Copper-catalyzed decarboxylative coupling of alkynyl carboxylates with 1,1-dibromo-1-alkenes

Article abstract of DOI:10.1021/jo400616r

A copper-catalyzed decarboxylative coupling reaction of potassium alkynyl carboxylates with 1,1-dibromo-1-alkenes was developed for the synthesis of unsymmetrical 1,3-diyne and 1,3,5-triyne derivatives. Diverse aryl, alkenyl, alkynyl, and alkyl substituted 1,1-dibromo-1-alkenes can react smoothly with aryl and alkyl substituted propiolates to produce unsymmetrical 1,3-diynes and 1,3,5-triynes with high selectivity and good functional group compatibility.

Full text of DOI:10.1021/jo400616r

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Article
Cu-Catalyzed Decarboxylative Coupling of
Alkynyl Carboxylates with 1,1-Dibromo-1-alkenes
Zheng Huang, Rui Shang, Zi-Rong Zhang, Xiao-Dan Tan, Xiao Xiao, and Yao Fu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo400616r • Publication Date (Web): 11 Apr 2013
Downloaded from http://pubs.acs.org on April 13, 2013
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Copper-Catalyzed
Decarboxylative
Coupling
of
Alkynyl
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Carboxylates with 1,1-Dibromo-1-alkenes
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Zheng Huang, Rui Shang, ZiꢀRong Zhang, XiaoꢀDan Tan, Xiao Xiao and Yao Fu*
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Anhui Province Key Laboratory of Biomass Clean Energy, Collaborative Innovative Center of
Chemistry for Energy Materials, and Department of Chemistry, University of Science and
Technology of China, Hefei 230026, P. R. China
fuyao@ustc.edu.cn
ABSTRACT: A copperꢀcatalyzed decarboxylative coupling reaction of potassium alkynyl
carboxylates with 1,1ꢀdibromoꢀ1ꢀalkenes was developed for the synthesis of unsymmetrical
1,3ꢀdiyne and 1,3,5ꢀtriyne derivatives. Diverse aryl, alkenyl, alkynyl and alkyl substituted
1,1ꢀdibromoꢀ1ꢀalkenes can react smoothly with aryl and alkyl substituted propiolates to produce
unsymmetrical 1,3ꢀdiynes and 1,3,5ꢀtriynes with high selectivity and good functional group
compatibility.
1. Introduction
Due to their unique chemical and physical properties, conjugated 1,3ꢀdiynes and polyynes occur
widely in nature products,1 pharmaceutical intermediates,1 and functional materials.2 Therefore,
synthetic methods to construct 1,3ꢀdiynes and polyynes have drawn the attention of chemists for
decades.1a GlaserꢀHay coupling, which involves oxidative coupling of two terminal alkynes
promoted or catalyzed by copper salts, was the first successful method to construct 1,3ꢀdiynes
(Figure 1, a).3 But when considering the synthesis of unsymmetrical 1,3ꢀdiynes, the GlaserꢀHay
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coupling often suffers from low selectivity, giving a mixture of homo and cross coupled
products.1a,4 CadiotꢀChodkiewicz coupling5 and its modifications6 which can directly couple a
haloalkyne and an alkyne under copper catalysis are the major methods used for unsymmetrical
1,3ꢀdiyne synthesis nowadays (Figure 1, b).1a Although successful in many circumstances,
CadiotꢀChodkiewicz coupling is plagued with considerable amount of undesired homocouplings,
especially when the substituents attached to the haloalkynes and the terminal alkynes have similar
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4,
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electronic properties.1a,
Hiyama et al. also reported a copperꢀcatalyzed coupling of
alkynylsilanes and 1ꢀchloroalkynes to produce unsymmetrical 1,3ꢀdiynes (Figure 1, c).7 Recently,
guided by kinetic investigations, Lei et al. reported that a palladiumꢀ catalyticꢀsystem can improve
the crossꢀcoupling selectivity of the CadiotꢀChodkiewicz type reaction.8 However, from an
economic point of view, a highly selective copperꢀcatalyzed 1,3ꢀdiyne synthesis using readily
accessible reactants is more attractive.
Catalytic decarboxylative coupling has already been demonstrated to be powerful in catalytic CꢀC
bond formation.9 Due to their easy accessibility and stability, alkynyl carboxylic acids have been
used as alkynyl nucleophiles instead of alkyne and alkynyl organometallic reagents in
transitionꢀmetalꢀcatalyzed alkynylation reactions.10 And 1,1ꢀDibromoꢀ1ꢀalkenes which can be
easily accessed from aldehyde11, have been used as alkynyl electrophile in copper and palladium
catalyzed reactions.12 In this manuscript, we report a new copperꢀcatalyzed reaction to construct
1,3ꢀdiynes and 1,3,5ꢀtriynes via decarboxylative coupling of alkynyl carboxylates with
1,1ꢀdibromoꢀ1ꢀalkenes (Figure 1, d). This method is not only a new method for 1,3ꢀdiyne
synthesis which is complementary with the traditional GlaserꢀHay and CadiotꢀChodkiewicz
coupling,13 but also a new type of copperꢀcatalyzed14 decarboxylative alkynylation reaction.
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Figure 1. Copper catalyzed synthesis of 1,3ꢀdiyne.
2. Results and discussion
Our study began by examining the crossꢀcoupling of 1ꢀ(2,2ꢀdibromovinyl)ꢀ4ꢀmethoxybenzene
with potassium 3ꢀphenylpropiolate (Table 1). To our delight, after short optimization, the desired
product 1 was obtained in 76% yield when using CuI as catalyst, 1,10ꢀphenanthroline as ligand,
and cesium carbonate as base in diglyme solvent. However, we also observed 16% and 7% of the
two homocoupling byproducts (Table 1, Entry 1). We subsequently investigated the effect of
various ligands on the reaction’s yield and selectivity. Monodentate phosphine, bidentate
phosphine and NHCꢀtype ligand all gave inferior results (Entry 2ꢀ6). When neocuproine
(2,9ꢀdimethylꢀ1,10ꢀphenanthroline) was used, we were delighted to find that the product was
produced in 96% yield together with only 2% and 1% of the two homocoupling byproducts (Entry
7). Compared with the results obtained by using 1,10ꢀphenanthroline (Entry 1) and
bathophenanthroline (Entry 8), neocuproine was found through this observation that the two
methyl substituents on 2ꢀ and 9ꢀ positions of it play a key role to suppress the homocoupling side
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reactions. The use of less rigid bipyridine ligand resulted in a lower yield and poorer selectivity
(Entry 9). Both TMEDA and DMEDA ligands gave satisfactory yield, but the amount of
homocoupling was relatively higher than that with neocuproine (Entries 10 and 11).
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Table 1. Ligand Optimization.
Yield a
Entry
Ligand
1
2
3
1d
2
3
4
5
6
7
8
1,10-phen
76%
44%
29%
55%
52%
41%
96%
74%
74%
83%
88%
16%
24%
27%
24%
25%
11%
2%
19%
25%
6%
7%
10%
5%
11%
11%
3%
1%
9%
b
PPh3
dppp
dppf
S-Phos
IMesc
neocuproine
bathophen
dtbpy
9
10
11
10%
3%
3%
TMEDA
DMEDA
5%
a
Yield was detected by GC, average of two runs. b 20 mol% of PPh3 was used. c IMes was used as its
hydrochloride salt. d 6% of 1 was obtained by using K2CO3 (3.0 equiv.) as base.
After finding the optimal conditions, we examined the efficiency of this reaction on a gram scale
(Scheme 1). With the use of only 1% of the copperꢀcatalyst and the neocuproine ligand, we
obtained 1.24 g of 1 (89% yield) without any decrease of selectivity (2, 2 % and 3, 1 %).
Scheme 1. Gram scale synthesis with 1mol% catalyst loading.
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We next examined the scope of this reaction with respect to the 1,1ꢀdibromoꢀ1ꢀalkene coupling
partner (Table 2). The results in Table 2 show that substrates possessing both electron rich (2a and
2b) and electron deficient (2c-j) aryl substituents on the 2ꢀposition of 1,1ꢀdibromoꢀ1ꢀalkenes were
transformed well in this reaction. A number of useful functional groups including alkoxy (2a),
alkyl (2b), alkenyl (2j), fluoro (2c), chloro (2d), bromo (2e), tosylate (2f), trifluoromethyl (2g),
cyano (2h), nitro (2i) and ester (2j) are all well tolerated. The products containing arylꢀCl, arylꢀBr
and arylꢀOTs bond can easily be further transformed via Pd or Ni catalyzed crossꢀcoupling
reactions. It is worth to note that this reaction still gives a high yield and high selectivity even
when the electronic properties of the substitution on the alkynyl carboxylate and the
dibromoalkene are quite similar (2b, 91% yield, homocoupling <3%). 1,1ꢀDibromoꢀalkene
substrates containing hetero aromatic substituents such as furyl (2k), Bocꢀprotected indolyl (2l)
and pyridyl (2m) can all react in good yields of 60ꢀ74%. 1,1ꢀDibromoꢀ1ꢀalkene derived from
2ꢀnaphthaldehyde reacted well and the yield was 75% (2n). 1,3ꢀDiyne possessing carbazole
substituent can be synthesized using this method (2o).This type of molecules are often found
useful in the synthesis of electroluminescent devices.15 Pentafluoro 1,4ꢀdiphenylbutaꢀ1,3ꢀdiyne
which is of interest for superꢀmolecular chemistry16 can also be prepared using this method, but in
a
relatively low yield (2p, 23 %). Besides 2ꢀaryl substituent, 2ꢀalkenylꢀsubstituted
1,1ꢀdibromoꢀ1ꢀalkene was also converted smoothly. Cinnamaldehydeꢀderived
1,1ꢀdibromoꢀ1ꢀalkene reacted well with potassium 3ꢀphenylpropiolate to produce
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(E)ꢀhexaꢀ1ꢀenꢀ3,5ꢀdiyneꢀ1,6ꢀdiyldibenzene (2q). This example demonstrates that this reaction is
efficient for the construction of 1ꢀenꢀ3,5ꢀhexadiyne skeleton from the corresponding vinyl
aldehyde. In addition, 1ꢀalkylꢀ4ꢀarylꢀ1,3ꢀbutadiyne can be prepared by this method (2r).
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Table 2. Scope of 1,1ꢀDibromoalkenes. a
b
a Yields based on 1,1-dibromoalkenes. DMEDA (10 mol%) was used as ligand. c The reaction was
carried out at 80 oC.d [Cu(MeCN)4]PF6 (10 mol%) was used instead of CuI.
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The scope of the alkynyl carboxylate is described in Table 3. Aryl propiolates carrying both
electronꢀdonating (3a and 3b) and electronꢀwithdrawing groups (3c-f) are amenable substrates.
Potassium 3ꢀ(naphthalenꢀ2ꢀyl) propiolate can be coupled with 1ꢀ(2,2ꢀdibromovinyl)ꢀ4ꢀ
methoxybenzene in a moderate yield (3g). A number of functional groups on the aryl propiolates
including alkoxy (3a), alkyl (3b), chloro (3c), trifluoromethyl (3d), ester (3e) and nitro (3f) were
all tolerated well. Please note that although we only obtained moderate yields in these cases (3c,
3d, 3f, 3g), the selectivities for cross coupling were still excellent as in all of these cases we
observed only a small amount (<5%) of the homocoupling byproduct.
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To our delight, we found that alkyl substituted propiolates can be well coupled with 2ꢀaryl
substituted 1,1ꢀdibromoꢀ1ꢀalkenes to produce 1ꢀalkylꢀ4ꢀarylꢀ1,3ꢀbutadiynes. Potassium
octꢀ2ꢀynoate
4ꢀ(2,2ꢀdibromovinyl)benzonitrile to give the corresponding 1,3ꢀdiynes in 96% and 80% yields
respectively (3h and 3i). Potassium butꢀ2ꢀynoate reacted with
reacted
with
both
1ꢀ(2,2ꢀdibromovinyl)ꢀ4ꢀmethoxybenzene
and
(2,2ꢀdibromovinyl)ꢀ4ꢀmethoxybenzene to give 1ꢀmethoxyꢀ4ꢀ(pentaꢀ1,3ꢀdiynꢀ1ꢀyl)benzene (3j) in
a high yield. In this case, potassium butꢀ2ꢀynoate is a white, crystalized solid, but propꢀ1ꢀyne is a
o
troublesome gas in laboratory operation (b.p. ꢀ23.2 C). This case demonstrates the advantage of
the decarboxylative coupling methodology of alkynyl carboxylate. Alkyl substituted propiolates
also couple well with 2ꢀalkylꢀ1,1ꢀdibromoꢀ1ꢀalkene to afford 1,4ꢀdialkylꢀ1,3ꢀbutadiyne.
Potassium octꢀ2ꢀynoate reacts with (2,2ꢀdibromovinyl)cyclohexane and 1,1ꢀdibromooctꢀ1ꢀene to
give the corresponding 1,4ꢀdialkylꢀ1,3ꢀbutadiynes in 78% and 70% yield respectively, combined
with only a trace amount of the homocoupling byproduct (3k and 3l). Please note that, in
GlaserꢀHay and CadiotꢀChodkiewicz couplings, these 1,4ꢀdialkylꢀ1,3ꢀbutadiynes carrying
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substituents with similar structural and electronic properties on 1ꢀ and 4ꢀ positions are sometimes
plagued with a significant amount of homocoupling diynes which are difficult to separate from
each other.1a, 17
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Table 3. Scope of Potassium Alkynyl Carboxylates.a
NC
OMe
F
3a
75%
3b
74%
Me
NC
Me
MeO
Me
3d
49%c
3c
54%
Cl
CF3
NO2
3e
61%b, d
COOEt
3f
51%b, d
MeO
NC
MeO
3h
96%b
3g
47%c
MeO
Me
3i
80%b
3j
91%b, e
3k
78%f
3l
70%f
a Yields based on 1,1-dibromoalkenes. b CuI/neocuproine (20 mol%) was used. t-BuOLi (3 equiv.) was
c
used instead of Cs2CO3. d1h reaction time. e1.5 equiv. potassium salt was used. homocoupling
f
byproduct <5%.
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We also extended our method to the synthesis of unsymmetrical 1,3,5ꢀtriynes (Table 4). 2ꢀAlkynyl
substituted 1,1ꢀdibromoꢀ1ꢀalkene can couple with phenyl propiolate in reasonable yields (4a, 53%
and 4b, 73%) with high selectivity. 2ꢀAlkynyl substituted 1,1ꢀdibromoꢀ1ꢀalkene can also couple
with alkyl substituted potassium propiolate. Potassium octꢀ2ꢀynoate can react with ethyl
3ꢀ(4,4ꢀdibromobutꢀ3ꢀenꢀ1ꢀynꢀ1ꢀyl) benzoate to give 4c in 40% yield. This example demonstrates
1ꢀalkylꢀ6ꢀarylꢀsubstituted 1,3,5ꢀhexatriyne can also be constructed by this method.
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Table 4. Synthesis of unsymmetrical 1,3,5ꢀtriynes.a
a Yields based on 1,1-dibromoalkenes used.
1,3ꢀDiynes are important building blocks in organic synthesis. Here we show that
2,5ꢀdiarylpyrroles which possess organic semiconductor behavior18, can be easily accessed from
unsymmetrical 1,4ꢀdiarylꢀ1,3ꢀbutadiynes (Scheme 2).19
Scheme 2. Synthesis of 2,5ꢀdiarylpyrroles from 1,3ꢀdiyne.
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3. Conclusions
In summary, we have developed a copperꢀcatalyzed decarboxylative coupling between alkynyl
carboxylates and 1,1ꢀdibromoꢀ1ꢀalkenes for highly selective synthesis of unsymmetrical
1,3ꢀdiynes and 1,3,5ꢀtriynes. This method is not only a new type of copperꢀcatalyzed method for
1,3ꢀdiyne construction, but also the first example of transitionꢀmetalꢀcatalyzed decarboxylative
coupling using 1,1ꢀdibromoꢀ1ꢀalkenes as alkynyl electrophiles. Various aryl, alkenyl, alkynyl and
alkyl substituted 1,1ꢀdibromoꢀ1ꢀalkenes can react smoothly with aryl and alkyl substituted
propiolate to produce unsymmetrical 1,3ꢀdiynes and 1,3,5ꢀtriynes with high selectivity and good
functional group compatibility.
4. Experimental Section
All chemical and solvents used in this work were purchased from chemical suppliers and used
without further purification. 1HꢀNMR, 13CꢀNMR spectra were recorded at ambient temperature in
CDCl3 unless otherwise noted. Data for 1HꢀNMR are reported as follows: chemical shift (δ ppm),
multiplicity, integration, and coupling constant (Hz). Data for 13CꢀNMR are reported in terms of
chemical shift (δ ppm), multiplicity, and coupling constant (Hz). Highꢀresolution mass spectra
were measured on TOFꢀMS with EI probe. Gas chromatographic (GC) analysis was acquired on a
GC System equipped with a flameꢀionization detector. Infrared spectra are reported in reciprocal
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centimeters (cmꢀ1). Melting points were measured on digital melting point apparatus and are
uncorrected. Flash column chromatographic purification of products was accomplished using
forcedꢀflow chromatography on Silica Gel (200ꢀ300 mesh). 1,1ꢀdibromoꢀ1ꢀalkenes used in this
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20
work were prepared according to published literature. Potassium alkynyl carboxylates used in
this work were synthesized according to published literature. 21
General Procedures for the decarboxylative alkynylation of potassium alkynyl carboxylate A
10 mL ovenꢀdried Schlenk tube was charged with copper source (CuI or Cu[(MeCN)4PF6], 10 %
mol or 20% mol), ligand (neocuproine hemihydrate or DMEDA, 10 % mol or 20% mol, if solid),
1,1ꢀdibromoalkenes (0. 5 mmol, if solid), potassium alkynyl carboxylates (0.6 mmol or 0.75 mmol)
and base (3 equiv., Cs2CO3 or LiOtBu). The tube was evacuated and filled with argon (this
procedure was repeated for three times). Then ligand (neocuproine hemihydrate or DMEDA, 10 %
mol or 20% mol, if liquid), 1,1ꢀdibromoalkenes (0. 5 mmol, if liquid) and diglyme (1 mL) were
added with a syringe under a counter flow of argon. The tube was sealed with a screw cap, stirred
at room temperature for 1 min, and connected to the Schlenk line which was filled with argon,
o
o
stirred in a preheated oil bath at 80 C or 100 C for 1 or 10 h. Upon completion of the reaction,
the mixture was cooled to room temperature. The mixture was poured into water (10 mL) and
extracted three times with ethyl acetate (10 mL each time). The combined organic layer was
washed with water (30 mL), brine (30 mL) and dried over MgSO4. It was then filtered and the
filtrate was concentrated in vacuo. Purification of the residue by column chromatography (silica
gel, ethyl acetate/petroleum ether gradient) yielded the corresponding product.
1-methoxy-4-(phenylbuta-1,3-diyn-1-yl)benzene (2a): 108 mg, 93% yield (from neocuproine
ligand) and 101 mg, 87% yield (from DMEDA ligand); white solid; 1H NMR (400 MHz, CDCl3) δ
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7.51 (dd, J = 7.2, 1.6 Hz, 2H), 7.46 (dt, J = 8.8, 2.4 Hz, 2H), 7.38 – 7.27 (m, 3H), 6.85 (dt, J = 8.8,
2.4 Hz, 2H), 3.80 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.4, 134.1, 132.4, 129.0, 128.4, 122.1,
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114.2, 113.8, 81.9, 81.1, 74.2, 72.8, 55.3. The NMR data meet the literature report 8c
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1-methyl-4-(phenylbuta-1,3-diyn-1-yl)benzene (2b): 98 mg, 91% yield; yellow solid; H NMR
(400 MHz, CDCl3) δ 7.52 (dd, J = 7.7, 1.7 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 7.36 – 7.29 (m, 3H),
7.13 (d, J = 7.9 Hz, 2H), 2.36 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 139.6, 132.5, 132.4, 129.2,
129.1, 128.4, 122.0, 118.7, 81.9, 81.2, 74.1, 73.3, 21.6. The NMR data meet the literature report
22a
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1-fluoro-4-(phenylbuta-1,3-diyn-1-yl)benzene (2c): 89 mg, 81% yield; pale yellow solid; H
NMR (400 MHz, CDCl3) δ 7.55 – 7.46 (m, 4H), 7.38 – 7.29 (m, 3H), 7.03 (tt, J = 8.6, 2.1 Hz, 2H);
13C NMR (101 MHz, CDCl3) δ 163.0 (d, JF = 251.5 Hz), 134.5 (d, JF = 8.6 Hz), 132.5, 129.3,
128.4, 121.7, 118.0 (d, JF = 3.6 Hz), 115.9 (d, JF = 22.2 Hz), 81.6, 80.5, 73.8, 73.8. The NMR data
meet the literature report 22b
.
1-chloro-2-(phenylbuta-1,3-diyn-1-yl)benzene (2d): 97 mg, 82% yield; white solid; m. p. 62ꢀ63
oC; 1H NMR (400 MHz, CDCl3) δ 7.60 – 7.49 (m, 3H), 7.45 – 7.26 (m, 5H), 7.23 (td, J = 7.6, 1.2
Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 136.9, 134.3, 132.6, 130.1, 129.5, 129.4, 128.5, 126.6,
122.0, 121.6, 83.1, 78.8, 78.0, 73.7; IR (KBr) 3062, 2217, 1471, 1435, 1255, 1157, 1127, 1060,
1031, 949, 912, 763, 752, 685 cm ꢀ1; HRMS (EIꢀTOF) calcd for C16H9Cl (M+) 236.0393; found:
236.0398.
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1-bromo-4-(phenylbuta-1,3-diyn-1-yl)benzene (2e): 134 mg, 95% yield; white solid; H NMR
(400 MHz, CDCl3) δ 7.52 (dd, J = 7.6, 1.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.41 – 7.29 (m, 5H);
13C NMR (101 MHz, CDCl3) δ 133.8, 132.5, 131.8, 129.4, 128.5, 123.7, 121.6, 120.8, 82.2, 80.4,
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75.1, 73.7. The NMR data meet the literature report 22c
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4-(phenylbuta-1,3-diyn-1-yl)phenyl 4-methylbenzenesulfonate (2f): 136 mg, 73% yield; yellow
solid; m. p. 160ꢀ164 oC; 1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 8.3 Hz, 2H), 7.54 – 7.49 (m,
2H), 7.43 (dt, J = 8.8, 2.2 Hz, 2H), 7.38 – 7.28 (m, 5H), 6.96 (dt, J = 8.8, 2.2 Hz, 2H), 2.44 (s, 3H);
13C NMR (101 MHz, CDCl3) δ 148.9, 144.6, 132.8, 131.5, 131.1, 128.9, 128.4, 127.48, 127.46,
121.6, 120.5, 119.9, 81.2, 79.0, 74.0, 72.6, 20.7; IR (KBr) 2924, 2846, 2217, 2143, 1601, 1566,
1509, 1485, 1461, 1432, 1356, 1320, 1310, 1249, 1159, 1072, 1035, 904, 834, 805, 725, 694, 659
cm ꢀ1; HRMS (EIꢀTOF) calcd for C23H16O3S (M+) 372.0820; found: 372.0812.
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1-(phenylbuta-1,3-diyn-1-yl)-3-(trifluoromethyl)benzene (2g): 109 mg, 81% yield; white solid;
m. p. 120ꢀ121 oC; 1H NMR (400 MHz, CDCl3) δ 7.77 (s, 1H), 7.68 (d, J = 7.7 Hz, 1H), 7.60 (d, J
= 7.9 Hz, 1H), 7.56 – 7.50 (m, 2H), 7.46 (t, J = 7.8 Hz, 1H), 7.41 – 7.29 (m, 3H); 13C NMR (101
MHz, CDCl3) δ 135.5, 132.6, 131.2 (q, JF = 32.8 Hz), 129.5, 129.3 (q, JF = 3.8 Hz), 129.0, 128.5,
125.7 (q, JF = 3.7 Hz), 123.6 (q, JF = 273.51 Hz), 122.9, 121.4, 82.5, 79.7, 75.5, 73.5; IR (KBr)
2962, 2925, 2854, 2219, 1484, 1435, 1353, 1321, 1310, 1278, 1263, 1196, 1156, 1117, 1094, 1072,
896, 802, 755, 687 cm ꢀ1; HRMS (EIꢀTOF) calcd for C17H9F3 (M+) 270.0656; found: 270.0653.
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4-(phenylbuta-1,3-diyn-1-yl)benzonitrile (2h): 89 mg, 78% yield; pale yellow solid; H NMR
(400 MHz, CDCl3) δ 7.62 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.56 – 7.52 (m, 2H), 7.41
(t, J = 7.4 Hz, 1H), 7.38 – 7.32 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 132.9, 132.6, 132.1, 129.8,
128.6, 126.8, 121.2, 118.2, 112.4, 84.0, 79.3, 78.2, 73.3. The NMR data meet the literature report
8c
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1-nitro-3-(phenylbuta-1,3-diyn-1-yl)benzene (2i): 88 mg, 71% yield; yellow solid; H NMR
(400 MHz, CDCl3) δ 8.36 (s, 1H), 8.21 (dd, J = 8.3, 1.3 Hz, 1H), 7.81 (d, J = 7.7 Hz, 1H), 7.58 –
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7.49 (m, 3H), 7.44 – 7.32 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 148.2, 138.0, 132.7, 129.7,
129.6, 128.6, 127.2, 123.84, 123.76, 121.2, 83.2, 78.6, 76.5, 73.2. The NMR data meet the
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literature report 22d
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(E)-butyl 3-(3-(phenylbuta-1,3-diyn-1-yl)phenyl)acrylate (2j): 136 mg, 83% yield; yellow solid;
m. p. 69ꢀ70 oC; 1H NMR (400 MHz, CDCl3) δ 7.66 (s, 1H), 7.62 (d, J = 16.0 Hz, 1H), 7.56 – 7.47
(m, 4H), 7.40 – 7.29 (m, 4H), 6.44 (d, J = 16.0 Hz, 1H), 4.21 (t, J = 6.7 Hz, 2H), 1.69 (quint, J =
7.1 Hz, 2H), 1.44 (sext, J = 7.4 Hz, 2H), 0.97 (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ
166.7, 143.2, 134.9, 133.8, 132.6, 131.8, 129.4, 129.0, 128.6, 128.5, 122.7, 121.6, 119.6, 82.0,
80.6, 74.7, 73.7, 64.6, 30.8, 19.2, 13.8; IR (KBr) 3059, 2957, 1708, 1643, 1593, 1486, 1419, 1308,
1262, 1222, 1187, 1091, 1065, 1027, 856, 801, 751, 686, 675 cm ꢀ1; HRMS (EIꢀTOF) calcd for
C23H20O2 (M+) 328.1463; found: 328.1461.
o
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2-(phenylbuta-1,3-diyn-1-yl)furan (2k): 71 mg, 74% yield; brownish solid; m. p. 37ꢀ38 C; H
NMR (400 MHz, CDCl3) δ 7.54 – 7.50 (m, 2H), 7.41 (dd, J = 1.8, 0.6 Hz, 1H), 7.38 – 7.30 (m,
3H), 6.74 (dd, J = 3.4, 0.6 Hz, 1H), 6.41 (dd, J = 3.4, 1.9 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ
144.6, 136.5, 132.6, 129.5, 128.5, 121.4, 118.1, 111.2, 84.3, 78.7, 73.4, 71.0; IR (KBr) 2925, 2207,
2147, 1492, 1478, 1442, 1327, 1200, 1152, 1076, 1022, 1000, 917, 902, 884, 816, 753, 686 cm ꢀ1;
HRMS (EIꢀTOF) calcd for C14H8O (M+) 192.0575; found: 192.0578.
tert-butyl 3-(phenylbuta-1,3-diyn-1-yl)-1H-indole-1-carboxylate (2l): 104 mg, 61% yield;
yellow oil; 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.1 Hz, 1H), 7.87 (s, 1H), 7.72 (d, J = 8.0
Hz, 1H), 7.57 – 7.51 (m, 2H), 7.41 – 7.28 (m, 5H), 1.67 (s, 9H); 13C NMR (101 MHz, CDCl3) δ
148.8, 134.6, 132.5, 131.1, 130.5, 129.2, 128.4, 125.5, 123.5, 121.9, 120.2, 115.4, 102.1, 84.7,
81.6, 77.2, 74.2, 74.1, 28.1; IR (KBr) 2965, 2930, 2360, 2341, 2212, 2149, 1741, 1555, 1453,
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1378, 1336, 1309, 1296, 1261, 1226, 1152, 1098, 1025, 803, 753, 688 cm ꢀ1; HRMS (EIꢀTOF)
calcd for C23H19NO2 (M+) 341.1416; found: 341.1418.
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3-(phenylbuta-1,3-diyn-1-yl)pyridine (2m): 61 mg, 60% yield; brownish solid; H NMR (400
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MHz, CDCl3) δ 8.76 (s, 1H), 8.58 (d, J = 4.1 Hz, 1H), 7.80 (dt, J = 7.9, 1.8 Hz, 1H), 7.57 – 7.50
(m, 2H), 7.43 – 7.31 (m, 3H), 7.28 (dd, J = 7.6, 4.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 153.1,
149.2, 139.3, 132.6, 129.6, 128.5, 123.1, 121.4, 119.3, 82.8, 78.0, 77.2, 73.4. The NMR data meet
the literature report 22e
2-(phenylbuta-1,3-diyn-1-yl)naphthalene (2n): 95 mg, 75% yield; white solid; H NMR (400
MHz, CDCl3) δ 8.05 (s, 1H), 7.83 – 7.74 (m, 3H), 7.59 – 7.44 (m, 5H), 7.39 – 7.27 (m, 3H); 13
NMR (101 MHz, CDCl3) δ 133.2, 133.1, 132.9, 132.6, 129.3, 128.5, 128.2, 127.91, 127.87, 127.3,
126.8, 121.9, 119.1, 82.1, 81.8, 74.3, 74.2. The NMR data meet the literature report 19
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9-(4-(phenylbuta-1,3-diyn-1-yl)phenyl)-9H-carbazole (2o): 94 mg, 51% yield; white solid; m. p.
172ꢀ174 oC; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 7.7 Hz, 2H), 7.75 (dt, J = 8.4, 2.0 Hz, 2H),
7.59 – 7.53 (m, 4H), 7.46 – 7.40 (m, 4H), 7.40 – 7.34 (m, 3H), 7.34 – 7.26 (m, 2H); 13C NMR
(101 MHz, CDCl3) δ 140.4, 138.5, 134.1, 132.6, 129.4, 128.5, 126.8, 126.2, 123.7, 121.7, 120.6,
120.4, 109.8, 82.2, 80.8, 74.9, 73.9; IR (KBr) 3052, 2355, 1596, 1514, 1480, 1451, 1366, 1335,
1316, 1231, 1181, 1120, 1101, 1016, 914, 835, 749, 723, 686, 624 cm ꢀ1; HRMS (EIꢀTOF) calcd
for C28H17N (M+) 367.1361; found: 367.1353.
1,2,3,4,5-pentafluoro-6-(phenylbuta-1,3-diyn-1-yl)benzene (2p): 34 mg, 23% yield; white solid;
1H NMR (400 MHz, CDCl3) δ 7.59 – 7.54 (m, 2H), 7.43 (tt, J = 7.4, 1.9 Hz, 1H), 7.40 – 7.33 (m,
2H); 13C NMR (101 MHz, CDCl3) δ 148.3 (dm, JF = 256.0 Hz), 142.1 (dm, JF = 258.9 Hz), 137.7
(dm, JF = 259.7 Hz), 132.7, 130.0, 128.6, 120.7, 99.4 (td, JF = 17.9, 4.3 Hz), 85.4 (q, JF = 3.4 Hz),
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85.2, 72.8, 64.6 (q, JF = 4.0 Hz); 19F NMR (377 MHz, CDCl3) δ ꢀ134.87 (dd, JF = 23.1, 9.2 Hz,
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2F), ꢀ150.63 (t, JF = 21.9 Hz, 1F), ꢀ161.13 (m, 2F). The NMR data meet the literature report 15
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(E)-hexa-1-en-3,5-diyne-1,6-diyldibenzene (2q): 74 mg, 65% yield; pale yellow solid; 1H NMR
(400 MHz, CDCl3) δ 7.50 (dd, J = 7.8, 1.6 Hz, 2H), 7.40 (dd, J = 7.9, 1.4 Hz, 2H), 7.36 – 7.29 (m,
6H), 7.11 (d, J = 16.3 Hz, 1H), 6.26 (d, J = 16.3 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 144.6,
135.8, 132.5, 129.3, 129.2, 128.8, 128.5, 126.5, 121.9, 106.8, 82.2, 81.4, 76.1, 74.2. The NMR
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(cyclohexylbuta-1,3-diyn-1-yl)benzene (2r): 43 mg, 41% yield; white solid; 1H NMR (400 MHz,
CDCl3) δ 7.50 – 7.44 (m, 2H), 7.35 – 7.26 (m, 3H), 2.60 – 2.50 (m, 1H), 1.90 – 1.80 (m, 2H), 1.79
– 1.67 (m, 2H), 1.59 – 1.45 (m, 3H), 1.41 – 1.27 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 132.5,
128.8, 128.3, 122.2, 88.6, 75.3, 74.4, 65.0, 32.2, 29.8, 25.8, 24.8. The NMR data meet the
literature report 22g
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1-fluoro-4-((4-methoxyphenyl)buta-1,3-diyn-1-yl)benzene (3a): 94 mg, 75% yield; white solid;
1H NMR (400 MHz, CDCl3) δ 7.54 – 7.43 (m, 4H), 7.02 (tt, J = 8.2, 2.2 Hz, 2H), 6.85 (dt, J = 8.8,
2.4 Hz, 2H), 3.81 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 162.9 (d, JF = 251.2 Hz), 160.4, 134.4 (d,
JF = 8.5 Hz), 134.2, 118.2 (d, JF = 3.6 Hz), 115.8 (d, JF = 22.2 Hz), 114.2, 113.6, 81.8, 79.9, 74.0
(d, JF = 1.4 Hz), 72.6, 55.4. The NMR data meet the literature report 13b
.
4-(m-tolylbuta-1,3-diyn-1-yl)benzonitrile (3b): 89 mg, 74% yield; yellow solid; m. p. 171ꢀ173
oC; 1H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 8.5 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H), 7.35 (d, J =
8.1 Hz, 2H), 7.27 – 7.18 (m, 2H), 2.35 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 138.4, 133.1, 132.9,
132.1, 130.7, 129.8, 128.4, 126.9, 121.0, 118.2, 112.3, 84.3, 79.2, 78.3, 72.9, 21.2; IR (KBr) 2922,
2225, 1599, 1499, 1483, 1405, 1384, 1272, 1092, 906, 874, 841, 832, 784, 685 cm ꢀ1; HRMS
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(EIꢀTOF) calcd for C18H11N (M+) 241.0891; found: 241.0883.
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4-((3-chlorophenyl)buta-1,3-diyn-1-yl)benzonitrile (3c): 71 mg, 54% yield; yellow solid; m. p.
159ꢀ160 oC; 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 8.6 Hz, 2H), 7.60 (d, J = 8.6 Hz, 2H), 7.51
(t, J = 1.4 Hz, 1H), 7.41 (d, J = 7.6 Hz, 1H), 7.40 – 7.35 (m, 1H), 7.29 (t, J = 7.9 Hz, 1H); 13C
NMR (101 MHz, CDCl3) δ 134.5, 133.0, 132.3, 132.1, 130.7, 130.0, 129.8, 126.5, 123.0, 118.2,
112.6, 82.2, 80.0, 77.7, 74.3; IR (KBr) 2963, 2228, 1591, 1561, 1472, 1405, 1262, 1095, 1023,
871, 839, 801, 678 cm ꢀ1; HRMS (EIꢀTOF) calcd for C17H8ClN (M+) 261.0345; found: 261.0344.
1-((4-methoxyphenyl)buta-1,3-diyn-1-yl)-3-(trifluoromethyl) benzene (3d): 74 mg, 49% yield;
brownish solid; m. p. 119ꢀ121 oC; 1H NMR (400 MHz, CDCl3) δ 7.77 (s, 1H), 7.67 (d, J = 7.7 Hz,
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1H), 7.60 (d, J = 7.9 Hz, 1H), 7.52 – 7.43 (m, 3H), 6.87 (dt, J = 8.8, 2.4 Hz, 2H), 3.83 (s, 3H); 13
C
NMR (101 MHz, CDCl3) δ 160.6, 135.4, 134.3, 131.1 (q, JF = 32.8 Hz), 129.2 (q, JF = 3.8 Hz),
129.0, 125.5 (q, JF = 3.7 Hz), 123.6 (q, JF = 273.5 Hz), 123.2, 114.2, 113.3, 82.8, 79.2, 75.8, 72.4,
55.4; IR (KBr) 3065, 2921, 2216, 2149, 1594, 1497, 1487, 1444, 1402, 1378, 1196, 1180, 1170,
ꢀ1
1152, 1091, 1015, 865, 845, 816, 772, 758, 731, 708, 692, 661 cm ; HRMS (EIꢀTOF) calcd for
C18H11F3O (M+) 300.0762; found: 300.0756.
ethyl 3-(p-tolylbuta-1,3-diyn-1-yl)benzoate (3e): 88 mg, 61% yield; yellow solid; m. p. 113ꢀ114
oC; 1H NMR (400 MHz, CDCl3) δ 8.19 (t, J = 1.5 Hz, 1H), 8.03 (dt, J = 7.6, 1.4 Hz, 1H), 7.68 (dt,
J = 7.6, 1.4 Hz, 1H), 7.47 – 7.37 (m, 3H), 7.15 (d, J = 7.9 Hz, 2H), 4.38 (q, J = 7.1 Hz, 2H), 2.37
(s, 3H), 1.40 (t, J = 7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 165.6, 139.8, 136.3, 133.5, 132.5,
131.0, 130.0, 129.3, 128.6, 122.4, 118.5, 82.4, 80.1, 75.0, 73.1, 61.3, 21.6, 14.3; IR (KBr) 2924,
2214, 1715, 1577, 1469, 1368, 1344, 1304, 1289, 1261, 1194, 1176, 1101, 1077, 1016, 812, 755,
680 cm ꢀ1; HRMS (EIꢀTOF) calcd for C20H16O2 (M+) 288.1150; found: 288.1154.
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1-nitro-3-(p-tolylbuta-1,3-diyn-1-yl)benzene (3f): 67 mg, 51% yield; brownish solid; m. p.
141ꢀ143 oC; 1H NMR (400 MHz, CDCl3) δ 8.35 (t, J = 1.8 Hz, 1H), 8.20 (ddd, J = 8.3, 2.2, 1.0 Hz,
1H), 7.80 (dt, J = 7.6, 1.2 Hz, 1H), 7.52 (t, J = 8.0 Hz, 1H), 7.44 (d, J = 8.1 Hz, 2H), 7.16 (d, J =
7.9 Hz, 2H), 2.38 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 148.2, 140.2, 137.9, 132.6, 129.5, 129.3,
127.2, 124.0, 123.6, 118.1, 83.5, 78.3, 76.7, 72.6, 21.7; IR (KBr) 3072, 2926, 2353, 2214, 1731,
1601, 1520, 1506, 1472, 1352, 1300, 1273, 893, 882, 814, 806, 760, 735, 667 cm ꢀ1; HRMS
(EIꢀTOF) calcd for C17H11NO2 (M+) 261.0790; found: 261.0799.
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1-((4-methoxyphenyl)buta-1,3-diyn-1-yl)naphthalene (3g): 66 mg, 47% yield; white solid; m. p.
99ꢀ100 oC; 1H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 8.3 Hz, 1H), 7.84 (d, J = 8.3 Hz, 2H), 7.76
(dd, J = 7.2, 1.0 Hz, 1H), 7.58 (ddd, J = 8.3, 6.9, 1.3 Hz, 1H), 7.55 – 7.48 (m, 3H), 7.42 (dd, J =
8.2, 7.3 Hz, 1H), 6.87 (dt, J = 8.8, 2.4 Hz, 2H), 3.81 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.5,
134.2, 134.0, 133.1, 131.9, 129.6, 128.4, 127.2, 126.7, 126.2, 125.2, 119.8, 114.2, 113.8, 82.9,
79.4, 78.9, 73.0, 55.4; IR (KBr) 3040, 2920, 2841, 2209, 2137, 1603, 1506, 1397, 1331, 1304,
ꢀ1
1291, 1252, 1177, 1168, 1153, 1110, 1025, 864, 825, 792, 766, 693, 619 cm ; HRMS (EIꢀTOF)
calcd for C21H14O (M+) 282.1045; found: 282.1039.
1-methoxy-4-(nona-1,3-diyn-1-yl)benzene (3h): 109 mg, 96% yield; white solid; 1H NMR (400
MHz, CDCl3) δ 7.40 (dt, J = 8.8, 2.4 Hz, 2H), 6.81 (dt, J = 8.8, 2.4 Hz, 2H), 3.79 (s, 3H), 2.34 (t, J
= 7.1 Hz, 2H), 1.57 (quint, J = 7.4 Hz, 2H), 1.45 – 1.27 (m, 4H), 0.91 (t, J = 7.2 Hz, 3H); 13C
NMR (101 MHz, CDCl3) δ 160.1, 134.0, 114.1, 114.1, 84.2, 74.8, 73.2, 65.2, 55.3, 31.0, 28.0,
22.2, 19.6, 13.9. The NMR data meet the literature report 22h
.
4-(nona-1,3-diyn-1-yl)benzonitrile (3i): 89 mg, 80% yield; white solid; m. p. 72ꢀ73 oC; 1H NMR
(400 MHz, CDCl3) δ 7.59 (d, J = 8.8 Hz, 2H), 7.54 (d, J = 8.8 Hz, 2H), 2.38 (t, J = 7.1 Hz, 2H),
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1.59 (quint, J = 7.3 Hz, 2H), 1.47 – 1.28 (m, 4H), 0.92 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz,
CDCl3) δ 133.0, 132.0, 127.3, 118.3, 112.0, 87.7, 78.8, 72.7, 64.6, 31.0, 27.8, 22.2, 19.6, 13.9; IR
(KBr) 2961, 2860, 2228, 1601, 1500, 1465, 1407, 1262, 1184, 1099, 1019, 841, 802 cm ꢀ1; HRMS
(EIꢀTOF) calcd for C16H15N (M+) 221.1204; found: 221.1203.
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1-methoxy-4-(penta-1,3-diyn-1-yl)benzene (3j): 77 mg, 91% yield; pale yellow solid; H NMR
(400 MHz, CDCl3) δ 7.41 (dt, J = 8.8, 2.3 Hz, 2H), 6.82 (dt, J = 8.8, 2.4 Hz, 2H), 3.80 (s, 3H),
2.00 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.1, 134.1, 114.1, 114.0, 79.6, 74.3, 73.2, 64.5,
55.3, 4.6. The NMR data meet the literature report 22i
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nona-1,3-diyn-1-ylcyclohexane (3k): 79 mg, 78% yield; colorless oil; H NMR (400 MHz,
CDCl3) δ 2.43 (ddd, J = 12.6, 8.7, 3.6 Hz, 1H), 2.25 (td, J = 7.1, 0.9 Hz, 2H), 1.83 – 1.75 (m, 2H),
1.74 – 1.65 (m, 2H), 1.58 – 1.40 (m, 5H), 1.40 – 1.22 (m, 7H), 0.89 (t, J = 7.1 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 81.3, 78.1, 65.2, 65.2, 32.3, 31.0, 29.5, 28.1, 25.8, 24.8, 22.2, 19.2, 13.9; IR
(neat) 2931, 2857, 2664, 2359, 2339, 2251, 2230, 2143, 1713, 1673, 1614, 1449, 1378, 1341, 1140,
1046, 965, 934, 890, 860, 842, 815, 766, 730 cm ꢀ1; HRMS (EIꢀTOF) calcd for C15H22 (M+)
202.1722; found: 202.1724.
pentadeca-6,8-diyne (3l): 72 mg, 70% yield; colorless oil; 1H NMR (400 MHz, CDCl3) δ 2.24 (t,
J = 7.0 Hz, 4H), 1.58 – 1.46 (m, 4H), 1.43 – 1.21 (m, 10H), 0.90 (t, J = 7.1 Hz, 3H), 0.89 (t, J =
7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 77.5, 65.3, 31.3, 31.0, 28.6, 28.4, 28.1, 22.5, 22.2,
19.2, 19.2, 14.0, 13.9; IR (neat) 2932, 2859, 2353, 2257, 2158, 1465, 1427, 1378, 1323, 1108,
1022, 726 cm ꢀ1; HRMS (EIꢀTOF) calcd for C15H24 (M+) 204.1878; found: 204.1884.
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1-methoxy-4-(phenylhexa-1,3,5-triyn-1-yl)benzene (4a): 68 mg, 53% yield; brownish solid; H
NMR (400 MHz, CDCl3) δ 7.55 – 7.50 (m, 2H), 7.47 (dt, J = 9.2, 2.3 Hz, 2H), 7.41 – 7.29 (m,
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3H), 6.85 (d, J = 8.9 Hz, 2H), 3.82 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.8, 134.7, 133.0,
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129.6, 128.5, 121.2, 114.3, 112.8, 79.0, 78.4, 74.6, 73.5, 66.9, 66.1, 55.4. The NMR data meet the
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literature report 22a
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ethyl 3-(phenylhexa-1,3,5-triyn-1-yl)benzoate (4b): 109 mg, 73% yield; white solid; m. p. 69ꢀ71
oC; 1H NMR (400 MHz, CDCl3) δ 8.19 (t, J = 1.5 Hz, 1H), 8.05 (dt, J = 8.0, 1.5 Hz, 1H), 7.68 (dt,
J = 7.6, 1.5 Hz, 1H), 7.56 – 7.50 (m, 2H), 7.45 – 7.28 (m, 4H), 4.38 (q, J = 7.1 Hz, 2H), 1.40 (t, J
= 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 165.5, 136.8, 134.0, 133.0, 131.1, 130.6, 129.8,
128.7, 128.5, 121.5, 120.9, 78.9, 77.4, 75.2, 74.4, 67.0, 66.2, 61.4, 14.3; IR (KBr) 2974, 2926,
2853, 2192, 1712, 1600, 1489, 1468, 1443, 1432, 1394, 1369, 1282, 1226, 1169, 1118, 1017, 910,
ꢀ1
862, 811, 759, 749, 689, 677 cm ; HRMS (EIꢀTOF) calcd for C21H14O2 (M+) 298.0994; found:
298.0996.
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ethyl 3-(undeca-1,3,5-triyn-1-yl)benzoate (4c): 58 mg, 40% yield; yellow oil; H NMR (400
MHz, CDCl3) δ 8.17 (t, J = 1.5 Hz, 1H), 8.03 (dt, J = 7.9, 1.3 Hz, 1H), 7.66 (dt, J = 7.7, 1.3 Hz,
1H), 7.40 (t, J = 7.8 Hz, 1H), 4.38 (q, J = 7.1 Hz, 2H), 2.34 (t, J = 7.1 Hz, 2H), 1.57 (quint, J = 7.1
Hz, 2H), 1.44 – 1.27 (m, 7H), 0.91 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 165.5,
136.8, 134.0, 131.0, 130.3, 128.6, 121.7, 83.2, 75.5, 74.3, 67.9, 65.6, 61.4, 59.2, 31.0, 27.7, 22.1,
19.6, 14.3, 13.9; IR (neat) 3071, 2959, 2933, 2861, 2352, 2214, 1724, 1599, 1577, 1465, 1431,
1392, 1368, 1281, 1261, 1181, 1104, 1079, 1025, 914, 861, 815, 799, 753, 682 cm ꢀ1; HRMS
(EIꢀTOF) calcd for C20H20O2 (M+) 292.1463; found: 292.1464.
Procedures for the experiment described in Scheme 1: A 50 mL ovenꢀdried Schlenk flask was
charged with CuI (0.06 mmol, 1 % mol), neocuproine hemihydrate (0.06 mmol, 1 % mol),
1ꢀ(2,2ꢀdibromovinyl)ꢀ4ꢀmethoxybenzene (6 mmol), potassium 3ꢀphenylpropiolate (7.2 mmol) and
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Cs2CO3 (3 equiv.). The tube was evacuated and filled with argon (this procedure was repeated for
three times). Then diglyme (12 mL) were added with a syringe under a counter flow of argon. The
tube was sealed with a screw cap, stirred at room temperature for 1 min, and connected to the
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Schlenk line which was filled with argon, stirred in a preheated oil bath at 100 C for 10 h. Upon
completion of the reaction, the mixture was cooled to room temperature. The mixture was poured
into water (100 mL) and extracted three times with ethyl acetate (100 mL each time). The
combined organic layer was washed with water (300 mL), brine (300 mL) and dried over MgSO4.
It was then filtered and the filtrate was concentrated in vacuo. Purification of the residue by
column chromatography (silica gel, ethyl acetate/petroleum ether gradient) yielded the
1ꢀmethoxyꢀ4ꢀ(phenylbutaꢀ1,3ꢀdiynꢀ1ꢀyl)benzene (1.24 g, 5.34 mmol, 89 % yield) as a white solid;
1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 7.2, 1.6 Hz, 2H), 7.47 (dt, J = 8.8, 2.4 Hz, 2H), 7.38 –
7.27 (m, 3H), 6.86 (dt, J = 9.2, 2.4 Hz, 2H), 3.82 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.4,
134.1, 132.4, 129.0, 128.4, 122.1, 114.2, 113.8, 81.9, 81.1, 74.2, 72.8, 55.3. The NMR data meet
the literature report 8c
.
General Procedures for the experiments described in Scheme 2:18 A mixture of
1,4ꢀdiarylꢀ1,3ꢀbutadiyne (0.5 mmol) and CuCl (0.05 mmol) in aniline (5 mmol) was stirred at 100
oC for 24 h under argon atmosphere. Then the reaction mixture was cooled to room temperature
and directly purified by column chromatography on silica gel.
2-(4-methoxyphenyl)-1,5-diphenyl-1H-pyrrole (Scheme 2, a): 124 mg, 76% yield; yellow solid;
m. p. 163ꢀ164 oC; 1H NMR (400 MHz, CDCl3) δ 7.24 – 7.19 (m, 3H), 7.18 – 7.10 (m, 3H), 7.08 –
6.95 (m, 6H), 6.71 (dt, J = 8.8, 2.4 Hz, 2H), 6.46 (d, J = 3.6 Hz, 1H), 6.40 (d, J = 3.6 Hz, 1H),
3.74 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 158.2, 139.0, 135.7, 135.3, 133.4, 130.0, 128.9, 128.7,
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128.6, 127.8, 127.1, 126.1, 125.9, 113.4, 109.8, 109.2, 55.1; IR (KBr) 3049, 2932, 2838, 2360,
1674, 1598, 1574, 1547, 1523, 1491, 1447, 1420, 1387, 1335, 1287, 1245, 1178, 1106, 1070, 1031,
957, 911, 831, 812, 775, 756, 697 cm ꢀ1; HRMS (EIꢀTOF) calcd for C23H19NO (M+) 325.1467;
found: 325.1469.
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1,2-diphenyl-5-(3-(trifluoromethyl)phenyl)-1H-pyrrole (Scheme 2, b): 91 mg, 50% yield;
white solid; m. p. 173ꢀ174 oC; 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 7.6 Hz, 1H), 7.33 – 7.22
(m, 5H), 7.22 – 7.12 (m, 4H), 7.11 – 7.05 (m, 2H), 7.05 – 6.97 (m, 2H), 6.55 (d, J = 3.7 Hz, 1H),
6.49 (d, J = 3.7 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 138.6, 136.7, 134.2, 134.0, 133.0, 131.5,
130.4 (q, JF = 32.1 Hz), 129.0, 128.9, 128.8, 128.3, 128.0, 127.7, 126.5, 125.2 (q, JF = 3.9 Hz),
124.0 (q, JF = 273.4 Hz), 122.7 (q, JF = 3.7 Hz), 110.7, 110.2; IR (KBr) 2925, 1598, 1547, 1497,
1470, 1448, 1425, 1391, 1356, 1344, 1323, 1257, 1177, 1164, 1125, 1099, 1076, 1049, 903, 811,
776, 756, 699 cm ꢀ1; HRMS (EIꢀTOF) calcd for C23H16F3N (M+) 363.1235; found: 363.1234.
ASSOCIATED CONTENT
1
Supporting Information. Copies of H and 13C spectra for all compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
fuyao@ustc.edu.cn
ACKNOWLEDGMENT
This work was supported by the National Basic Research Program of China (2012CB215306), the
National Natural Science Foundation of China (21172209) and Chinese Academy of Science
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(KJCX2ꢀEWꢀJ02). Zheng Huang and Xiao Xiao thank the National Undergraduate Training
Program for Innovation of China (201210358060) for financial support.
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