Metal-free and recyclable route to synthesize polysubstituted olefins via C-C bond construction from direct dehydrative coupling of alcohols or alkenes with alcohols catalyzed by sulfonic acid-functionalized ionic liquids

Article abstract of DOI:10.1002/adsc.201301150

A direct synthesis of polysubstituted olefins via construction of C-C bonds, which involves the direct dehydrative coupling of alcohols or alkenes with alcohols, was realized using a series of alkanesulfonic acid group-functionalized ionic liquids (SO₃H-functionlization ILs) without additives. The metal-free and recyclable catalyst system avoided the disposal and neutralization of acidic catalysts after reaction and tolerated a broad range of substrates, including benzylic, allyl, propargylic, aliphatic and aromatic or aliphatic olefins. Additionally, the catalytic system was suitable for a gram-scale preparation. Preliminary mechanistic studies indicated that the C-H bond cleavage in this reaction might be involved in the rate-determining step.

Full text of DOI:10.1002/adsc.201301150

FULL PAPERS
DOI: 10.1002/adsc.201301150
Metal-Free and Recyclable Route to Synthesize Polysubstituted
À
Olefins via C C Bond Construction from Direct Dehydrative
Coupling of Alcohols or Alkenes with Alcohols Catalyzed by
Sulfonic Acid-Functionalized Ionic Liquids
Feng Han,a Lei Yang,a,* Zhen Li,a Yingwei Zhao,a and Chungu Xiaa,*
a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese
Academy of Sciences, Lanzhou 730000, Peopleꢀs Republic of China
Fax : (+86)-931-827-7088; phone: (+86)-931-496-8129; e-mail: lyang@licp.cas.cn or cgxia@licp.cas.cn
Received: December 19, 2013; Revised: March 24, 2014; Published online: June 25, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201301150.
Abstract: A direct synthesis of polysubstituted ole- and aromatic or aliphatic olefins. Additionally, the
À
fins via construction of C C bonds, which involves catalytic system was suitable for a gram-scale prepa-
the direct dehydrative coupling of alcohols or alk- ration. Preliminary mechanistic studies indicated that
À
G
anesulfonic acid group-functionalized ionic liquids volved in the rate-determining step.
(SO3H-functionlization ILs) without additives. The
metal-free and recyclable catalyst system avoided
the disposal and neutralization of acidic catalysts Keywords: alcohols; alkenes; C C bond construc-
after reaction and tolerated a broad range of sub- tion; direct dehydrative coupling; sulfonic acid-func-
strates, including benzylic, allyl, propargylic, aliphatic tionalized ionic liquids
À
Introduction
for further functionalization, have been developed to
date.
Nucleophilic substitution reactions of electrophiles
A seminal work on the direct coupling of alcohols
with activated nucleophiles, such as thiols, amines, and simple alkenes was reported by Muzart and co-
and indoles, are among the most powerful tools for workers, in which 2,3-dihydro-1-styryl-1H-indene was
the formation of carbon-carbon and carbon-hetero- generated in low yield and the selectivity from 1-
ACHTUNGTRENNUNG ACHTUNGTRENoNNGU l and styrene was achieved by using
atom bonds.[1] Traditionally, activated electrophilic re- indan
agents (C X, X=halide, tosylate, triflate, mesylate, H6P2W18O62 as the catalyst.[5] Yamamoto et al. devel-
etc.) with good leaving groups are usually used as the oped the Pd(II)-catalyzed direct coupling of benzylic
partner in this type of reaction.[2] However, the addi- alcohols with styrenes by using PPh3 as the ligand and
tional steps for synthesis of these reagents and the (CF3CO)2O as the additive.[6] Subsequently, Liu et al.
potential generation of stoichiometric amounts of developed FeCl3·6H2O-catalyzed direct dehydrative
wastes make such a protocol fairly unattractive. Ap- coupling of alcohols with aromatic olefins or alcohols
parently, the direct coupling of alcohols with various in the presence of stoichiometric amounts of TsOH.[7]
nucleophiles would be preferable because of its en- Liu et al. established a novel protocol for producing
vironmentally benign and atom-efficient features, 4H-chromene derivatives via dehydrative coupling of
since only H2O is formed as a by-product.[3] In the corresponding 2-(hydroxymethyl)phenols with
this context, the acid- or transition-metal-catalyzed ketene dithioacetals using CuBr2 as the catalyst.[8] Yi
Friedel–Crafts-type alkylation of alcohols with allyl, and co-workers reported the selective coupling of al-
À
À
aryl, and alkynyl partners has been widely investigat- kenes with aliphatic alcohols via the vinyl C H acti-
ed and developed.[4] However, few examples for vation pathway with the cationic ruthenium complex
À
the direct dehydrative coupling of alcohols with [(C6H6)
G
simple alkenes to generate substituted alkenes, which the sole catalyst.[9] Wang et al. reported the use of
possess biological activities or provide an opportunity a FeCl3-catalyzed propargylic substitution reaction to
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Metal-Free and Recyclable Route to Synthesize Polysubstituted Olefins
synthesize diarylalkenyl propargylic compounds di- rate-determining step as indicated by intermolecular
rectly from propargylic alcohols with 1,1-diarylal- competing kinetic isotope effect (KIE) experiments.
kenes.[10] Subsequently, Zhang, Pan and co-workers
discovered that the propargylic substitution reaction
could be extended to other terminal aromatic alkenes Results and Discussion
in the presence of catalytic amounts of CuACTHNUTRGNEUNG
(OTf)2.[11]
More recently, two novel protocols for the direct cou- Initially, we chose the direct dehydrative coupling be-
pling of various alcohols with alkenes have also been tween 1a and 2a as the model reaction and various re-
achieved by employing simple TfOH and NaHSO4/ action parameters have been screened, as shown in
SiO2 as catalyst and promoter, respectively.[12] Despite Table 1. A variety of ionic liquids derived from 1-
these important achievements, the reported methods methylimidazolium, guanidine, pyridine, pyrrolidine
for the direct coupling of alcohols with alkenes suf- was first screened. The results indicated that [Bmim]
fered from difficult catalyst reusability, narrow sub- [BF4] and [Bmim]ACTHNUTRGNEUNG[PF6] had no catalytic activities
strate scope, transition metal utilization, and disposal toward the reaction (entries 1 and 2). Interestingly,
of strong acidic catalysts after the reaction leading to a 31% yield of the desired product was obtained on
the necessity of performing additional procedures.
employing [BsMim]ACTHNGUTERN[UNG HSO4] as the catalyst and this
Inspired by our previous research on the sulfonic yield could be improved up to 55% by adjusting the
acid-functionalized ionic liquids-catalyzed direct ami- anion from [HSO4]À to [OTf]À (entry 3 vs. entry 4).
nation of alcohols[13] and previous reports on carbo- Additionally, a series of ionic liquids based on 1-men-
cation chemistry,[4c] we envisioned that the formed thylimidazolium, guanidinium, pyridinium and pyrro-
carbocation intermediate from an alcohol under the lidinium as the cations and OTfÀ as the anion was
action of SO3H-functionalized ionic liquids could par- then tested (entries 5–12). To our delight, [BsOdP]
ticipate in a nucleophilic addition of olefins to afford [OTf] exhibited the best activity in the reaction and
new carbon-carbon bonds with water as the only by- an 80% yield of the desired 3aa was obtained. The
product. In addition, the olefin coupling partner can acidities of the above mentioned pyrrolidinium-based
be obtained in situ by the dehydration of the corre- SO3H-functionalized ionic liquids were evaluated
sponding inexpensive and often easily available alco- from the Hammett acidity function using UV-visible
hols bearing H at the b position.
spectroscopy with 2-nitroanline as the indicator in di-
Based on the above mentioned hypothesis, a series chloromethane (DCM)[14] (see the Supporting Infor-
of alkanesulfonic acid group-functionalized ionic liq- mation, Table S1 and Figure S1). Interestingly, it was
uids derived from pyrrolidine, imidazole, pyridine and found that the acidities of the SO3H-functionalized
guanidine was used as metal-free and recyclable cata- ionic liquids decreased with increasing carbon atom
lysts to synthesize polysubstituted olefins from alco- number in the side chain of the pyrrolidine ring,
hols or alkenes with alcohols (Figure 1). Among the whereas the catalyst activities increased until a maxi-
ionic liquid catalysts tested, [BsOdP]ACTHNUGTRNEUNG[OTf] exhibited mum was reached. The effects of reaction tempera-
the best activity and could be reused at least six times ture and catalyst loading on the reaction were also
without significant loss of activity, effectively avoiding screened. We found that 808C is the best reaction
the disposal and neutralization of the acidic catalysts temperature and 10 mol% of [BsOdP]ACTHUNRTGNE[GNU OTf] is the
after the reaction. Notably, the catalytic system has best catalyst loading (entries 13–20). The yield re-
a wide substrate scope and various alcohols and al- markably increased when the temperature increased
kenes including benzylic, allyl, propargylic, aliphatic from 408C to 808C (entries 12, 14 and 15) and no sig-
alcohols, and aromatic, aliphatic alkenes could partici- nificant change was observed with further increase in
pate in the transformation. Moreover, it was found temperature (entries 16 and 17). Catalyst loading also
À
that C H bond cleavage might be involved in the substantially affected yield with variation of loading
Figure 1. Functionalized ionic liquids used in the direct dehydrative coupling reactions.
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Table 1. Screening the activities of SO3H-functionalized
ratios of the two alcohols were also investigated. It
was found that an excess of olefin-generating benzylic
alcohol can promote the coupling reaction (en-
tries 22–26). Additionally, some control experiments
were also conducted to compare the catalytic activi-
ties between traditional Brønsted acids catalysis and
SO3H-functionalized ionic liquids catalysis. As expect-
ed, only 63% yield of the desired product was ob-
tained with TfOH catalyst. Additionally, the reaction
became very sluggish when using TsOH as the cata-
lyst, and only trace amounts of the desired product
was detected under the same reaction conditions (en-
tries 27 and 28).
ionic liquids.[a]
With the optimized reaction conditions in hand, we
next surveyed the substrate scope of this protocol for
the formation of polysubstituted olefins via direct de-
hydrative coupling of two different alcohols (Table 2).
Initially, a series of diphenylmethanol and derivatives
was studied employing 1-phenylethanol in situ gener-
ating styrene as the coupling partner. Interestingly,
the reactivities of diphenylmethanol derivatives with
one substituent on one of the aryl rings had a slight
relationship with the electronic properties and steric
hindrance. The substrates with meta- or ortho-sub-
stituent produced relatively lower yields compared
with para-substituted ones (3ab, 3ac and 3ad vs. 3aa).
An electron-donating group such as methyl was bene-
ficial for the reaction, giving 87% yield of the desired
product (3ae). Interestingly, bis(4-chlorophenyl)me-
thanol and bis(4-fluorophenyl)methanol also afforded
the desired products 3ag and 3ah in 89% and 83%
yields, respectively. The effect of the electronic prop-
erties and steric hindrance of 1-phenylethanol deriva-
tives was then investigated with (4-chlorophenyl)-
Entry Catalyst
Cat. amount
[mol%]
T
Yield
[oC] [%][b]
1
N
N
10
10
80
80
80
80
80
80
80
80
80
80
80
80
25
40
60
NR[c]
NR[c]
31
55
63
67
58
65
69
2
N
ACHTUNGTRENNUNG
3
A
ACHTUNGTRENNUNG[HSO4] 10
4
A
G
5
A
10
10
10
10
10
10
10
6
N
U
7
N
U
8
N
U
9
N
U
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
N
E
74
77
G
[OTf] 10
80
NR[c]
59
E
10
71
[OTf] 10
100 82
120 83
G
1
5
80
80
80
80
80
80
80
80
80
80
80
39
68
82
83
E
R
E
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
[OTf] 20
AHCTUNGTREG(NNUN phenyl)methanol as the coupling partner (3ba–3ea).
78[d]
75[e]
70[f]
67[g]
61[h]
63
Yields of 75% to 79% of the desired products were
obtained on employing 1d or 1e with an ortho-sub-
stituent as the olefin source (3da and 3ea). Addition-
ally, homo-coupling of 1-phenylethanol derivatives
also gave 1,3-diarylbut-1-ene derivatives in moderate
yields (3aa’–3dd’). Interestingly, direct dehydrative
coupling of 1b and 2i selectively generated 3bi as the
product. To our delight, tert-butyl alcohol (1f) was
also compatible with the reaction conditions and the
desired product 3ff was obtained in 81% yield.
Subsequent studies showed that olefins could be di-
rectly used as the direct dehydrative coupling partner
under the optimized reaction conditions. Various ole-
fins can participate in the coupling reaction, and the
results are summarized in Table 3. The coupling reac-
tions of styrene with a series of alcohols were initially
investigated. Obviously, benzhydrol and its deriva-
tives, which contain electron-donating and electron-
10
10
trace
[a]
Reaction conditions: 1a: 1.0 mmol, 2a: 0.50 mmol, cata-
lyst: 10 mol%, reaction temperature: 808C, solvent:
DCM, 2.0 mL, reaction time: 12 h.
Isolated yield.
NR=no reaction.
1a: 0.75 mmol, 2a: 0.50 mmol.
1a: 0.60 mmol, 2a: 0.50 mmol.
1a: 0.50 mmol, 2a: 0.60 mmol.
1a: 0.50 mmol, 2a: 0.75 mmol.
1a: 0.50 mmol, 2a: 1.0 mmol.
[b]
[c]
[d]
[e]
[f]
[g]
[h]
from 1 mol% to 10 mol% (entries 18, 19 and 12). withdrawing groups on the aryl rings, were suitable
However, the yield slightly changed when the catalyst substrates for this protocol, and the corresponding
loading was in the range of 10 mol% to 30 mol% products were obtained in 35–82% yields (3aa–3ah,
(entry 13 vs. entries 20 and 21). Meanwhile, material 3ja–3ka). In these cases, a significant steric effect was
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Table 2. Direct dehydrative coupling of benzylic alcohols with alcohols.[a]
[a]
Reaction conditions: alcohol 1: 1.0 mmol, alcohol 2: 0.50 mmol; catalyst: [BsOdP]ACTHNUTRGNEU[GN OTf], 10 mol% (referred to
alcohol 2), solvent: DCM, 2.0 mL, reaction temperature: 808C, reaction time: 12 h. Isolated yields are shown.
Only the E isomer was observed in all cases.
t=24 h.
Alcohol 1: 1.0 mmol.
tert-Butyl alcohol (1f) as alcohol 1, 2.0 mmol, diphenylmethanol (2f) as alcohol 2.
[b]
[c]
[d]
observed (3ac and 3ad). In addition, the reactions of were also investigated (Supporting Information,
allyl alcohol and propargyl alcohol were also tested Table S4). However, only benzylic alcohols with elec-
and 72% yield of dialkene 5la and 67% yield of tron-donating groups on the aryl ring could result in
enyne 5ma were obtained. Aromatic primary alcohols a satisfactory reaction (5na). Then, the reactivities of
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Table 3. Direct dehydrative coupling of alcohols with alkenes.[a]
[a]
Reaction conditions: alcohol: 0.50 mmol, olefin: 1.0 mmol, catalyst: [BsOdP]OTf, 10 mol% (referred
to alcohol), solvent: DCM, 2.0 mL, temperature: 808C, reaction time: 12 h. Isolated yields are shown.
Only the E isomer was observed in all cases.
t=24 h.
t=48 h.
[b]
[c]
[d]
[e]
[f]
t=2 h.
Olefin, 2.0 mmol, t=6 h.
1-Methylcyclohex-1-ene as substrate.
Methylenecyclohexane as substrate.
[g]
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several kinds of olefins were examined employing successfully demonstrated by using 1,1-diphenylethy-
benzhydrol as the alcohol partner. Styrene derivatives lene and diphenylmethanol as substrates. After stir-
bearing electron-withdrawing groups provided the ring at 808C in DCM for 3 h, the desired product 5fj
corresponding product in good to excellent yields could be isolated in 91% yield through simple recrys-
(5fc–5fg), while an electron-donating group was not tallization with petroleum ether as the solvent.
beneficial for the reaction (5fb). Interestingly, olefins
Another practical feature of the current catalyst
with larger steric hindrance, such as naphthalene eth- system is the facile separation of the product and the
ylene and styrene derivatives with a substitutents, recyclability of the catalyst. To test the catalystꢀs reus-
showed better activities than styrene (5fh–5fj). Nota- ability, the reaction was carried out in the presence of
bly, up to a 98% yield of 5fj was obtained via direct catalytic amounts of [BsOdP]ACTHNUTRGNE[UNG OTf] under the optimal
coupling of stilbene and benzhydrol. Additionally, reaction conditions using 1a and 2a as substrates.
cyclic internal olefins also exhibited excellent activi- After each cycle, the catalyst and the product were
ties (5fk–5fo). It is worth mentioning that 1-methylcy- separated by petroleum ether and water. Subsequent-
clohex-1-ene and methylenecyclohexane reacted with ly, the water layer containing the catalyst was concen-
diphenylmethanol to offer the same desired product trated and dried under reduced pressure at 808C for
5fo. Furthermore, SO3H-functionalized ionic liquids 24 h in order to be reused directly. The results shown
also promoted the intramolecular cyclization reac- in Figure 2 indicate that the isolated yield of the prod-
tions of an aliphatic diol 2o and an alkenyl alcohol 2p uct is almost consistent after six runs and [BsOdP]
to form furan ring 2oo’ and pyranoid ring 2pp’ in ex- [OTf] can be reused at least six times without signifi-
cellent conversions (Scheme 1).
cant loss of activity.
The present synthetic protocol for the synthesis of
To gain insights into the mechanism of the present
olefins via direct dehydrative coupling of alcohol and reaction, some control experiments were conducted
olefin can be carried out as a gram-scale preparation, (Scheme 3). Under the typical conditions for 5 min,
which is significant from the standpoint of practical employing styrene 4a and diphenylmethanol 2f as the
applications (Scheme 2). Starting with 10 mmol of (4-
chlorophenyl)ACHTUNGTRENNUNG(phenyl)methanol and 20 mmol of sty-
rene as substrates, the corresponding product 3aa
could be isolated in 72% yield under the typical con-
ditions. Moreover, the gram-scale reaction was also
Scheme 1. Intramolecular cyclization reactions of 2o and 2p
catalyzed by [BsOdP]OTf.
Figure 2. Recyclability of [BsOdP]
tive coupling of 1a and 2a.
ACHTUNGERTN[NUNG OTf] in direct dehydra-
Scheme 2. Gram-scale synthesis of polysubstituted olefins.
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Scheme 3. Control experiments.
substrates gave the desired product 3af along with the ed by [BsOdP]ACTHNUTRGENUG[N OTf] would generate a carbocation in-
dimeric ether 5a in yields of 7% and 83%, respective- termediate A,[7,13] which in turn reacts with 2f to form
ly. By contrast, after a prolonged reaction time (12 h), oxonium salt B and etheric compound 5a. The ether
a 70% yield of 3af was obtained, and 5a disappeared. 5a then reacts with styrene 4a to produce the desired
Similarly, when employing 4a and 5a as the substrate product 3af. Another probable pathway could be
also the desired product 3af was also furnished in a direct alkylation of styrene 4a and alcohol 2f to pro-
75% yield. These results suggested that dimeric ether duce carbocation intermediate C, which would be fol-
5a might be an intermediate in the reaction.
lowed by deprotonation to give the corresponding
Finally, kinetic isotope effect (KIE) experiments product 3af. In both pathways, styrene 4a could be
were also performed (Scheme 4). The observed signif- generated in situ from benzylic alcohol 1a via dehy-
icant isotopic effects (kH/kD =2.1) indicated that the dration under the reaction conditions.
À
C H bond cleavage reaction might be involved in the
rate-determining step.[15]
Although the exact reaction mechanism is not Conclusions
known at this stage, on the basis of the experimental
results and previous work by others,[4d,12,16] two plausi- In summary, we have successfully developed a conven-
À
ble pathways for this dehydrative coupling reaction ient and efficient method for C C bond formation by
are proposed as shown in Scheme 5. One possible direct dehydrative coupling of various alcohols with
pathway involves ether 5a as an intermediate of the alcohols and alkenes using SO3H-functionlized ionic
reaction.[11,12a,16a] Diphenylmethanol 2f initially activat- liquids as metal-free, highly efficient and reusable cat-
Scheme 4. Competing KIE experiments.
Scheme 5. Proposed mechanisms for the direct dehydrative coupling.
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119.9 (q, JC,F =316.4 Hz, CF3); IR: 3327, 2950, 1621, 1589,
1458, 1406, 1290, 1227, 1167, 1067, 1030, 897, 761, 719, 638,
573, 574, 476; MS (ESI): [m/z]+ =460.2, [m/z]À =148.9.
alysts under mild reaction conditions. The present
protocol provides an effective approach to synthesize
a diverse range of polysubstituted olefins in good to
excellent yields. The kinetic competition experiment
Typical Procedure for the Direct Dehydrative
Coupling of Alcohols with Alcohols and Reuse of
[BsOdP]ACTHNUGRTNEUNG[OTf]
À
shows that the C H bond cleavage might be involved
in the rate-determining step. Further investigations on
the detailed mechanism and its application are ongo-
ing in our laboratory.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
(109 mg, 0.5 mmol), and dry dichloromethane (2.0 mL) were
added into the screw-cap vial. Then the mixture was stirred
continuously at 808C for 12 h and monitored by TLC. At
the end of the reaction, the catalyst and the product were
separated using petroleum ether and water. The combined
organic extracts were washed with brine, dried (MgSO4) and
concentrated under vacuum. Flash column chromatography
(petroleum ether) on silica gel of the residue gave (E)-(3-(4-
chlorophenyl)prop-1-ene-1,3-diyl)dibenzene (3aa) as a color-
less oil in high purity as assessed by NMR and GC-mass
spectroscopy; yield: 121.6 mg (80%). 1H NMR (400 MHz,
CDCl3): d=4.86 (d, J=7.2 Hz, 1H), 6.33 (d, J=16.0 Hz,
1H), 6.62 (dd, J=7.6, 16.0 Hz, 1H), 7.15–7.18 (m, 2H),
7.20–7.38 (m, 12H); 13C NMR (100 MHz, CDCl3): d=53.5,
126.3, 126.7, 127.5, 128.6, 128.6, 128.6, 130.0, 131.8, 132.0,
132.3, 137.1, 142.0, 143.0; GC-MS (EI): [m/z]+ =304.1
Experimental Section
General Remarks
NMR spectra were recorded on Bruker AvanceTM III spec-
trometers. 1H NMR (400 MHz) and 13C NMR (100 MHz)
spectra were obtained as solutions in CDCl3, D2O or
(CD3)2SO. Chemical shifts are reported in parts per million
(ppm, d) and referenced to CHCl3 (d=7.26), D2O (d=4.88)
or (CD3)2SO (d=2.50); GC-MS analyses were performed
using an Agilent 6850 system (FID) and ion source of the
mass spectrometer is EI. Mass spectra (MS) were recorded
on Waters ZQ4000 mass instrument (ESI). UV-vis spectra
were recorded on Agilent Cary 60. Silica gel (200–300 mi-
crons) was used for all chromatographic separations. IR
spectra were recorded FT-IR spectroscopy Nexus 870. An-
hydrous organic solvents were dried and stored under nitro-
gen. All other chemicals used for synthetic procedures were
reagent grade or better. Solutions were concentrated under
vacuum with a rotary evaporator and the residue was puri-
fied using a silica gel column unless specified otherwise. All
reactions were monitored by TLC with silica gel coated
plates and detection was conducted by UV absorption
(254 nm).
The ionic liquid ([BsOdP]OTf) obtained by concentrating
the water layer and drying under vacuum at 808C for 24 h
could be reused for another five runs without significant de-
creases in catalytic activity as shown in Figure 2.
Typical Procedure for Direct Dehydrative Coupling
of Alcohols with Alkenes
A mixture of alcohol (0.50 mmol), olefin (1.0 mmol), [BsOd-
P]OTf (10 mol%), and dry dichloromethane (2.0 mL) was
heated at 808C for the indicated time until complete con-
sumption of alcohol as monitored by TLC. After the reac-
tion had finished, the mixture was extracted by petroleum
ether and water. Then the water layer containing the cata-
lyst was concentrated and dried under reduced pressure at
808C for 24 h in order to be reused directly. The petroleum
ether layer was evaporated under vacuum and purified by
flash column chromatography (petroleum ether) to afford
the desired product.
Experimental Procedure for Ionic Liquid N-Octa-
decyl-[N-(4-butanesulfonyl)pyrrolidine] Trifluoro-
methanesulfonate ([BsOdP]ACTHNUTRGNE[UNG OTf])
N-Octadecylpyrrolidine (6.46 g, 0.020 mol) and 1,4-butane-
sultone (2.25 mL, 0.022 mol) were charged into a 100-mL
round-bottom flask. Then the mixtures were stirred at 408C
for 10 h. The white solid zwitterion was washed repeatedly
with ether to remove non-ionic residues and dried under
vacuum. After washing the salt with ether and toluene to
remove any unreacted starting materials, the solid was dried
under vacuum. Then, a stoichiometric amount of trifluoro-
methanesulfonic acid (1.80 mL, 0.020 mol) was added drop-
wise and the mixture stirred for 12 h at 808C, which resulted
in the formation of N-octadecyl-[N-(4-sulfonbutyl)pyrroli-
Characterization of the Products
(E)-[3-(4-Chlorophenyl)prop-1-ene-1,3-diyl]dibenzene
(3aa): Colorless oil, this compound is known.[7,12a,17] 1H NMR
(400 MHz, CDCl3): d=4.86 (d, J=7.2 Hz, 1H), 6.33 (d, J=
16.0 Hz, 1H), 6.62 (dd, J=7.6, 16.0 Hz, 1H), 7.15–7.18 (m,
2H), 7.20–7.38 (m, 12H); 13C NMR (100 MHz, CDCl3): d=
53.5, 126.3, 126.7, 127.5, 128.6, 128.6, 128.6, 130.0, 131.8,
132.0, 132.3, 137.1, 142.0, 143.0; GC-MS (EI): [m/z]+ =304.1.
(E)-[3-(3-Chlorophenyl)prop-1-ene-1,3-diyl)dibenzene
dine] trifluoromethanesulfonate ([BsOdP]ACTHNUGRTENUNG[OTf]). The ionic
liquid phase was then washed repeatedly with toluene and
ether to remove non-ionic residues, and dried under
vacuum. The product (11.9 g, 98% yield) was formed quanti-
tatively and in high purity as assessed by NMR, IR and
mass spectroscopy. 1H NMR (400 MHz, D2O): d=0.73 (t,
J=4.8 Hz, 3H), 1.15–1.22 (m, 30H), 1.55–1.74 (m, 6H),
2.00–2.07 (m, 4H), 2.77 (t, J=7.2 Hz, 2H), 3.09–3.19 (m,
4H), 3.38–3.42 (m, 4H); 13C NMR (100 MHz, D2O): d=
13.8, 21.5, 21.6, 21.8, 22.5, 22.7, 22.8, 23.0, 26.3, 28.8, 29.1,
29.6, 29.8, 29.9, 30.0, 30.1, 30.2, 32.0, 50.1, 59.4, 59.7, 62.7,
1
(3ab): Colorless oil, this compound was unknown. H NMR
(400 MHz, CDCl3): d=4.86 (d, J=7.6 Hz, 1H), 6.35 (d, J=
16.0 Hz, 1H), 6.62 (dd, J=7.6, 16.0 Hz, 1H), 7.10–7.13 (m,
1H), 7.19–7.38 (m, 13H); 13C NMR (100 MHz, CDCl3): d=
53.9, 126.4, 126.7, 126.8, 126.9, 127.6, 128.6, 128.6, 128.7,
129.8, 131.7, 132.0, 134.4, 137.0, 142.8, 145.7; GC-MS (EI):
[m/z]+ =304.1.
Adv. Synth. Catal. 2014, 356, 2506 – 2516
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2513

FULL PAPERS
Feng Han et al.
(E)-[3-(2-Chlorophenyl)prop-1-ene-1,3-diyl]dibenzene
(3ac): Colorless oil, this compound was unknown. H NMR
(E)-1-Chloro-2-[3-(4-chlorophenyl)-3-phenylprop-1-enyl]-
benzene (3da): Colorless oil, this compound is known.[7]
1H NMR (400 MHz, CDCl3): d=4.91 (d, J=7.6 Hz, 1H),
6.58 (dd, J=7.6, 15.6 Hz, 1H), 6.77 (d, J=15.6 Hz, 1H),
7.14–7.34 (m, 12H), 7.54 (d, J=7.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=53.7, 126.7, 126.8, 126.9, 128.1, 128.4,
128.5, 128.6, 129.7, 129.9, 132.3, 133.0, 134.7, 135.2, 141.8,
142.7; GC-MS (EI): [m/z]+ =339.2.
1
(400 MHz, CDCl3): d=5.40 (d, J=6.8 Hz, 1H), 6.28 (dd, J=
1.2, 16.0 Hz, 1H), 6.63 (dd, J=6.8, 15.6 Hz, 1H), 7.16–7.26
(m, 7H), 7.27–7.40 (m, 7H); 13C NMR (100 MHz, CDCl3):
d=50.2, 126.4, 126.6, 126.9, 127.4, 127.8, 128.5, 128.6, 128.8,
129.8, 130.2, 131.3, 132.0, 134.3, 137.2, 141.0, 142.1; GC-MS
(EI): [m/z]+ =304.1.
(E)-[3-(2-Bromophenyl)prop-1-ene-1,3-diyl]dibenzene
(3ad): Colorless oil, this compound was unknown. H NMR
(E)-1-Bromo-2-[3-(4-chlorophenyl)-3-phenylprop-1-enyl]-
benzene (3ea): Colorless oil, this compound was unknown.
1H NMR (400 MHz, CDCl3): d=4.90 (d, J=7.6 Hz, 1H),
6.53 (dd, J=7.6, 15.6 Hz, 1H), 6.72(d, J=15.6 Hz, 1H), 7.05–
7.34 (m, 10H), 7.52 (d, J=8.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=27.0, 53.6, 123.6, 126.8, 127.1, 127.5, 128.6, 128.7,
128.8, 130.0, 130.8, 132.4, 132.9, 134.9, 137.1, 141.8, 142.7;
GC-MS (EI): [m/z]+ =382.0.
(E)-But-1-ene-1,3-diyldibenzene (3aa’): Colorless oil, this
compound is known.[7,12a,17] 1H NMR (400 MHz, CDCl3): d=
1.39 (d, J=6.8 Hz, 3H), 3.53–3.64 (m, 1H), 6.27–6.36 (m,
2H), 7.08–7.29 (m, 10H); 13C NMR (100 MHz, CDCl3): d=
20.2, 41.5, 125.1, 125.2, 126.0, 126.3, 127.4, 134.2, 136.5,
144.6; GC-MS (EI): [m/z]+ =208.2.
1
(400 MHz, CDCl3): d=5.39 (d, J=6.8 Hz, 1H), 6.27 (dd, J=
1.2, 16.0 Hz, 1H), 6.60 (dd, J=6.8, 15.6 Hz, 1H), 7.04–7.08
(m, 1H), 7.16–7.24 (m, 7H), 7.26–7.29 (m, 3H), 7.30–7.35
(m, 2H), 7.56 (d, J=7.6 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=52.9, 125.3, 126.5, 126.7, 127.6, 127.6, 128.2,
128.6, 128.7, 129.0, 130.6, 131.5, 132.2, 133.3, 137.3, 142.2,
142.7; GC-MS (EI): [m/z]+ =348.1.
(E)-(3-para-Tolylprop-1-ene-1,3-diyl)dibenzene
(3ae):
Colorless oil, this compound is known.[7,12a] 1H NMR
(400 MHz, CDCl3): d=2.25 (s, 3H), 4.78 (d, J=7.6 Hz, 1H),
6.27 (d, J=15.6 Hz, 1H), 6.64 (dd, J=7.6, 16.0 Hz, 1H),
7.05 (s, 4H), 7.11–7.25 (m, 8H), 7.28–7.31 (m, 2H);
13C NMR (100 MHz, CDCl3): d=20.0, 52.8, 125.2, 125.3,
126.2, 127.4, 127.5, 127.5, 127.6, 128.1, 130.2, 131.8, 134.9,
136.3, 139.5, 142.7; GC-MS (EI): [m/z]+ =284.2.
(E)-4,4’-(But-1-ene-1,3-diyl)bis(methylbenzene)
(3bb’):
Colorless oil, this compound is known.[7,18] 1H NMR
(400 MHz, CDCl3): d=1.43 (d, J=6.8 Hz, 3H), 2.30 (s, 3H),
2.31 (s, 3H), 3.55–3.61 (m, 1H), 6.30 (dd, J=6.0, 16.0 Hz,
1H), 6.37 (d, J=16.0 Hz, 1H), 7.07–7.16 (m, 6H), 7.24 (d,
J=8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=21.0, 21.1,
21.3, 42.1, 126.0, 127.2, 128.2, 129.1, 134.4, 134.8, 135.6,
136.7, 142.8; GC-MS (EI): [m/z]+ =236.2.
(E)-Prop-2-ene-1,1,3-triyltribenzene (3af): White solid,
mp 102–1038C, this compound is known.[7,12a,17] 1H NMR
(400 MHz, CDCl3): d=4.89 (d, J=7.2 Hz, 1H), 6.34 (dd, J=
1.2, 15.6 Hz, 1H), 6.64–6.70 (m, 1H), 7.18–7.37 (m, 15H);
13C NMR (100 MHz, CDCl3): d=54.2, 126.4, 126.5, 127.4,
128.5, 128.6, 128.7, 131.5, 132.6, 137.3, 143.6; GC-MS (EI):
[m/z]+ =270.1.
(E)-4,4’-(3-Phenylprop-2-ene-1,1-diyl)bis(chlorobenzene)
(3ag): Colorless oil, this compound is known.[7,12a] 1H NMR
(400 MHz, CDCl3): d=4.84 (d, J=7.2 Hz, 1H), 6.32 (d, J=
15.6 Hz, 1H), 6.54–6.60 (m, 1H), 7.13–7.15 (m, 4H), 7.22–
7.38 (m, 9H); 13C NMR (400 MHz, CDCl3): d=52.8, 126.3,
127.6, 128.6, 128.7, 129.9, 131.4, 132.1, 132.5, 136.8, 141.5;
GC-MS (EI): [m/z]+ =339.3.
(E)-4,4’-(But-1-ene-1,3-diyl)bis(chlorobenzene)
(3cc’):
Colorless oil, this compound is known.[7,16b] 1H NMR
(400 MHz, CDCl3): d=1.43 (d, J=7.2 Hz, 3H), 3.57–3.63
(m, 1H), 6.26–6.36 (m, 2H), 7.16–7.19 (m, 2H), 7.23–7.30
(m, 6H); 13C NMR (100 MHz, CDCl3): d=21.1, 41.9, 127.4,
127.8, 128.6, 128.7, 128.8, 132.0, 132.8, 135.3, 135.8, 143.7;
GC-MS (EI): [m/z]+ =276.0.
(E)-2,2’-(But-1-ene-1,3-diyl)bis(chlorobenzene)
(3dd’):
Colorless oil, this compound is known.[7,18] 1H NMR
(400 MHz, CDCl3): d=1.47 (d, J=7.2 Hz, 3H), 4.17–4.25
(m, 1H), 6.34 (dd, J=6.4, 16.0 Hz, 1H), 6.86 (dd, J=1.6,
16.0 Hz, 1H), 7.11–7.25 (m, 4H), 7.28–7.38 (m, 3H), 7.29
(dd, J=2.0, 7.6 Hz, 1H); 13C NMR (400 MHz, CDCl3): d=
19.8, 38.6, 125.6, 126.7, 126.8, 127.1, 127.5, 128.1, 128.2,
129.6, 129.7, 132.9, 133.6, 135.7, 136.3, 142.6; GC-MS (EI):
[m/z]+ =276.1.
(E)-4,4’-(3-Phenylprop-2-ene-1,1-diyl)bis(fluorobenzene)
1
(3ah): Colorless oil, this compound was unknown. H NMR
(400 MHz, CDCl3): d=4.86 (d, J=7.6 Hz, 1H), 6.30 (d, J=
16.0 Hz, 1H), 6.59 (dd, J=7.2, 16.0 Hz, 1H), 6.97–7.03 (m,
4H), 7.14–7.25 (m, 5H), 7.28–7.38 (m, 4H); 13C NMR
(100 MHz, CDCl3): d=52.8, 115.5, 115.7, 126.5, 127.8, 128.8,
130.2, 130.3, 132.0, 132.3, 138.2 (JCÀF =206.8 Hz), 161.8
(JCÀF =243.5 Hz); GC-MS (EI): [m/z]+ =306.1.
(E)-1-Chloro-4-(1-phenyl-3-para-tolylallyl)benzene (3ba):
Colorless oil, this compound is known.[7] 1H NMR
(400 MHz, CDCl3): d=2.32 (s, 3H), 4.84 (d, J=7.6 Hz, 1H),
6.29 (d, J=15.6 Hz, 1H), 6.55 (dd, J=7.2, 15.6 Hz, 1H),
7.09–7.16 (m, 4H), 7.19–7.23 (m, 3H), 7.25–7.33 (m, 6H);
13C NMR (100 MHz, CDCl3): d=21.1, 53.5, 126.2, 126.6,
128.3, 128.6, 128.7, 129.2, 130.0, 130.9, 132.6, 133.2, 134.2,
137.3, 142.2, 143.1; GC-MS (EI): [m/z]+ =318.1.
(E)-4,4’-(3-Phenylprop-1-ene-1,3-diyl)bis(chlorobenzene)
(3ca): Colorless oil, this compound is known.[7] 1H NMR
(400 MHz, CDCl3): d=4.85 (d, J=7.6 Hz, 1H), 6.27 (dd, J=
1.2, 16.0 Hz, 1H), 6.59 (dd, J=7.6, 16.0 Hz, 1H), 7.14–7.34
(m, 13H); 13C NMR (100 MHz, CDCl3): d=53.5, 126.8,
127.5, 128.5, 128.6, 128.7, 130.0, 130.6, 132.4, 132.7, 133.1,
135.5, 141.8, 142.7; GC-MS (EI): [m/z]+ =338.1.
(E)-(3-para-Tolylbut-2-ene-1,1-diyl)benzene (3bi): White
solid; mp 82–848C, this compound is known.[7,19] 1H NMR
(400 MHz, CDCl3): d=1.29 (d, J=6.8 Hz, 3H), 2.25 (s, 3H),
3.45–3.53 (m, 1H), 6.12 (d, J=10.4 Hz, 1H), 7.03 (s, 4H),
7.11–7.19 (m, 7H), 7.23–7.33 (m, 3H); 13C NMR (400 MHz,
CDCl3): d=21.0, 22.4, 38.9, 126.8, 126.9, 127.0, 127.3, 128.1,
128.2, 129.2, 129.8, 134.4, 135.5, 139.9, 140.2, 142.5, 143.2;
GC-MS (EI): [m/z]+ =298.2.
(3-Methylbut-2-ene-1,1-diyl)dibenzene (3ff): Colorless oil,
this compound is known.[12b] 1H NMR (400 MHz, CDCl3):
d=1.71 (s, 3H), 1.78 (s, 3H), 4.88 (d, J=9.6 Hz, 1H), 5.61–
5.64 (m, 1H), 7.15–7.29 (m, 10H); 13C NMR (100 MHz,
CDCl3): d=18.1, 26.0, 49.5, 126.0, 127.4, 128.3, 128.4, 132.5,
145.2; GC-MS (EI): [m/z]+ =222.2.
(E)-9-Styryl-9H-fluorene (5ja): White solid; mp 99–
1018C, this compound is known.[7] 1H NMR (400 MHz,
2514
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Adv. Synth. Catal. 2014, 356, 2506 – 2516

FULL PAPERS
Metal-Free and Recyclable Route to Synthesize Polysubstituted Olefins
CDCl3): d=4.65 (d, J=9.2 Hz, 1H), 6.04 (dd, J=8.8,
15.6 Hz, 1H), 6.89 (d, J=16.0 Hz, 1H), 7.21–7.25 (m, 1H),
7.29–7.34 (m, 4H), 7.38–7.42 (m, 4H), 7.51 (d, J=7.2 Hz,
2H), 7.79 (d, J=7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=52.4, 119.9, 121.5, 122.9, 125.4, 126.3, 127.2, 127.4, 127.5,
128.6, 129.0, 132.5, 146.1; GC-MS (EI): [m/z]+ =268.2.
CDCl3): d=54.1, 124.6, 126.2, 126.6, 127.3, 128.5, 128.6,
129.7, 130.2, 134.2, 134.5, 139.2, 143.2; GC-MS (EI):
AHCTUNGTRENNUNG
[m/z]+ =304.1.
(E)-[3-(2-Chlorophenyl)prop-2-ene-1,1-diyl]dibenzene
(5ff): White solid; mp 80–818C, this compound was un-
1
known. H NMR (400 MHz, CDCl3): d=4.94 (d, J=7.6 Hz,
(E)-5-Styryl-10,11-dihydro-5H-dibenzo
[a,d]cycloheptene
1H), 6.64 (dd, J=8.0, 16.0 Hz, 1H), 6.79 (d, J=16.0 Hz,
1H), 7.14–7.34 (m, 13H), 7.55–7.57 (m, 1H); 13C NMR
(100 MHz, CDCl3): d=54.4, 126.6, 126.8, 126.9, 127.8, 128.4,
128.5, 128.6, 129.7, 133.0, 135.3, 135.5, 143.3; GC-MS (EI):
[m/z]+ =304.1.
(5ka): Colorless oil, this compound is known.[7] 1H NMR
(400 MHz, CDCl3): d=2.80–2.89 (m, 2H), 3.39–3.48 (m,
2H), 4.78 (dd, J=2.4, 4.0 Hz, 1H), 5.99 (dd, J=2.0, 15.6 Hz,
1H), 6.62 (dd, J=4.4, 16.0 Hz, 1H), 7.11–7.26 (m, 13H);
13C NMR (100 MHz, CDCl3): d=32.8, 56.5, 126.3, 127.2,
128.5, 130.0, 130.5, 130.7, 134.9, 137.4, 139.9, 140.2; GC-MS
(EI): [m/z]+ =296.2.
(E)-[3-(4-Nitrophenyl)prop-2-ene-1,1-diyl]dibenzene
(5fg): Yellow solid; mp 128–1308C, this compound was un-
1
known. H NMR (400 MHz, CDCl3): d=4.86 (d, J=7.2 Hz,
A
1H), 6.32 (d, J=15.6 Hz, 1H), 6.80 (dd, J=7.6, 16.0 Hz,
1H), 7.14–7.19 (m, 6H), 7.24–7.27 (m, 4H), 7.39–7.41 (m,
2H), 8.07 (d, J=8.8 Hz, 2H); 13C NMR (400 MHz, CDCl3):
d=53.2, 122.9, 125.7, 127.5, 127.6, 128.5, 131.3, 136.6, 141.5,
142.6, 145.7; GC-MS (EI): [m/z]+ =315.4.
less oil, this compound is known.[12a] 1H NMR (400 MHz,
CDCl3): d=4.38–4.41 (m, 1H), 6.44–6.53 (m, 4H), 7.20–7.41
(m, 15H); 13C NMR (100 MHz, CDCl3): d=51.6, 126.3,
126.6, 127.3, 128.1, 128.5, 128.6, 130.8, 131.8, 137.3, 142.8;
GC-MS (EI): [m/z]+ =296.4.
(E)-2-(3,3-Diphenylprop-1-enyl)naphthalene (5fh): White
solid; mp 106–1078C, this compound was unknown.
1H NMR (400 MHz, CDCl3): d=4.96 (d, J=7.6 Hz, 1H),
6.51 (d, J=16.0 Hz, 1H), 6.81 (dd, J=7.6, 16.0 Hz, 1H),
7.22–7.26 (m, 3H), 7.29–7.35 (m, 7H), 7.39–7.46 (m, 2H),
7.62 (dd, J=1.6, 8.4 Hz, 1H), 7.69 (s, 1H), 7.75–7.79 (m,
3H); 13C NMR (100 MHz, CDCl3): d=54.3, 123.7, 125.7,
126.1, 126.2, 126.5, 127.7, 127.9, 128.1, 128.5, 128.7, 131.6,
132.9, 133.1, 133.6, 134.7, 143.5; GC-MS (EI): [m/z]+ =320.4.
(E)-But-2-ene-1,1,3-triyltribenzene (5fi): Colorless oil, this
compound is known.[7,12a,b] 1H NMR (400 MHz, CDCl3): d=
2.12 (s, 3H), 5.07 (d, J=9.2 Hz, 1H), 6.24 (d, J=9.6 Hz,
1H), 7.17–7.37 (m, 13H), 7.42 (d, J=7.2 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=16.4, 50.1, 126.0, 126.3, 127.0, 128.3,
128.5, 128.6, 130.8, 135.7, 143.6, 144.7; GC-MS (EI):
(E)-Pent-1-en-4-yne-1,3,5-triyltribenzene (5ma): Yellow
oil, this compound is known.[20] 1H NMR (400 MHz, CDCl3):
d=4.76 (d, J=6.0 Hz, 1H), 6.35 (dd, J=6.4, 15.6 Hz, 1H),
6.78 (dd, J=1.2, 15.6 Hz, 1H), 7.21–7.25 (m, 1H), 7.28–7.34
(m, 6H), 7.35–7.41 (m, 4H), 7.48–7.53 (m, 4H); 13C NMR
(100 MHz, CDCl3): d=41.2, 85.4, 88.8, 123.4, 126.5, 127.1,
127.5, 127.7 128.0, 128.2, 128.5, 128.7, 129.6, 130.4, 131.7,
136.8, 140.3; GC-MS (EI): [m/z]+ =294.1.
1-Cinnamyl-4-methoxybenzene (5na): Colorless oil, this
compound is known.[21] 1H NMR (400 MHz, CDCl3): d=
3.48 (d, J=3.2 Hz, 2H), 3.78 (s, 3H), 6.30–6.45 (m, 2H),
6.83–6.87 (m, 2H), 7.14–7.23 (m, 3H), 7.26–7.36 (m, 4H);
13C NMR (100 MHz, CDCl3): d=38.4, 55.3, 113.9, 126.1,
127.0, 128.5, 129.6, 129.7, 130.7, 132.1, 137.5, 158.0; GC-MS
(EI): [m/z]+ =224.1.
AHCTUNGTRENNUNG
[m/z]+ =284.2.
(E)-(3-para-Tolylprop-2-ene-1,1-diyl)dibenzene
(5fb):
Prop-1-ene-1,1,3,3-tetrayltetrabenzene (5fj): White solid;
Colorless oil, this compound is known.[7,12a] 1H NMR
(400 MHz, CDCl3): d=2.32 (s, 3H), 4.88 (d, J=7.6 Hz, 1H),
6.31 (d, J=15.6 Hz, 1H), 6.61 (dd, J=7.6, 16.0 Hz, 1H),
7.10 (d, J=8.0 Hz, 2H), 7.17–7.32 (m, 12H); 13C NMR
(100 MHz, CDCl3): d=21.2, 54.2, 126.2, 126.4, 128.5, 128.7,
129.2, 131.3, 131.6, 134.5, 137.1, 143.7; GC-MS (EI):
mp: 131–1328C, this compound is known.[7,12a,b] 1H NMR
(400 MHz, CDCl3): d=4.81 (d, J=10.8 Hz, 1H), 6.54 (d, J=
10.8 Hz, 1H), 7.15–7.38 (m, 20H); 13C NMR (100 MHz,
CDCl3): d=50.5, 126.3, 127.2, 127.3, 127.5, 128.1, 128.3,
128.4, 128.5, 129.8, 131.0, 139.7, 141.6, 142.2, 144.5; GC-MS
(EI): [m/z]+ =346.3.
A
2-Benzhydryl-1H-indene (5fk): White solid; mp 109–
1108C, this compound was unknown. 1H NMR (400 MHz,
CDCl3): d=3.28 (s, 2H), 5.15 (s, 1H), 6.24 (s, 1H), 7.01–7.05
(m, 1H), 7.13–7.26 (m, 13H); 13C NMR (100 MHz, CDCl3):
d=41.1, 53.8, 120.6, 123.6, 124.3, 126.4, 126.6, 128.5, 129.0,
130.2, 143.1, 143.5, 144.9, 152.3; GC-MS (EI): [m/z]+ =282.1.
(E)-3-(3,3-Diphenylprop-1-enyl)-1,2-dihydronaphthalene
(5fl): White solid; mp 78–808C, this compound is
known.[7,12b] 1H NMR (400 MHz, CDCl3): d=2.26–2.29 (m,
2H), 2.80–2.85 (m, 2H), 4.90 (s, 1H), 5.97 (s, 1H), 6.91 (d,
J=3.2 Hz, 1H), 7.09 (s, 3H), 7.23–7.32 (m, 10H); 13C NMR
(100 MHz, CDCl3): d=28.0, 28.4, 58.5, 125.8, 126.1, 126.4,
126.5, 126.6, 127.2, 128.3, 129.4, 134.5, 134.6, 142.0, 143.7;
GC-MS (EI): [m/z]+ =322.2.
(5fc): White solid; mp: 86–878C, this compound is
known.[12a] 1H NMR (400 MHz, CDCl3): d=4.88 (d, J=
7.2 Hz, 1H), 6.27 (d, J=15.2 Hz, 1H), 6.66 (dd, J=7.6,
16.0 Hz, 1H), 7.21–7.41 (m, 14H); 13C NMR (100 MHz,
CDCl3): d=54.2, 121.0, 126.6, 127.9, 128.6, 128.7, 130.3,
131.6, 133.5, 136.2, 143.2; GC-MS (EI): [m/z]+ =348.1.
(E)-[3-(4-Chlorophenyl)prop-2-ene-1,1-diyl]dibenzene
(5fd): White solid; mp 72–738C, this compound is
known.[7,17] 1H NMR (400 MHz, CDCl3): d=4.88 (d, J=
7.6 Hz, 1H), 6.28 (d, J=16.8 Hz, 1H), 6.65 (dd, J=7.6,
15.6 Hz, 1H), 7.21–7.33 (m, 14H); 13C NMR (100 MHz,
CDCl3): d=54.2, 126.6, 127.5, 128.5, 128.6, 128.7, 130.3,
132.9, 133.3, 135.8, 143.3; GC-MS (EI): [m/z]+ =304.1.
(E)-[3-(3-Chlorophenyl)prop-2-ene-1,1-diyl]dibenzene
(5fe): White solid; mp 75–768C, this compound was un-
[(2-Phenylcyclohex-1-enyl)methylene]dibenzene
(5fm):
White solid; mp 124–1268C, this compound is known.[12a]
1H NMR (400 MHz, CDCl3): d=1.69–1.72 (m, 4H), 1.93–
1.95 (m, 2H), 2.35–2.36 (m, 2H), 5.01 (s, 1H), 7.06–7.08 (m,
4H), 7.12–7.15 (m, 2H), 7.17–7.29 (m, 9H); 13C NMR
(100 MHz, CDCl3): d=23.0, 23.3, 26.0, 33.2, 53.3, 125.9,
1
known. H NMR (400 MHz, CDCl3): d=4.89 (d, J=7.6 Hz,
1H), 6.28 (dd, J=1.2, 15.6 Hz, 1H), 6.69 (dd, J=7.6,
15.6 Hz, 1H), 7.16–7.36 (m, 14H); 13C NMR (100 MHz,
Adv. Synth. Catal. 2014, 356, 2506 – 2516
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FULL PAPERS
Feng Han et al.
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GC-MS (EI): [m/z]+ =324.1.
[(2-Methylcyclopent-1-enyl)methylene]dibenzene (5fn):.
Colorless oil, this compound is known.[12a] 1H NMR
(400 MHz, CDCl3): d=1.70 (s, 3H), 1.74–1.80 (m, 2H), 2.20
(brs, 2H), 2.36 (t, J=6.8 Hz, 2H), 5.16 (s, 1H), 7.12–7.19
(m, 6H), 7.25 (t, J=7.2 Hz, 4H); 13C NMR (100 MHz,
CDCl3): d=14.3, 21.9, 34.3, 38.8, 49.9, 126.1, 128.2, 129.1,
134.7, 135.7, 143.5; GC-MS (EI): [m/z]+ =248.2.
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(400 MHz, CDCl3): d=1.56 (brs, 4H), 1.68 (brs, 5H), 2.07
(brs, 2H), 5.34 (s, 1H), 7.11 (d, J=8.0 HZ, 3H), 7.17 (t, J=
7.20 Hz, 3H), 7.25 (t, J=7.6 Hz, 4H); 13C NMR (100 MHz,
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Oxybis(methanetriyl)tetrabenzene (5a): White solid; mp
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CDCl3): d=5.39 (s, 2H), 7.22–7.37 (m, 20H); 13C NMR
(100 MHz, CDCl3): d=79.9, 127.3, 127.4, 128.4, 142.2; GC-
MS (EI): [m/z]+ =350.0.
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Acknowledgements
We are grateful to the National Science Foundation of China
(No. 21303231, 21173241 and 21133011), the National Basic
Research Program of China (2011CB201404) and the Chi-
nese Academy of Sciences for support of this research.
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Adv. Synth. Catal. 2014, 356, 2506 – 2516