yield in the absence of AgNO3 (entries 14ꢀ15). Finally, by changing the amount of K2S2O8,
the yield of 3a was further improved to 92% (entries 16ꢀ19).
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Table 1. Optimization of the Reaction Conditionsa
entry
1
catalyst
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
AgBF4
Ag2CO3
Ag2SO4
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
ꢀ
oxidant (equiv)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
Na2S2O8 (3)
solvent
temp (oC) yield (%)b
CH3CN
50
50
12
trace
64
trace
88
87
85
84
79
77
28
70
82
ꢀ
2
H2O
3
acetone/H2O
CH2Cl2/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
50
4
50
5
50
6
50
7
50
8
50
9
50
10
11
12
13
14
15
16
17
18
19
(NH4)2S2O8 (3) CH3CN/H2O
50
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
ꢀ
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
CH3CN/H2O
rt(24)
40
60
50
K2S2O8 (3)
K2S2O8 (0.2)
K2S2O8 (0.4)
K2S2O8 (0.6)
K2S2O8 (0.8)
50
89
58
87
92
91
ꢀ
50
ꢀ
50
ꢀ
50
ꢀ
50
aReaction conditions: 1a (0.2 mmol), 2a (0.3 mmol, 1.5 equiv), K2S2O8 (1 equiv = 0.2 mmol), silver salt catalyst
(20 mol %), solvent (2 mL), 12 h under an argon atmosphere. bIsolated yields based on 1a. TIPS = triisopropylsilyl
Scheme 2. Scope of aꢀKeto Acidsa,b
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aReaction conditions: 1 (0.2 mmol), 2a (0.3 mmol, 1.5 equiv), K2S2O8 (0.12 mmol, 0.6 equiv), CH3CN/H2O (V:V =
o
b
c
1:1, 2 mL), 50 C for 12 h under an argon atmosphere. Isolated yields based on 1. The reaction was carried out
for 24 h.
With the optimal conditions in hand, we explored the scope of αꢀketo acids to examine the
compatibility of the present reaction (Scheme 2). It was found that various αꢀketo acids could
smoothly perform decarboxylative alkynylation to generate the desired ynones products in modest
to high yields. Both electronꢀdonating substituents such as methy (3b, 3k, 3p, 3u), ethyl (3e),
methoxyl (3c, 3l, 3q, 3v), and electronꢀwithdrawing groups such as trifluoromethyl (3j) could be
well tolerated in current reaction system. It is interesting to note that the reaction could tolerate an
unprotected OH group (3o), and the corresponding product could further perform cyclization to
led to the formation of chromone.8b Additionally, the halide groups, such as F (3f, 3m, 3r), Cl (3g,
3n, 3s), Br (3h, 3t), I (3i) were also well compatible with the reaction, enabling possibly further
functionalization at these positions. The αꢀketo acids bearing ortho- and meta-substituents could
work well to give the corresponding ynones of 29ꢀ87% yields (3kꢀt). The reactions of
disubstituted αꢀketo acids gave the desired products in 68ꢀ82% yields under the above conditions
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(3uꢀy). Furthermore, the reaction could also tolerate heterocyclic αꢀketo acids such as thiophene,
benzo[b]thiophene and indole, giving the desired products in low yields of 31ꢀ36% (3z, 3aaꢀab).
However, no product was detected when 2ꢀ(furanꢀ2ꢀyl)ꢀ2ꢀoxoacetic acid was employed as a
heterocyclic substrate (3ac). On the other hand, when aliphatic αꢀketo acids were employed for the
transformation, the corresponding products were obtained in 48ꢀ72% yields (3adꢀag).
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Next, we further explored the scope of various hypervalent iodine alkynyl reagents (Scheme 3).
Alkyne bearing alkylꢀsubstituent such as linear hexyl group could well react with benzoylformic
acid 1a to give the desired products in 52% yield (4a). Substrates with bulky silyl groups
t
including SiEt3, SiMe2 Bu, SitBuPh2 groups could be also well applicable for the reaction (4bꢀd).
Furthermore, various arylꢀsubstituent alkynes, bearing electronꢀrich methyl, methoxyl, phenyl,
diphenyl and electronꢀdeficient chloride, nitrile, ketone, aldehyde, could successfully convert to
the corresponding ynones in 25ꢀ81% yields (4eꢀl).
Scheme 3. Scope of Alkynyl Reagentsa, b
aReaction conditions: 1a (0.2 mmol), 2 (0.3 mmol, 1.5 equiv), K2S2O8 (0.12 mmol, 0.6 equiv), CH3CN/H2O (V:V
= 1:1, 2 mL), 50 oC for 12 h under an argon atmosphere. bIsolated yields based on 1a.
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To elucidate the plausible mechanism of reaction, the following experiment was conducted
(Scheme 4). Under the optimal conditions, when a radicalꢀtrapping reagent TEMPO
(2,2,6,6ꢀtetramethylꢀ1ꢀoxylpiperidine) was added to the reaction, no product was detected. The
result suggested that the reaction may proceed by a radical pathway.
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Scheme 4. Investigation of the Mechanism
According to the above experimental result and the previous studies,18 we proposed a possible
reaction mechanism shown in scheme 5. Firstly, peroxydisulfate ion, S2O82ꢀ performs homolysis to
give sulfate ion radical, which reacts with αꢀketo acids 1 to produce carboxyl radicals. Carboxyl
radical undergoes fast decarboxylation to generate acyl radical, and then attacks the triple bonds of
hypervalent iodine alkynyl reagents 2 to achieve the radical intermediate I. Subsequently, I occurs
βꢀelimination to give the desired products and benziodoxolonyl radical II. Finally, 2ꢀiodobenzoic
acid is afforded via reductionꢀprotonation of benziodoxolonyl radical II.
Scheme 5. Proposed Reaction Mechanism
In conclusion, we developed a new efficient reaction system for decarboxylative alkynylation of
αꢀketo acids using K2S2O8 as an oxidant. The present reaction could tolerate many important
functional groups and be conducted under very mild conditions. Furthermore, the reaction
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provided a general and efficient method for the synthesis of ynones without transitionꢀmetal
catalysts.
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Experimental section
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General Information and Materials
All the reactions were conducted in ovenꢀdried Schlenk tubes under an argon atmosphere. All
solvents were obtained from commercial suppliers and used without further purification. αꢀKeto
Acids were obtained from commercial suppliers or prepared according to the literature reported
procedures.19 Hypervalent iodine alkynyl reagents were prepared according to the literature
reported procedure.20 1H NMR, 13C NMR, 19F NMR spectra were recorded on a 600 MHz
1
spectrometer in CDCl3. Data for H NMR are reported as follows: chemical shift (δppm),
multiplicity, integration, and coupling constant (Hz). Data for 13C NMR are reported in terms of
chemical shift (δppm), multiplicity, and coupling constant (Hz). Data for 19F NMR are reported in
chemical shift and multiplicity. Highꢀresolution mass spectra were obtained by ESI on a TOF mass
analyzer.
Typical procedure for the synthesis of ynones via decarboxylative alkynylation of αꢀketo
acids
A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with benzoylformic acid
1a (0.2 mmol), 1ꢀ[(triisopropylsilyl)ethynyl]ꢀ1,2ꢀbenziodoxolꢀ3(1H)ꢀone 2a (1.5 equiv), and
K2S2O8 (0.6 equiv). The tube was evacuated and backfilled with argon (this operation was
repeated three times). CH3CN (1 mL) and H2O (1 mL) were added by syringe under a flow of
argon. The tube was sealed and the mixture was allowed to stir at 50 oC for 12 h. After completion
of the reaction, the mixture was cooled to room temperature. Then the mixture was diluted with
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EtOAc, and washed with water. The organic phase was separated and the aqueous phase was
extracted with EtOAc in three times. The combined organic phase was dried over anhydrous
MgSO4 and the solvent was removed under vacuo. The residue was purified by column
chromatography on silica gel to give the desired product 3a.
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Characterization data for the products
1ꢀphenylꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3a):17 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (52.8 mg,
92% yield); 1H NMR (600 MHz, CDCl3) δ 8.19 – 8.15 (m, 2H), 7.60 (t, J = 6.8 Hz, 1H), 7.48 (t, J
= 7.8 Hz, 2H), 1.25 – 1.14 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 177.5, 136.8, 134.0, 129.5,
128.6, 103.1, 98.0, 18.6, 11.1.
1ꢀ(pꢀtolyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3b):17 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (52.3 mg,
87% yield); 1H NMR (600 MHz, CDCl3) δ 8.06 (d, J = 7.8 Hz, 2H), 7.27 (d, J = 7.9 Hz, 2H), 2.42
(s, 3H), 1.23 – 1.05 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 177.2, 145.1, 134.5, 129.7, 129.3,
103.2, 97.3, 21.8, 18.6, 11.1.
1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3c):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a light yellow oil
(55.8 mg, 88% yield); 1H NMR (600 MHz, CDCl3) δ 8.13 (d, J = 8.6 Hz, 2H), 6.94 (d, J = 8.6 Hz,
2H), 3.87 (s, 3H), 1.22 – 1.08 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 176.2, 164.4, 131.9, 130.2,
113.8, 103.2, 96.8, 55.6, 18.6, 11.1.
1ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3d): The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil
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(66.1 mg, 91% yield); 1H NMR (600 MHz, CDCl3) δ 8.26 – 8.21 (m, 2H), 7.71 (d, J = 8.1 Hz, 2H),
7.64 (d, J = 7.4 Hz, 2H), 7.47 (t, J = 7.5 Hz, 2H), 7.40 (t, J = 7.3 Hz, 1H), 1.26 – 1.11 (m, 21H).
13C NMR (151 MHz, CDCl3) δ 177.1, 146.7, 139.7, 135.7, 130.1, 129.0, 128.4, 127.3, 127.2,
103.2, 98.0, 18.6, 11.2. HRMS calcd for C24H31OSi [M+H]+ 363.2144; found: 363.2140.
1ꢀ(4ꢀethylphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3e): The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (56.7
mg, 90% yield); 1H NMR (600 MHz, CDCl3) δ 8.09 (d, J = 8.1 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H),
2.71 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H), 1.23 – 1.08 (m, 21H). 13C NMR (151 MHz,
CDCl3) δ 177.2, 151.3, 134.7, 129.8, 128.1, 103.2, 97.3, 29.1, 18.6, 15.1, 11.1. HRMS calcd for
C20H31OSi [M+H]+ 315.2144; found: 315. 2142.
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1ꢀ(4ꢀfluorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3f):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (53.6
mg, 88% yield); 1H NMR (600 MHz, CDCl3) δ 8.18 (dd, J = 8.3, 5.7 Hz, 2H), 7.15 (t, J = 8.5 Hz,
2H), 1.25 – 1.01 (m, 21H).13C NMR (151 MHz, CDCl3) δ 175.9, 166.4 (d, J = 256.5 Hz), 133.3 (d,
J = 2.8 Hz), 132.2 (dd, J = 9.6, 3.3 Hz), 115.8 (d, J = 22.2 Hz), 102.7, 98.4, 18.6, 11.1. 19F NMR
(564 MHz, CDCl3) δ ꢀ103.27 – ꢀ103.39 (m).
1ꢀ(4ꢀchlorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3g):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (53.3
mg, 83% yield); 1H NMR (600 MHz, CDCl3) δ 8.09 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H),
1.25 – 1.01 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 176.1, 140.7, 135.2, 130.8, 129.0, 102.7,
98.8, 18.6, 11.1.
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1ꢀ(4ꢀbromophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3h):17The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (56.3
mg, 77% yield); 1H NMR (600 MHz, CDCl3) δ 8.01 (d, J = 8.2 Hz, 2H), 7.63 (d, J = 8.2 Hz, 2H),
1.25 – 1.01 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 176.3, 135.6, 131.9, 130.9, 129.5, 102.6,
98.9, 18.6, 11.1.
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1ꢀ(4ꢀiodophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3i):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (60.9
mg, 74% yield); 1H NMR (600 MHz, CDCl3) δ 7.86 (s, 4H), 1.21 – 1.08 (m, 21H). 13C NMR (151
MHz, CDCl3) δ 176.7, 138.0, 136.1, 130.7, 102.6, 102.5, 98.9, 18.6, 11.1.
1ꢀ(4ꢀ(trifluoromethyl)phenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3j):17 The product was
isolated by column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light
yellow oil (26.2 mg, 37% yield); 1H NMR (600 MHz, CDCl3) δ 8.27 (d, J = 8.1 Hz, 2H), 7.76 (d,
J = 8.2 Hz, 2H), 1.25 – 1.08 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 176.2, 139.2, 135.2 (d, J =
32.8 Hz), 129.8 (d, J = 2.4 Hz), 125.7 (q, J = 3.6 Hz), 123.5 (d, J = 272.8 Hz), 102.5, 99.9, 18.6,
11.1. 19F NMR (564 MHz, CDCl3) δ ꢀ63.22 (s).
1ꢀ(oꢀtolyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3k):17 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (48.1 mg,
80% yield); 1H NMR (600 MHz, CDCl3) δ 8.28 (d, J = 7.8 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.32
(t, J = 7.6 Hz, 1H), 7.23 (s, 1H), 2.63 (s, 3H), 1.22 – 1.05 (m, 21H). 13C NMR (151 MHz, CDCl3)
δ 179.2, 140.6, 135.4, 133.4, 132.9, 132.1, 125.8, 104.5, 96.3, 22.0, 18.6, 11.1.
1ꢀ(2ꢀmethoxyphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3l):21 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a colorless oil
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(55.1mg, 87% yield); 1H NMR (600 MHz, CDCl3) δ 8.02 (d, J = 7.7 Hz, 1H), 7.50 (t, J = 7.8 Hz,
1H), 7.02 – 6.95 (m, 2H), 3.89 (s, 3H), 1.20 – 1.04 (m, 21H). 13C NMR (151 MHz, CDCl3) δ
176.4, 159.7, 134.8, 132.9, 126.7, 120.1, 112.0, 105.1, 96.0, 55.7, 18.5, 11.1.
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1ꢀ(2ꢀfluorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3m):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (35.9
mg, 59% yield); 1H NMR (600 MHz, CDCl3) δ 8.06 (dd, J = 10.8, 4.3 Hz, 1H), 7.55 (dd, J = 13.1,
7.2 Hz, 1H), 7.23 (d, J = 7.4 Hz, 1H), 7.14 (dd, J = 10.4, 8.8 Hz, 1H), 1.23 – 1.07 (m, 21H). 13
NMR (151 MHz, CDCl3) δ 173.8, 162.1 (d, J = 262.5 Hz), 135.5 (d, J = 9.2 Hz), 132.0, 125.5 (d, J
C
= 7.8 Hz), 124.1 (d, J = 4.0 Hz), 117.1 (d, J = 21.8 Hz), 104.2, 98.2 (d, J = 3.0 Hz), 18.5, 11.1. 19
NMR (564 MHz, CDCl3) δ ꢀ110.86 – ꢀ111.15 (m).
F
1ꢀ(2ꢀchlorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3n):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (44.9
mg, 70% yield); 1H NMR (600 MHz, CDCl3) δ 8.06 (t, J = 6.7 Hz, 1H), 7.45 (d, J = 4.0 Hz, 2H),
7.36 (dt, J = 8.3, 4.3 Hz, 1H), 1.21 – 1.07 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 176.2, 135.5,
133.6, 133.3, 132.8, 131.5, 126.7, 104.0, 99.1, 18.5, 11.1.
1ꢀ(2ꢀhydroxyphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3o):8b The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil
(17.6 mg, 29% yield); 1H NMR (600 MHz, CDCl3) δ 11.67 (s, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.50
(t, J = 7.8 Hz, 1H), 6.96 (dd, J = 13.8, 7.8 Hz, 2H), 1.26 – 1.07 (m, 21H). 13C NMR (151 MHz,
CDCl3) δ 181.7, 162.9, 137.1, 133.0, 120.7, 119.4, 118.1, 101.6, 101.5, 18.6, 11.1.
1ꢀ(mꢀtolyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3p): The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (38.5 mg,
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64% yield); 1H NMR (600 MHz, CDCl3) δ 8.00 – 7.96 (m, 2H), 7.41 (d, J = 7.5 Hz, 1H), 7.36 (t, J
= 7.6 Hz, 1H), 2.41 (s, 3H), 1.24 – 1.09 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 177.7, 138.4,
136.8, 134.8, 130.0, 128.5, 126.9, 103.2, 97.7, 21.2, 18.6, 11.1. HRMS calcd for C19H29OSi
[M+H]+ 301.1988; found:301.1985.
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1ꢀ(3ꢀmethoxyphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3q):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil
(34.8 mg, 55% yield); 1H NMR (600 MHz, CDCl3) δ 7.79 (d, J = 7.5 Hz, 1H), 7.66 (s, 1H), 7.38 (t,
J = 7.9 Hz, 1H), 7.15 (dd, J = 8.2, 2.5 Hz, 1H), 3.85 (s, 3H), 1.23 – 1.09 (m, 21H). 13C NMR (151
MHz, CDCl3) δ 177.2, 159.7, 138.1, 129.6, 122.6, 121.3, 112.7, 103.1, 97.8, 55.4, 18.6, 11.1.
1ꢀ(3ꢀfluorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3r): The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (38.4
mg, 63% yield); 1H NMR (600 MHz, CDCl3) δ 7.96 (d, J = 7.7 Hz, 1H), 7.82 (d, J = 9.2 Hz, 1H),
7.46 (td, J = 7.9, 5.6 Hz, 1H), 7.30 (td, J = 8.2, 2.4 Hz, 1H), 1.23 – 1.08 (m, 21H). 13C NMR (151
MHz, CDCl3) δ 176.1 (d, J = 2.6 Hz), 162.7 (d, J = 248.4 Hz), 138.8 (d, J = 6.6 Hz), 130.3 (d, J =
7.6 Hz), 125.4 (d, J = 2.9 Hz), 121.1 (d, J = 21.6 Hz), 115.9 (d, J = 22.8 Hz), 102.6, 99.0, 18.5,
11.1. 19F NMR (564 MHz, CDCl3) δ ꢀ111.75 – ꢀ111.85 (m). HRMS calcd for C18H26FOSi
305.1737; found: 305.1739.
1ꢀ(3ꢀchlorophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3s):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (48.1
mg, 75% yield); 1H NMR (600 MHz, CDCl3) δ 8.14 (s, 1H), 8.04 (d, J = 7.6 Hz, 1H), 7.57 (dd, J
= 7.9, 0.7 Hz, 1H), 7.42 (t, J = 7.9 Hz, 1H), 1.25 – 1.09 (m, 21H). 13C NMR (151 MHz, CDCl3) δ
176.0, 138.2, 134.9, 133.9, 129.9, 129.6, 127.5, 102.5, 99.3, 18.5, 11.1.
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1ꢀ(3ꢀbromophenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3t):17The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a yellow oil (36.5
mg, 50% yield); 1H NMR (600 MHz, CDCl3) δ 8.31 (s, 1H), 8.08 (d, J = 7.7 Hz, 1H), 7.72 (d, J =
7.9 Hz, 1H), 7.36 (t, J = 7.9 Hz, 1H), 1.23 – 1.09 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 175.9,
138.4, 136.8, 132.6, 130.2, 127.9, 122.8, 102.5, 99.5, 18.6, 11.1.
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1ꢀ(2,4ꢀdimethylphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3u):17 The product was isolated
by column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow
oil (44.7 mg, 71% yield); 1H NMR (600 MHz, CDCl3) δ 8.19 (d, J = 8.0 Hz, 1H), 7.12 (d, J = 7.9
Hz, 1H), 7.05 (s, 1H), 2.60 (s, 3H), 2.36 (s, 3H), 1.22 – 1.05 (m, 21H). 13C NMR (151 MHz,
CDCl3) δ 178.8, 143.8, 140.8, 133.9, 132.94, 132.93, 126.5, 104.6, 95.5, 22.0, 21.5, 18.6, 11.1.
1ꢀ(3,4ꢀdimethoxyphenyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3v): The product was isolated
by column chromatography on silica gel (ethyl acetate: petroleum ether = 1:30) as a colorless oil
(51.3 mg, 74% yield); 1H NMR (600 MHz, CDCl3) δ 7.87 (dd, J = 8.3, 1.7 Hz, 1H), 7.64 (d, J =
1.5 Hz, 1H), 6.93 (d, J = 8.4 Hz, 1H), 3.95 (s, 3H), 3.92 (s, 3H), 1.21 – 1.08 (m, 21H). 13C NMR
(151 MHz, CDCl3) δ 176.1, 154.2, 148.9, 130.3, 125.2, 110.6, 110.2, 103.1, 96.8, 56.1, 56.0, 18.6,
11.1. HRMS calcd for C20H31O3Si [M+H]+ 347.2042; found:347.2041.
1ꢀ(naphthalenꢀ2ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3w):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a yellow oil (50.5
mg, 75% yield); 1H NMR (600 MHz, CDCl3) δ 8.79 (s, 1H), 8.15 (dd, J = 8.6, 1.3 Hz, 1H), 7.95
(d, J = 8.1 Hz, 1H), 7.89 (t, J = 7.8 Hz, 2H), 7.62 (t, J = 7.5 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 1.28
– 1.14 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 177.4, 136.1, 134.4, 133.0, 132.4, 129.8, 129.0,
128.4, 127.9, 126.9, 123.8, 103.2, 97.9, 18.6, 11.2.
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1ꢀ(naphthalenꢀ1ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3x):17 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a yellow oil (45.8
mg, 68% yield); 1H NMR (600 MHz, CDCl3) δ 9.20 (d, J = 8.7 Hz, 1H), 8.62 (d, J = 7.3 Hz, 1H),
8.07 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.67 – 7.63 (m, 1H), 7.56 (td, J = 7.4, 4.1 Hz,
2H), 1.24 – 1.11 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 179.2, 135.0, 134.6, 133.8, 132.8,
130.7, 128.9, 128.5, 126.7, 126.0, 124.4, 104.6, 96.2, 18.6, 11.2.
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1ꢀ(benzo[d][1,3]dioxolꢀ5ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3y): The product was
isolated by column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a
colorless oil (54.2 mg, 82% yield); 1H NMR (600 MHz, CDCl3) δ 7.83 (dd, J = 8.1, 1.4 Hz, 1H),
7.56 (d, J = 1.3 Hz, 1H), 6.87 (d, J = 8.2 Hz, 1H), 6.06 (s, 2H), 1.25 – 1.03 (m, 21H). 13C NMR
(151 MHz, CDCl3) δ 175.6, 152.8, 148.2, 132.0, 127.1, 108.3, 108.0, 103.0, 102.1, 97.1, 18.6,
11.1. HRMS calcd for C19H27O3Si [M+H]+ 331.1729; found: 331.1728.
1ꢀ(thiophenꢀ3ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3z):8d The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a colorless oil
(18.2 mg, 31% yield); 1H NMR (600 MHz, CDCl3) δ 8.28 – 8.25 (m, 1H), 7.61 (t, J = 4.5 Hz, 1H),
7.32 (dd, J = 4.9, 3.1 Hz, 1H), 1.21 – 1.08 (m, 21H). 13C NMR (151 MHz, CDCl3) δ 170.9, 143.0,
135.4, 126.77, 126.75, 103.6, 95.9, 18.6, 11.1.
1ꢀ(benzo[b]thiophenꢀ2ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3aa):8d The product was
isolated by column chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a
yellow oil (24.7 mg, 36% yield); 1H NMR (600 MHz, CDCl3) δ 8.18 (s, 1H), 7.92 (d, J = 8.0 Hz,
1H), 7.86 (d, J = 8.2 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 1H), 1.24 – 1.11 (m,
21H). 13C NMR (151 MHz, CDCl3) δ 170.7, 144.3, 143.1, 138.7, 132.6, 128.0, 126.4, 125.2, 123.1,
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1ꢀ(1Hꢀindolꢀ3ꢀyl)ꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3ab): The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:5) as a light yellow solid
(21.5 mg, 33% yield);1H NMR (600 MHz, CDCl3) δ 9.62 (s, 1H), 8.41 – 8.38 (m, 1H), 8.11 (d, J
= 2.9 Hz, 1H), 7.48 – 7.45 (m, 1H), 7.29 (m, 2H), 1.18 – 1.07 (m, 21H). 13C NMR (151 MHz,
CDCl3) δ 171.9, 136.8, 135.8, 125.0, 124.2, 123.1, 122.2, 119.8, 111.9, 104.2, 92.1, 18.6, 11.1.
HRMS calcd for C20H28NOSi [M+H]+ 326.1940; found: 326.1943.
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5ꢀphenylꢀ1ꢀ(triisopropylsilyl)pentꢀ1ꢀynꢀ3ꢀone (3ad):8d The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a colorless oil (43.4 mg,
69% yield); 1H NMR (600 MHz, CDCl3) δ 7.28 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.3 Hz, 3H), 3.01
(t, J = 7.7 Hz, 2H), 2.90 (t, J = 7.7 Hz, 2H), 1.15 – 1.02 (m, 21H). 13C NMR (151 MHz, CDCl3) δ
186.5, 140.2, 128.5, 128.3, 126.3, 104.0, 96.1, 47.2, 30.1, 18.5, 11.0.
4ꢀ(triisopropylsilyl)butꢀ3ꢀynꢀ2ꢀone (3ae):17The product was isolated by column chromatography
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on silica gel (ethyl acetate: petroleum ether = 1:100) as a colorless oil (21.5 mg, 48% yield); H
NMR (600 MHz, CDCl3) δ 2.34 (d, J = 4.6 Hz, 3H), 1.14 – 1.03 (m, 21H). 13C NMR (151 MHz,
CDCl3) δ 184.2, 104.7, 95.2, 32.8, 18.4, 11.0.
1ꢀ(triisopropylsilyl)pentꢀ1ꢀynꢀ3ꢀone (3af): The product was isolated by column chromatography
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on silica gel (ethyl acetate: petroleum ether = 1:100) as a colorless oil (24.8 mg, 52% yield); H
NMR (600 MHz, CDCl3) δ 2.58 (q, J = 7.4 Hz, 2H), 1.15 (dd, J = 9.8, 5.0 Hz, 3H), 1.14 – 1.03 (m,
21H). 13C NMR (151 MHz, CDCl3) δ 188.3, 104.0, 95.5, 38.9, 18.5, 11.0, 8.2. HRMS calcd for
C14H27OSi [M+H]+ 239.1831; found: 239.1829.
1ꢀcyclopropylꢀ3ꢀ(triisopropylsilyl)propꢀ2ꢀynꢀ1ꢀone (3ag):8d The product was isolated by
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(36.1 mg, 72% yield); H NMR (600 MHz, CDCl3) δ 2.02 (ddd, J = 12.6, 8.1, 4.6 Hz, 1H), 1.26
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(td, J = 7.3, 3.5 Hz, 2H), 1.14 – 1.00 (m, 23H). 13C NMR (151 MHz, CDCl3) δ 188.1, 101.9, 94.9,
24.6, 18.5, 11.0, 10.8.
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1ꢀphenylnonꢀ2ꢀynꢀ1ꢀone (4a):22 The product was isolated by column chromatography on silica
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gel (ethyl acetate: petroleum ether = 1:50) as a light yellow oil (22.3 mg, 52% yield); H NMR
(600 MHz, CDCl3) δ 8.13 (d, J = 7.7 Hz, 2H), 7.59 (t, J = 7.3 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H),
2.49 (t, J = 7.1 Hz, 2H), 1.70 – 1.64 (m, 2H), 1.47 (dt, J = 14.7, 7.3 Hz, 2H), 1.35 – 1.30 (m, 4H),
0.93 – 0.86 (m, 3H). 13C NMR (151 MHz, CDCl3) δ 178.3, 136.9, 133.8, 129.5, 128.5, 96.9, 79.7,
31.2, 28.6, 27.8, 22.5, 19.2, 14.0.
1ꢀphenylꢀ3ꢀ(triethylsilyl)propꢀ2ꢀynꢀ1ꢀone (4b):23 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil (24.1
mg, 49% yield); 1H NMR (600 MHz, CDCl3) δ 8.15 (d, J = 7.5 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H),
7.48 (t, J = 7.6 Hz, 2H), 1.07 (t, J = 7.9 Hz, 9H), 0.74 (q, J = 7.9 Hz, 6H). 13C NMR (151 MHz,
CDCl3) δ 177.6, 136.6, 134.1, 129.6, 128.6, 102.1, 98.8, 7.4, 4.0.
3ꢀ(tertꢀbutyldimethylsilyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4c):24 The product was isolated by
column chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a colorless oil
(35.2 mg, 72% yield); 1H NMR (600 MHz, CDCl3) δ 8.14 (d, J = 7.7 Hz, 2H), 7.60 (t, J = 7.3 Hz,
1H), 7.48 (t, J = 7.7 Hz, 2H), 1.02 (s, 9H), 0.25 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 177.6,
136.6, 134.1, 129.6, 128.6, 101.6, 99.4, 26.1, 16.7, ꢀ5.1.
3ꢀ(tertꢀbutyldiphenylsilyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4d): The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil (47.2
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mg, 64% yield); 1H NMR (600 MHz, CDCl3) δ 8.23 (d, J = 7.4 Hz, 2H), 7.83 (d, J = 6.8 Hz, 4H),
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7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.43 (dt, J = 22.6, 7.3 Hz, 6H), 1.19 (s, 9H). 13
C
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NMR (151 MHz, CDCl3) δ 177.3, 136.7, 135.6, 134.3, 131.5, 130.1, 129.6, 128.7, 128.0, 104.4,
96.0, 27.1, 18.9. HRMS calcd for C25H25OSi [M+H]+ 369.1675; found:369.1673.
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1,3ꢀdiphenylpropꢀ2ꢀynꢀ1ꢀone (4e):24 The product was isolated by column chromatography on
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silica gel (ethyl acetate: petroleum ether = 1:100) as a light yellow oil (21.1 mg, 51% yield); H
NMR (600 MHz, CDCl3) δ 8.22 (d, J = 7.8 Hz, 2H), 7.68 (d, J = 7.5 Hz, 2H), 7.63 (t, J = 7.4 Hz,
1H), 7.50 (dt, J = 20.2, 7.6 Hz, 3H), 7.42 (t, J = 7.6 Hz, 2H). 13C NMR (151 MHz, CDCl3) δ 178.0,
136.9, 134.1, 133.1, 130.8, 129.6, 128.7, 128.6, 120.1, 93.1, 86.9.
1ꢀphenylꢀ3ꢀ(pꢀtolyl)propꢀ2ꢀynꢀ1ꢀone (4f):10 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a white solid (35.7 mg,
81% yield); 1H NMR (600 MHz, CDCl3) δ 8.22 (d, J = 7.7 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.58
(d, J = 8.0 Hz, 2H), 7.51 (t, J = 7.7 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 2.40 (s, 3H). 13C NMR (151
MHz, CDCl3) δ 178.1, 141.5, 137.0, 134.0, 133.1, 129.53, 129.47, 128.6, 117.0, 93.8, 86.8, 21.8.
3ꢀ(3ꢀmethoxyphenyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4g):9 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a yellow oil (11.8 mg, 25%
yield);1H NMR (600 MHz, CDCl3) δ 8.21 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.52 (t, J =
7.7 Hz, 2H), 7.35 – 7.26 (m, 2H), 7.19 (s, 1H), 7.05 – 7.00 (m, 1H), 3.84 (s, 3H). 13C NMR (151
MHz, CDCl3) δ 178.0, 159.4, 136.8, 134.1, 129.8, 129.6, 128.6, 125.6, 121.0, 117.56, 117.55, 93.0,
86.5, 55.4.
3ꢀ(4ꢀchlorophenyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4h):9 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a light yellow solid (27.4
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mg, 57% yield); 1H NMR (600 MHz, CDCl3) δ 8.20 (d, J = 7.6 Hz, 2H), 7.62 (dd, J = 17.5, 7.9 Hz,
3H), 7.51 (t, J = 7.7 Hz, 2H), 7.40 (d, J = 8.2 Hz, 2H). 13C NMR (151 MHz, CDCl3) δ 177.8,
137.2, 136.7, 134.24, 134.22, 129.6, 129.2, 128.7, 118.6, 91.6, 87.6.
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2ꢀ(3ꢀoxoꢀ3ꢀphenylpropꢀ1ꢀynꢀ1ꢀyl)benzonitrile (4i):9 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:20) as a white solid (12.5 mg,
27% yield); 1H NMR (600 MHz, CDCl3) δ 8.33 (d, J = 7.9 Hz, 2H), 7.81 (d, J = 7.8 Hz, 1H), 7.76
(d, J = 7.7 Hz, 1H), 7.69 – 7.62 (m, 2H), 7.59 (t, J = 7.7 Hz, 1H), 7.54 (t, J = 7.6 Hz, 2H). 13C
NMR (151 MHz, CDCl3) δ 177.5, 136.3, 134.6, 134.4, 133.0, 132.7, 130.8, 129.9, 128.8, 124.1,
117.1, 116.3, 91.2, 86.9.
3ꢀ(4ꢀacetylphenyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4j):9 The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:20) as a light yellow solid (21.4
mg, 43% yield); 1H NMR (600 MHz, CDCl3) δ 8.20 (d, J = 7.3 Hz, 2H), 7.99 (d, J = 8.3 Hz, 2H),
7.76 (d, J = 8.3 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H), 2.63 (s, 3H). 13C NMR
(151 MHz, CDCl3) δ 197.1, 177.7, 138.0, 136.6, 134.4, 133.1, 129.6, 128.7, 128.4, 124.7, 91.1,
88.7, 26.7.
4ꢀ(3ꢀoxoꢀ3ꢀphenylpropꢀ1ꢀynꢀ1ꢀyl)benzaldehyde (4k):9The product was isolated by column
chromatography on silica gel (ethyl acetate: petroleum ether = 1:20) as a light yellow solid (21.6
mg, 46% yield); 1H NMR (600 MHz, CDCl3) δ 10.06 (s, 1H), 8.20 (d, J = 7.5 Hz, 2H), 7.93 (d, J
= 8.0 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H), 7.65 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H). 13C
NMR (151 MHz, CDCl3) δ 191.1, 177.6, 137.1, 136.5, 134.5, 133.4, 129.6, 128.7, 126.1, 90.7,
89.1.
3ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀ1ꢀphenylpropꢀ2ꢀynꢀ1ꢀone (4l):9 The product was isolated by column
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chromatography on silica gel (ethyl acetate: petroleum ether = 1:50) as a light yellow solid (23.2
mg, 41% yield); 1H NMR (600 MHz, CDCl3) δ 8.24 (d, J = 7.6 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H),
7.67 – 7.60 (m, 5H), 7.53 (t, J = 7.7 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 7.4 Hz, 1H). 13C
NMR (151 MHz, CDCl3) δ 178.0, 143.6, 139.8, 136.9, 134.1, 133.6, 129.6, 129.0, 128.6, 128.2,
127.3, 127.1, 118.8, 93.2, 87.6.
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AUTHOR INFORMATION
Corresponding Authors
Eꢀmail: hjxu@hfut.edu.cn; fengyisi2008@126.com
ACKNOWLEDGE
We gratefully acknowledge financial support from the National Natural Science Foundation of
China (Nos. 21472033, 21371044, 21272050) and the Program for New Century Excellent Talents
in University of the Chinese Ministry of Education (NCETꢀ11ꢀ0627).
ASSOCIATED CONTENT
Supporting Information
13
1H NMR， C NMR and 19F NMR spectra of the products. This material is available free of charge
via the Internet at http://pubs.acs.org/.
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