Mechanistic insight into transition metal-catalyzed reaction of enynal/enynone with alkenes: Metal-dependent reaction pathway

Article abstract of DOI:10.1021/jo500838x

A systematic study of the transition metal-catalyzed reaction of enynal/enynone with alkenes has been reported. It was found that the reaction has two metal-dependent reaction pathways. One led to the formation of 1,2-DHN, while another led to cyclic-o-QDM.

Full text of DOI:10.1021/jo500838x

Article
pubs.acs.org/joc
Mechanistic Insight into Transition Metal-Catalyzed Reaction of
Enynal/Enynone with Alkenes: Metal-Dependent Reaction Pathway
Shifa Zhu,* Hua Huang, Zhicai Zhang, Tongmei Ma,* and Huanfeng Jiang
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 Guangdong, People’s
Republic of China
*
S Supporting Information
ABSTRACT: A systematic study of the transition metal-
catalyzed reaction of enynal/enynone with alkenes has been
reported. It was found that the reaction has two metal-
dependent reaction pathways. One led to the formation of 1,2-
DHN, while another led to cyclic-o-QDM.
INTRODUCTION
Scheme 2. Our Previous Work
■
Enynal/enynone is a versatile building block for the
construction of the benzannulated system. Among the different
methods, the transition metal-catalyzed reaction of enynal/
enynone with alkenes is one of the most efficient and
1
straightforward ways to construct aphthalene derivatives. For
example, Asao and Yamamoto synthesized a series of
functionalized 1,2-dihydronaphthalene through Cu(OTf)2-
catalyzed [4 + 2] cycloaddition of enynal with alkenes (Scheme
1
b
1).
Scheme 1. Copper-Catalyzed Reaction of Enynals/Enynones
with Alkenes
the desired propeller-like molecule II, was isolated as the only
product (eq 5). Interestingly, 1,2-DHN 4 could not be oxidized
into naphthalene 5 with 1,4-BQ as the oxidant (eq 6). It
indicated that naphthalene 5 may not simply come from the
oxidation of 1,2-DHN 4.
Through carefully controlling the reaction conditions, it was
found that the desired propeller-like product 6a was actually
generated during the reaction course. However, this molecule
was unstable and would aromatize into naphthalene 5a
immediately after treatment with silica gel/air (Scheme 5).
The propeller-like structure of 6a was confirmed by the X-ray
diffraction analysis of its single crystal (see the SI).
Recently, we reported a gold-catalyzed reaction of enynal/
enynone with different alkenes to synthesize differen2t
structurally unique polycyclic structures I−III (Scheme 2).
However, the reactions worked efficiently only when high-
reactive alkenes, norborenes, and 1,3-dienes were used as the
substrates (Scheme 2).
The reaction was believed to proceed through the gold-
catalyzed tandem Diels−Alder reactions via trapping of the key
3
,4
intermediate cyclic o-quinodimethane
(cyclic-o-QDM), a
highly reactive species (Scheme 3).
When styrene was tested as the substrate, however, the
expected propeller-like molecule I was not formed. 1,2-
Dihydronaphthalene (1,2-DHN) 4 was formed as the product
instead (Scheme 4, eq 4). It seems that the reaction is identical
The Cu(OTf) -catalyzed reaction of 1a, 2a, and 3a under
2
similar conditions resulted in a complex system. Both adducts
of 5a and 6a were not detected in the reaction system (Scheme
6
). It indicated that copper-catalyzed and gold-catalyzed
to the Cu(OTf) -catalyzed system reported by Asao and
2
1b
Yamamoto (Scheme 1). Trying to trap the proposed cyclic-o-
QDM intermediate by addition of 1,4-benzoquinone (1,4-BQ)
as the more reactive dienophile also failed. Naphthalene 5, not
Received: April 14, 2014
©
XXXX American Chemical Society
A
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 3. Possible Reaction Mechanism
were investigated. Styrene 2a and tetracyanoethylene (TCE) 3b
were chosen as the dienophiles for the model reactions (Table
1
). Among the different metal salts being tested, silver, copper,
a
Table 1. Screen Different Catalytic Conditions
entry
cat. (5 mol %)
add. (10 mol %)
yield (4b)
yield (6b)
1
2
3
4
5
6
7
8
AgSbF6
69%
55%
44%
72%
13%
32%
33%
19%
AgOTf
AgNTf2
Cu(OTf)2
CuCl •2H O
2
2
ZnCl2
ZnI2
FeCl3
b
9
CdCl2
Scheme 4
b
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
MnCl2
b
b
NiCl2
CoCl2
InCl3
CrCl2
PtCl2
HgI2
15%
40%
24%
28%
32%
32%
41%
57%
52%
81%
67%
46%
42%
KAuCl •2H O
4
2
PicAuCl2
IMes-AuCl3
IMes-AuCl
IMes-AuCl
SIMes-AuCl
IPr-AuCl
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
SIPr-AuCl
IMes-AuCl
c
d
5
93%
6
Scheme 5. Gold-Catalyzed Reaction of Enynal with Styrene
and 1,4-BQ
a
Unless otherwise noted, the reactions were performed in DCE at 80
C for 24 h using 5 mol % catalyst and 10 mol % additive under N , 1/
/3 = 1:5:1. [1] = 0.1 M. The yield was determined by H NMR with
°
2
2
1
MeNO as internal standard. Pic: 2-picolinate, IMes: 1,3-dimesityli-
2
midazol-2-ylidene; SIMes: 1,3-dimesitylimidazolin-2-ylidene; IPr: 1,3-
bis(2,6-diisopropylphenyl)-imidazol-2-ylidene; SIPr: 1,3-bis(2,6-
b
c
diisopropylphenyl)imidazolin-2-ylidene. No reaction. 1/2/3 =
d
1
:5:2. Isolated yield.
zinc, and iron salts furnished 1,2-DHN 4b in 13−72% yields
entries 1−8). Silver and copper salts functioned better than
zinc and iron. The yield is up to 72% when Cu(OTf) was used
reactions of enynal with alkenes might experience different
reaction mechanisms.
(
2
1b
as catalyst, which is consistent with the literature results.
CdCl , MnCl , NiCl , and CoCl were inefficient for this
RESULTS AND DISCUSSION
To figure out the underlying reaction mechanism, a systematic
study was then carried out. Initially, different metal catalysts
■
2
2
2
2
transformation (entries 9−12). InCl gave the mixture of 4b
3
and 6b, with the yields being 15% and 40%, respectively (entry
1
3). The desired product 6b could be obtained as the sole
Scheme 6. Copper-Catalyzed Reaction of Enynal with
Styrene and 1,4-BQ
product when chromium (CrCl ), platinum (PtCl ), mercury
2
2
(
HgI ), and gold (KAuCl *2H O) salts were used as catalysts,
2 4 2
albeit in modest yields (24−32%, entries 14−17). Comparing
with the inorganic gold salts, the organic gold-complex gave
superior results (entries 18−20). For instance, 2-picolinate and
N-heterocyclic carbene (NHC) supported gold complexes,
PicAuCl , IMes-AuCl , and IMes-AuCl, could catalyze the
2
3
B
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
a
Table 2. Substrate Scopes
a
b
The reaction was performed at 80 °C for 24 h using 5 mol % cat and 10 mol % add under N ; 1:2:3 = 1:5:2, [1] = 0.1 M, isolated yield. Purified by
2
c
crystallization. The stereochemistry was determined by its NOE spectrum (see the SI).
reaction smoothly to furnish the corresponding product 6b,
with the yields ranging from 41% to 57% (entries 18−20). The
functioned better than the other three. The yield of 6b was
improved to 81% for the combination of IMes-AuCl/
Selectfluor (entry 21). Increasing the amount of TCE 3b
could improve the yield further (93%, entry 25). The reaction
did not occur without NHC-AuCl (entry 26).
With the optimized reaction conditions (Table 1, entry 25)
in hand, the substrate scope was then examined. As summarized
in Table 2, the catalytic process could be successfully applied to
a variety of enynals/enynones 1 and alkenes 2. For example, in
addition to styrene 2a, various styrene derivatives could be
effectively reacted with enynal/enynone 1 as well (Table 2, 6a-
6n). The reaction was sensitive to the steric hindrance of the
alkenes. For example, bulky 2,5-dimethylstyrene and 2,4,6-
trimethylstyrene gave the products 6g and 6h only in 32% and
NHC-Au(III) complex proved to be better than PicAuCl and
2
NHC-Au(I). In our previous work, it was found that the
combination of NHC-Au(I)/Selectfluor was a more reliable
and efficient system than the NHC-Au(III) one for the reaction
2
,5
of enynal/enynone with alkenes.
It was proposed that
Selectfluor severed as a mild organic oxidant to oxidize NHC-
+
Au(I) into NHC-Au(III) , which is the real catalyst for the
reaction. Inspired by these facts, four different NHC-AuCl/
Selectfluor (1:2) combinations was then tested (entries 21−
24). As expected, a significant positive effect was observed
when the combination of NHC-AuCl/Selectfluor (1:2) was
applied. Among four different NHC-complexes, IMes-AuCl
C
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 7. Possible Pathways of Metal-Catalyzed Reaction of Enynal with Styrenes
2
9% yields, respectively. Electron-rich alkenes were better
To further prove the above reaction mechanism, especially
the reaction pathway of the cyclic-o-QDM, two control
reactions were then carried out. As shown in Scheme 7, 1,2-
DHN 4a would be formed when the reactions were set without
the dienophile or dioxygen. Therefore, the first set control
reactions without addition of the electron-deficient olefins were
substrates than the electron-poor ones (electron-rich: 6a-6f;
electron-poor: 6i-6m).
For the extremely electron-deficient 2,3,4,5,6-pentafluoros-
tyrene, the yield was only 12% (6m). Indene, a cyclic alkene,
was an efficient substrate for this transformation, with the yield
being almost quantitative (6n). In addition to styrene
derivatives, the aliphatic alkene could be used as the substrate
as well, giving the desired product 6o in 44% yield. Comparing
with the styrene derivatives 2, the reaction was less sensitive to
the properties of enynals/enynones 1 (6p-6x). For example,
both the enynals substituted with electron-donating and
electron-withdrawing groups furnished the desired products
in good to excellent yields (6p-6v). For enynal bearing the alkyl
group, the reactions proceed smoothly as well, giving the
product 6w in 99% yield. For the enynal with a cyclohexenyl
group, the product 6x could be obtained in 56% yield. In
addition to 1,4-BQ and TCE, N-methyl maleimide could be
used as a good dienophile as well (6y). However, acrylonitrile
and dimethyl acetylene-dicarboxylate were not efficient
dienophiles for this reaction (6z, 6aa). For all the products 6
in Table 2, only the endoadduct isomers were detected.
Based on the above results, the reaction mechanism was then
proposed (Scheme 7). The coordination of the triple bond of
enynal 1a to [M] enhanced the electrophilicity of alkyne, and
the subsequent nucleophilic attack of the carbonyl oxygen to
the electron-deficient alkyne would form the intermediate
then conducted under the N atmosphere. As shown in Table 3,
2
a variety of 1,2-DHNs 4 could be generated in good to
excellent yields as expected.
a
Table 3. Control Reaction
a
The reaction was performed at 80 °C for 24 h using 5 mol % cat., 10
6
pyrylium A. A Diels−Alder reaction between styrene and
mol % Selectfluor, and 1.0 equiv of H O under N ; 1:2 = 1:5; [1] =
0.05 M, isolated yield; the stereochemistry was determined by H
NMR.
2
2
1
pyrylium A then occurred to furnish the key intermediate B.
Two different possible reaction pathways would then follow.
Path a): β-H elimination of intermediate B led to the formation
of 1,2-DHN 4a; Path b): δ-metal elimination of intermediate B
led to the formation of the cyclic-o-QDM. In the absence of
dienophile or dioxygen, the 1,5-H shift would happen to furnish
As shown in Scheme 7, a peroxide 7a would be generated if
the cyclic-o-QDM was trapped by the dioxygen. Therefore,
another control reaction was then performed under the oxygen
atmosphere. As expected, the aromatization product naph-
thalene 5b was isolated in 71% yield when enynone 1b reacted
1
,2-DHN 4a. While in the presence of dienophile or dioxygen,
the cyclic-o-QDM could be trapped through the second Diels−
Alder reaction to form the adducts 6 and 7a. Among them, the
unstable peroxide 7a would decompose into naphthalene 5a.
Based on the results shown in Tables 1 and 2, the reaction
pathway is metal-dependent. When silver, copper, zinc, and
iron salts were used as the catalysts, reaction path a was
followed. While chromium, platinum, mercury, and gold salts
were applied as the catalysts, reaction path b was followed.
with styrene 2a (Scheme 8). Furthermore, the key intermediate
1
7
b, an unstable peroxide, could be detected by the H NMR
spectrum and HRMS analysis of the crude reaction mixture
(see the SI).
D
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
7
a
2
-(Phenylethynyl)benzaldehyde (1a). Eluent petroleum ether/
Scheme 8. Control Reaction under Oxygen Atmosphere
1
ethyl acetate (20/1), yellow oil, yield (198 mg, 96%). H NMR (400
MHz, CDCl ) δ 10.65 (s, 1H), 7.95 (d, J = 7.8 Hz, 1H), 7.64 (d, J =
3
7
(
.7 Hz, 1H), 7.60−7.54 (m, 3H), 7.44 (t, J = 7.5 Hz, 1H), 7.40−7.34
m, 3H); 13C NMR (100 MHz, CDCl ) δ 191.7, 135.9, 133.8, 133.2,
3
1
31.7, 129.1, 128.6, 128.5, 127.3, 126.9, 122.4, 96.4, 85.0.
7b
1
-[2-(Phenylethynyl)phenyl]ethanone (1b). Eluent petroleum
1
ether/ethyl acetate (20/1), yellow oil, yield (210 mg, 95%). H NMR
(
400 MHz, CDCl ) δ 7.76 (dd, J = 7.8, 1.1 Hz, 1H), 7.63 (dd, J = 7.7,
3
0
.8 Hz, 1H), 7.55 (ddd, J = 8.2, 4.0, 2.3 Hz, 2H), 7.48 (td, J = 7.6, 1.2
1
3
Hz, 1H), 7.43−7.39 (m, 1H), 7.39−7.34 (m, 3H), 2.80 (s, 3H);
NMR (100 MHz, CDCl ) δ 200.4, 140.8, 133.9, 131.5, 131.3, 128.8,
C
3
1
28.7, 128.5, 128.3, 122.9, 121.7, 95.1, 88.5, 30.0.
7a
2
-(p-Tolylethynyl)benzaldehyde (1c). Eluent petroleum ether/
1
ethyl acetate (20/1), yellow solid, yield (202 mg, 92%). H NMR (400
MHz, CDCl ) δ 10.62 (s, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.56 (d, J =
3
7
.7 Hz, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 7.2 Hz, 2H), 7.35 (t,
1
3
J = 7.5 Hz, 1H), 7.13 (d, J = 7.6 Hz, 2H), 2.32 (s, 3H); C NMR (100
MHz, CDCl ) δ 191.7, 139.4, 135.8, 133.8, 133.2, 131.7, 129.4, 128.4,
3
1
27.2 (2C), 119.4, 96.8, 84.5, 21.6.
-[(4-Methoxyphenyl)ethynyl]benzaldehyde (1d). Eluent petro-
7
a
CONCLUSIONS
2
■
1
leum ether/ethyl acetate (20/1), yellow solid, yield (233 mg, 98%). H
In conclusion, we have conducted a systematic study of the
transition metal-catalyzed reaction of enynals/enynones with
alkenes. It was found that the reactions have two metal-
dependent reaction pathways. The reactions started with the
nucleophilic attack of the carbonyl oxygen to the alkyne, which
was activated by the coordination of metal catalysts, forming
the intermediate pyrylium A. It subsequently reacted with
alkenes through the Diels−Alder reactions to form the bridge
intermediate B. When silver, copper, zinc, and iron salts were
used as the catalysts, a β-H elimination of the intermediate B
led to the formation of 1,2-DHN 4. When chromium, platinum,
mercury, and gold salts were applied as the catalysts, the δ-
metal elimination of the intermediate B led to the formation of
the cyclic-o-QDM. The highly reactive transient species could
rearrange to 1,2-DHN 4 through the 1,5-H shift. Furthermore,
the cyclic-o-QDM was also a good diene which could be
trapped by the dienophiles (electron deficient alkenes/alkynes
or dioxygen molecules) through the Diels−Alder reactions. We
believe such metal-dependent reaction mechanisms would
render useful information to the organometallic chemists in
understanding the catalytic behavior of different transition
metals.
NMR (400 MHz, CDCl ) δ 10.64 (s, 1H), 7.92 (d, J = 7.6 Hz, 1H),
3
7
2
.61 (d, J = 7.4 Hz, 1H), 7.55 (t, J = 7.4 Hz, 1H), 7.50 (d, J = 7.8 Hz,
H), 7.41 (t, J = 7.3 Hz, 1H), 6.90 (d, J = 7.8 Hz, 2H), 3.83 (s, 3H);
1
3
C NMR (100 MHz, CDCl ) δ 191.9, 160.3, 135.7, 133.8, 133.3,
3
1
33.1, 128.2, 127.4, 127.2, 114.4, 114.2, 96.6, 83.8, 55.4.
7a
2
-[(3-Fluorophenyl)ethynyl]benzaldehyde (1e). Eluent petrole-
1
um ether/ethyl acetate (20/1), yellow oil, yield (194 mg, 87%). H
NMR (400 MHz, CDCl ) δ 10.50 (s, 1H), 7.83 (d, J = 7.9 Hz, 1H),
3
7.54−7.45 (m, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.23 (dd, J = 5.3, 4.6 Hz,
1
3
2H), 7.14 (dd, J = 8.7, 1.8 Hz, 1H), 7.01−6.95 (m, 1H); C NMR
(100 MHz, CDCl
133.3, 130.2 (d, J = 8.6 Hz), 129.0, 127.6 (d, J = 3.1 Hz), 127.5, 126.2,
) δ 191.3, 162.4 (d, J = =247.2 Hz), 136.0, 133.8,
3
1
9
24.2 (d, J = 9.4 Hz), 118.5 (d, J = 22.9 Hz), 116.4 (d, J = 21.2 Hz),
4.8 (d, J = 3.4 Hz), 85.8; 19F NMR (376 MHz, CDCl ) δ −112.4.
3
7a
2
-[(4-Chlorophenyl)ethynyl]benzaldehyde (1f). Eluent petrole-
1
um ether/ethyl acetate (20/1), yellow solid, yield (218 mg, 91%). H
NMR (400 MHz, CDCl ) δ 10.60 (s, 1H), 7.94 (d, J = 7.5 Hz, 1H),
3
7
7
1
.59 (ddd, J = 14.9, 7.7, 4.1 Hz, 2H), 7.47 (dd, J = 14.2, 7.9 Hz, 3H),
13
.35 (d, J = 8.5 Hz, 2H); C NMR (100 MHz, CDCl ) δ 191.4, 135.9,
3
35.2, 133.8, 133.3, 132.9, 128.9 (2C), 127.5, 126.4, 120.8, 95.1, 85.9.
7
a,c
4-Methyl-2-(phenylethynyl)benzaldehyde (1g).
leum ether/ethyl acetate (20/1), yellow solid, yield (196 mg, 89%). H
NMR (400 MHz, CDCl ) δ 10.58 (s, 1H), 7.84 (d, J = 8.0 Hz, 1H),
.56 (dd, J = 3.9, 1.6 Hz, 2H), 7.45 (s, 1H), 7.38 (d, J = 1.8 Hz, 3H),
Eluent petro-
1
3
7
13
EXPERIMENTAL SECTION
7.25 (s, 1H), 2.41 (s, 3H); C NMR (100 MHz, CDCl
3
) δ 191.4,
44.9, 133.7, 133.6, 131.7, 129.7, 129.0, 128.5, 127.4, 126.9, 122.5,
5.9, 85.1, 21.6.
5-Methoxy-2-(phenylethynyl)benzaldehyde (1h). Eluent petro-
■
1
9
General Information. All reactions were carried out under an
inert atmosphere of dry N in a Schlenk tube, and solvents were
2
7c
1
13
19
purified by standard methods. H, C, and F NMR spectra were
recorded on 400 MHz, 100 MHz, and 376 MHz spectrometers,
respectively. H NMR and C NMR chemical shifts were determined
1
leum ether/ethyl acetate (20/1), yellow solid, yield (223 mg, 94%). H
1
13
NMR (400 MHz, CDCl ) δ 10.59 (s, 1H), 7.53 (d, J = 7.4 Hz, 3H),
3
1
3
19
7.40 (s, 1H), 7.34 (s, 3H), 7.11 (d, J = 8.5 Hz, 1H), 3.84 (s, 3H);
C
relative to internal standard TMS at δ 0.0, and F NMR chemical
shifts were determined relative to CFCl3 as external standard.
Chemical shifts (δ) are reported in ppm, and coupling constants (J)
are in Hertz (Hz). The following abbreviations were used to explain
the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br = broad. The mass analyzer type used for the HRMS is
Fourier transform ion cyclotron resonance mass spectrometry (FT-
ICR-MS). All reagents were used as received from commercial sources,
unless specified otherwise, or prepared as described in the literature.
General Procedure for the Preparation of 1a−k. PdCl (PPh )
NMR (100 MHz, CDCl ) δ 191.5, 159.8, 137.2, 134.6, 131.5, 128.8,
3
1
28.5, 122.7, 121.7, 119.6, 109.9, 94.9, 84.9, 55.6.
7c
5
-Fluoro-2-(phenylethynyl)benzaldehyde (1i). Eluent petroleum
1
ether/ethyl acetate (20/1), yellow solid, yield (211 mg, 95%). H
NMR (400 MHz, CDCl ) δ 10.56 (s, 1H), 7.58 (t, J = 6.9 Hz, 2H),
3
7
.54−7.50 (m, 2H), 7.35 (d, J = 4.9 Hz, 3H), 7.24 (dd, J = 10.9, 5.3
13
Hz, 1H); C NMR (100 MHz, CDCl ) δ 190.3, 162.4 (d, J = 252.6
3
Hz), 137.8 (d, J = 6.6 Hz), 135.3 (d, J = 7.6 Hz), 131.7, 129.2, 128.6,
123.0 (d, J = 3.4 Hz), 122.2, 121.3 (d, J = 22.8 Hz), 113.7 (d, J = 23.0
2
3 2
Hz), 96.1, 83.9; 19F NMR (376 MHz, CDCl
) δ −108.9.
3
7d
(
3% mmol) and CuI (5% mmol) were added to a solution of 2-
bromobenzaldehyde or 2-iodoacetophenone (1.0 mmol), phenyl-
2-(Cyclohex-1-en-1-ylethynyl)benzaldehyde (1j). Eluent petro-
1
acetylene (1.2 mmol), and NEt (2 mmol) in THF (1.2 mL). The
mixture was heated under reflux or RT overnight under N . The
leum ether/ethyl acetate (20/1), yellow oil, yield (201 mg, 95%). H
3
NMR (400 MHz, CDCl ) δ 10.56 (s, 1H), 7.92 (d, J = 7.9 Hz, 1H),
2
3
system was filtered by short silica, then the solvent was evaporated
under reduced pressure, and the residue was purified by flash
chromatography with petroleum to afford the desired products 1.
7.56−7.53 (m, 2H), 7.44−7.38 (m, 1H), 6.35−6.30 (m, 1H), 2.31−
2.25 (m, 2H), 2.20 (dd, J = 6.0, 2.3 Hz, 2H), 1.76−1.70 (m, 2H),
7
13
1.68−1.64 (m, 2H); C NMR (100 MHz, CDCl ) δ 192.0, 136.9,
3
E
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1
2
35.6, 133.7, 133.0, 128.0, 127.6, 127.1, 120.3, 98.5, 82.4, 29.0, 25.8,
2.2, 21.4.
1H), 6.84−6.77 (m, 3H), 5.69 (d, J = 2.5 Hz, 1H), 4.87 (d, J = 8.7 Hz,
13
1H), 4.12−4.02 (m, 1H), 2.09 (s, 3H); C NMR (100 MHz, CDCl )
3
7
a
2
-(Oct-1-yn-1-yl)benzaldehyde (1k). Eluent petroleum ether/
δ 201.4, 161.8 (d, J = 245.0 Hz), 139.0 (d, J = 3.2 Hz), 137.4, 135.3,
133.1, 132.8, 132.3, 129.5, 129.4, 128.7, 128.5, 127.7 (d, J = 3.1 Hz),
1
ethyl acetate (20/1), yellow oil, yield (199 mg, 93%). H NMR (400
MHz, CDCl ) δ 10.54 (s, 1H), 7.87 (d, J = 7.6 Hz, 1H), 7.49 (s, 2H),
1
9
127.6, 127.4, 123.4, 115.4 (d, J = 21.2 Hz), 54.1, 43.3, 19.3; F NMR
(376 MHz, CDCl ) δ −116.0. IR (KBr) ν 3062.3, 2924.4, 1680.7,
3
7
(
.36 (s, 1H), 2.47 (dd, J = 9.4, 4.4 Hz, 2H), 1.66−1.60 (m, 2H), 1.47
d, J = 5.3 Hz, 2H), 1.32 (s, 4H), 0.91 (s, 3H); 13C NMR (100 MHz,
CDCl ) δ 192.0, 136.0, 133.6, 133.3, 128.0, 127.8, 126.9, 98.2, 76.3,
3
max
1599.7, 1509.2, 1448.2, 1374.6, 1046.2, 833.0, 760.8, 694.4, 554.9
−
1
cm . MS (EI): m/z 340, 263, 236, 220, 202, 122, 105, 77, 61, 43.
3
31.3, 28.6, 28.5, 22.5, 19.6, 14.0.
HRMS (EI) calcd for C H FO [M]: 342.1420; Found: 342.1418.
24
19
General Procedure for the Preparation of Product 4a−i. The
[2-(4-Chlorophenyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
corresponding enynals/enynones (1.0 equiv, 0.2 mmol) and styrene
(
[
(phenyl)methanone (4f). Eluent petroleum ether/ethyl acetate (20/
1
5.0 equiv) were added to a solution of the catalyst combination of
AuCl(IMes)] (5% equiv) and Selectfluor (10% equiv) in DCE (4.0
1), yellow solid (mp 140−141 °C), yield (63 mg, 88%). H NMR (400
MHz, CDCl ) δ 7.87 (d, J = 7.5 Hz, 2H), 7.54 (t, J = 7.4 Hz, 1H),
3
mL) and H O (1.0 equiv). The reaction mixture was stirred under a
7.46−7.35 (m, 3H), 7.28 (d, J = 7.5 Hz, 1H), 7.19−7.07 (m, 5H), 6.86
(d, J = 7.5 Hz, 1H), 5.75 (d, J = 2.6 Hz, 1H), 4.94 (d, J = 8.6 Hz, 1H),
2
nitrogen atmosphere at 80 °C for 24 h. After the reaction was finished,
the mixture was filtered by short silica, then the solvent was evaporated
under reduced pressure, and the residue was purified by flash
1
3
4.17−4.07 (m, 1H), 2.16 (s, 3H); C NMR (100 MHz, CDCl ) δ
3
201.1, 141.9, 137.3, 135.2, 133.2, 132.6 (2C), 132.4, 129.4, 128.8,
128.7, 128.5, 127.8, 127.7 (2C), 127.0, 123.4, 53.9, 43.3, 19.3. IR
(KBr) νmax 3061.6, 2920.9, 1682.2, 1595.8, 1488.8, 1446.9, 1090.5,
1
b
chromatography on silica gel to afford the desired products 4.
Phenyl(2-phenyl-1,2-dihydronaphthalen-1-yl)methanone (4a).
−1
Eluent petroleum ether/ethyl acetate (20/1), yellow oil, yield (22
1015.0, 860.0, 821.1, 758.7, 697.7, 551.8 cm . MS (EI): m/z 358, 253,
1
mg, 36%). H NMR (400 MHz, CDCl ) δ 7.81 (d, J = 7.6 Hz, 2H),
238, 218, 202, 141, 105, 77, 55. HRMS (EI) calcd for C24
H19ClO [M]:
3
7
7
1
=
2
1
.45 (t, J = 7.4 Hz, 1H), 7.34 (t, J = 7.7 Hz, 2H), 7.18−7.12 (m, 5H),
.09 (d, J = 6.2 Hz, 2H), 7.00 (t, J = 7.3 Hz, 1H), 6.77 (d, J = 7.5 Hz,
H), 6.56 (d, J = 9.6 Hz, 1H), 5.90 (dd, J = 9.6, 4.1 Hz, 1H), 4.94 (d, J
358.1118; Found: 358.1119.
[2-(4-Bromophenyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
(
phenyl)methanone (4g). Eluent petroleum ether/ethyl acetate (20/
1
1
3
1), yellow oil, yield (75 mg, 94%). H NMR (400 MHz, CDCl ) δ
7.8 Hz, 1H), 4.20−4.02 (m, 1H); C NMR (100 MHz, CDCl ) δ
3
3
7
2
(
.87 (d, J = 7.6 Hz, 2H), 7.54 (t, J = 7.3 Hz, 1H), 7.43 (t, J = 7.6 Hz,
H), 7.37 (d, J = 7.8 Hz, 1H), 7.30 (dd, J = 15.4, 7.9 Hz, 3H), 7.09
dd, J = 11.4, 8.1 Hz, 3H), 6.86 (d, J = 7.5 Hz, 1H), 5.74 (d, J = 2.3
01.1, 142.9, 137.2, 133.7, 133.1, 131.9, 130.3, 128.7, 128.6, 128.0,
27.9, 127.8, 127.7, 127.4, 127.0, 126.7, 53.4, 44.0.
(
4-Methyl-2-phenyl-1,2-dihydronaphthalen-1-yl)(phenyl)-
methanone (4b). Eluent petroleum ether/ethyl acetate (20/1), yellow
Hz, 1H), 4.93 (d, J = 8.5 Hz, 1H), 4.12 (d, J = 5.9 Hz, 1H), 2.16 (s,
1
13
oil, yield (64 mg, 98%). H NMR (400 MHz, CDCl ) δ 7.88 (d, J =
3H); C NMR (100 MHz, CDCl ) δ 201.1, 142.4, 137.2, 135.2,
3
3
7
7
6
4
2
1
.4 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.40 (dd, J = 16.4, 8.3 Hz, 3H),
.30−7.22 (m, 2H), 7.20 (d, J = 4.1 Hz, 4H), 7.10 (t, J = 7.5 Hz, 1H),
.87 (d, J = 7.5 Hz, 1H), 5.88−5.72 (m, 1H), 4.99 (d, J = 8.2 Hz, 1H),
133.2, 132.6, 132.5, 131.7, 129.8, 128.8, 128.6, 127.8, 127.7 (2C),
126.9, 123.5, 120.7, 53.7, 43.3, 19.4. IR (KBr) νmax 3064.4, 2927.3,
1681.4, 1596.4, 1487.7, 1447.3, 1374.5, 1046.1, 1008.8, 895.9, 820.3,
13
−1
.22−4.05 (m, 1H), 2.16 (s, 3H); C NMR (100 MHz, CDCl ) δ
759.8, 695.3, 551.5 cm . MS (EI): m/z 402, 296, 244, 218, 202, 122,
3
01.4, 143.3, 137.3, 135.4, 133.0, 132.8, 132.0, 129.6, 128.7, 128.6,
28.5, 128.0, 127.9, 127.6, 127.4, 126.9, 123.4, 53.9, 44.0, 19.4. IR
105, 77, 43. HRMS (EI) calcd for C24
H19BrO [M]: 402.0619; Found:
402.0620.
(
KBr) νmax 3060.6, 2923.6, 1680.3, 1597.0, 1491.3, 1448.5, 1028.8,
[2-(Cyclohexylmethyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
−
1
(phenyl)methanone (4h). Eluent petroleum ether/ethyl acetate (20/
7
59.5, 697.6 cm .
2-(4-Methoxyphenyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
phenyl)methanone (4c). Eluent petroleum ether/ethyl acetate (20/
1
1
), yellow oil, yield (47 mg, 68%). H NMR (400 MHz, CDCl ) δ
[
3
(
7.96 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.3 Hz, 1H), 7.47 (t, J = 7.6 Hz,
2H), 7.31 (d, J = 7.4 Hz, 1H), 7.27 (s, 1H), 7.11 (t, J = 7.4 Hz, 1H),
6.94 (d, J = 7.5 Hz, 1H), 5.68 (d, J = 3.9 Hz, 1H), 4.52 (d, J = 5.9 Hz,
1
1
7
7
), yellow oil, yield (62 mg, 87%). H NMR (400 MHz, CDCl ) δ
.93 (d, J = 7.6 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.49−7.39 (m, 3H),
.31 (dd, J = 8.1, 3.5 Hz, 1H), 7.14 (t, J = 8.7 Hz, 3H), 6.90 (d, J = 7.5
3
1
H), 2.99−2.85 (m, 1H), 2.09 (s, 3H), 1.72−1.61 (m, 4H), 1.48−1.33
13
(m, 2H), 1.30−1.09 (m, 5H), 0.90−0.77 (m, 2H); C NMR (100
Hz, 1H), 6.78 (d, J = 8.5 Hz, 2H), 5.81 (d, J = 2.8 Hz, 1H), 4.99 (d, J
=
NMR (100 MHz, CDCl ) δ 201.4, 158.5, 137.3, 135.4, 133.0, 131.8,
13
MHz, CDCl ) δ 201.1, 137.1, 135.7, 133.1, 132.9, 131.3, 128.7, 128.6,
8.1 Hz, 1H), 4.18−4.06 (m, 1H), 3.76 (s, 3H), 2.19 (s, 3H);
C
3
1
2
1
1
3
28.3, 127.4, 127.2, 127.1, 123.2, 52.5, 42.0, 34.6, 34.2, 34.1, 32.7, 26.6,
3
6.3, 26.2, 19.4. IR (KBr) νmax 3061.5, 2922.6, 2850.3, 1684.9, 1596.7,
1
1
1
30.6, 129.6, 128.9, 128.7, 128.6, 127.9, 127.7, 127.5, 123.3, 114.0,
13.7, 55.2, 54.2, 43.1, 19.4. IR (KBr) νmax 3503.5, 2934.6, 2837.3,
680.8, 1607.4, 1512.4, 1448.9, 1374.2, 1178.5, 1109.4, 1035.0, 895.3,
−1
489.4, 1447.9, 1044.3, 756.8, 696.4 cm . MS (EI): m/z 344, 239,
57, 143, 115, 97, 77, 55, 41. HRMS (EI) calcd for C H O [M]:
25 28
−1
44.2140; Found: 344.2142.
830.2, 760.9, 694.9, 560.1 cm . MS (EI): m/z 368, 352, 275, 249, 234,
(
12-Methyl-5,5a,6,7,8,9,10,11-octahydrocycloocta[b]-
202, 105, 77, 43. HRMS (EI) calcd for C H O [M]: 354.1620;
25
22
2
naphthalen-5-yl)(phenyl)methanone (4i). Eluent petroleum ether/
Found: 354.1618.
1
ethyl acetate (20/1), yellow oil, yield (44 mg, 66%). H NMR (400
[
2-(4-(tert-Butyl)phenyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
MHz, CDCl ) δ 7.85−7.74 (m, 2H), 7.46 (t, J = 7.3 Hz, 1H), 7.37 (t, J
(phenyl)methanone (4d). Eluent petroleum ether/ethyl acetate (20/
3
1
=
7.5 Hz, 2H), 7.23 (d, J = 7.2 Hz, 1H), 7.19−7.16 (m, 1H), 6.98 (dd,
J = 7.3, 1.1 Hz, 1H), 6.93 (d, J = 7.3 Hz, 1H), 4.28 (d, J = 2.6 Hz, 1H),
.78 (d, J = 10.8 Hz, 1H), 2.55 (ddd, J = 14.9, 9.0, 3.4 Hz, 1H), 1.95
1
7
7
), yellow oil, yield (72 mg, 94%). H NMR (400 MHz, CDCl ) δ
.89 (d, J = 7.4 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.44−7.36 (m, 3H),
.27 (t, J = 7.5 Hz, 1H), 7.22 (d, J = 8.4 Hz, 2H), 7.10 (dd, J = 7.7, 5.8
3
2
(
s, 3H), 1.66−1.56 (m, 2H), 1.54−1.43 (m, 4H), 1.42−1.27 (m, 5H);
Hz, 3H), 6.89 (d, J = 7.5 Hz, 1H), 5.78 (d, J = 3.3 Hz, 1H), 4.97 (d, J
=
NMR (100 MHz, CDCl ) δ 201.1, 149.7, 140.2, 137.2, 135.6, 132.9,
1
3
13
C NMR (100 MHz, CDCl ) δ 200.1, 137.7, 137.1, 136.9, 132.5,
7.1 Hz, 1H), 4.11−4.02 (m, 1H), 2.15 (s, 3H), 1.24 (s, 9H);
C
3
132.0, 128.7, 128.6, 128.3, 127.5, 125.9, 125.0, 123.2, 54.2, 40.7, 34.1,
3
132.7, 131.7, 128.6 (2C), 128.1, 127.5 (2C), 127.3, 125.5, 123.4, 53.8,
43.4, 34.4, 31.3, 19.4. IR (KBr) νmax 3061.3, 2962.5, 2921.1, 1682.4,
1597.7, 1511.2, 1449.0, 1368.7, 1045.9, 828.9, 759.7, 694.3, 579.3
33.3, 28.7, 26.2, 25.5, 24.2, 14.4. IR (KBr) νmax 3061.4, 2924.9, 1685.4,
−1
1597.9, 1449.5, 1373.0, 1045.9, 760.5, 695.8 cm . MS (EI): m/z 330,
224, 181, 155, 141, 122, 105, 77, 61, 43. HRMS (EI) calcd for
−1
cm . MS (EI): m/z 394, 378, 275, 259, 219, 105, 77, 57, 41. HRMS
C
24
H
26O [M]: 330.1984; Found: 330.1981.
(
EI) calcd for C H O [M]: 380.2140; Found: 380.2139.
General Procedure for the Preparation of Product 5a and 5b.
28
28
[
2-(4-Fluorophenyl)-4-methyl-1,2-dihydronaphthalen-1-yl]-
The corresponding enynals/enynones (1.0 equiv, 0.25 mmol) and
styrene (5.0 equiv) were added to a solution of 1,4-benzoquinone (2.0
equiv) and the catalyst combination of [AuCl(IMes)] (5% equiv) and
Selectfluor (10% equiv) in DCE (5.0 mL). The reaction mixture was
stirred under a nitrogen atmosphere at 80 °C for 24 h. After the
(
phenyl)methanone (4e). Eluent petroleum ether/ethyl acetate (20/
1
1
7
7
), yellow oil, yield (59 mg, 87%). H NMR (400 MHz, CDCl ) δ
.79 (d, J = 7.3 Hz, 2H), 7.46 (t, J = 7.4 Hz, 1H), 7.37−7.29 (m, 3H),
.21 (d, J = 7.3 Hz, 1H), 7.12−7.06 (m, 2H), 7.03 (dd, J = 7.5, 6.6 Hz,
3
F
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
reaction was finished, the mixture was filtered by short silica, then the
solvent was evaporated under reduced pressure, and the residue was
purified by flash chromatography on silica gel to afford the desired
3.7 Hz, 1H); 13C NMR (100 MHz, CDCl ) δ 195.9, 139.8, 136.0,
3
134.8, 133.0, 131.5, 130.9, 130.7, 130.3, 130.0, 129.7, 128.8, 128.7,
127.6, 127.5, 112.0, 111.6, 111.1, 110.9, 68.2, 49.2, 47.1, 45.1, 42.8,
30.7. IR (KBr) νmax 2926.3, 2853.5, 2027.3, 1659.2, 1592.5, 1492.7,
1452.4, 1269.2, 1087.0, 1016.7, 886.9, 770.4, 731.8, 697.5, 639.6, 558.4
8
products 5.
Phenyl(2-phenylnaphthalen-1-yl)methanone (5a). Eluent petro-
1
−1
leum ether/ethyl acetate (20/1), yellow oil, yield (39 mg, 50%). H
cm . MS (ESI): m/z 462.0, 461.0, 457.0, 456.1, 439.0. HRMS (ESI)
NMR (400 MHz, CDCl ) δ 7.95 (d, J = 8.5 Hz, 1H), 7.87 (d, J = 8.1
calcd for C H N ONa [M + Na]: 461.1378; Found: 461.1373.
3
29 18
4
Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 7.9 Hz, 2H), 7.50 (d, J
1-Benzoyl-4-methyl-10-(p-tolyl)-1,4-ethanonaphthalene-2,2,3,3-
=
=
8.5 Hz, 1H), 7.45 (t, J = 7.4 Hz, 1H), 7.41−7.35 (m, 1H), 7.31 (dd, J
(1H,4H)-tetracarbonitrile (6d). Eluent petroleum ether/ethyl acetate
13
1
14.2, 7.0 Hz, 3H), 7.19−7.12 (m, 4H), 7.12−7.06 (m, 1H);
C
(8/1), purple solid (mp 199−200 °C), yield (103 mg, 88%). H NMR
NMR (100 MHz, CDCl ) δ 199.7, 140.2, 138.0, 137.5, 135.7, 133.2,
(400 MHz, CDCl ) δ 7.78−7.70 (m, 2H), 7.49−7.41 (m, 2H), 7.32
3
3
132.4, 130.7, 129.6, 129.5, 128.3, 128.2, 127.6, 127.4, 127.2, 126.3,
(d, J = 7.4 Hz, 1H), 7.18 (d, J = 7.6 Hz, 2H), 6.96 (t, J = 7.9 Hz, 2H),
6.69 (d, J = 8.0 Hz, 2H), 6.40 (d, J = 8.1 Hz, 2H), 4.02 (dd, J = 10.5,
5.6 Hz, 1H), 3.01 (dd, J = 15.3, 10.5 Hz, 1H), 2.31 (dd, J = 15.3, 5.6
1
25.6.
(
4-Methyl-2-phenylnaphthalen-1-yl)(phenyl)methanone (5b).
Hz, 1H), 2.15 (s, 3H), 2.11 (s, 3H); 13C NMR (100 MHz, CDCl
) δ
Eluent petroleum ether/ethyl acetate (20/1), yellow solid (mp 145−
3
1
1
46 °C), yield (80 mg, 99%). H NMR (400 MHz, CDCl ) δ 8.00 (d,
196.1, 138.6, 137.1, 136.6, 136.1, 132.6, 131.3, 130.9, 130.7, 130.6,
129.5, 129.4, 129.3, 127.3, 124.9, 112.2, 111.3, 111.1, 110.4, 67.9, 52.8,
50.1, 45.4, 43.3, 37.6, 20.8, 20.3. IR (KBr) νmax 2923.9, 2851.6, 2025.4,
1656.7, 1515.2, 1385.4, 1235.5, 1099.6, 821.0, 787.0, 759.6, 737.8,
3
J = 8.4 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.53 (d, J = 7.3 Hz, 2H),
7
3
.48−7.43 (m, 1H), 7.36 (dd, J = 12.5, 5.3 Hz, 2H), 7.30−7.22 (m,
13
H), 7.15−7.09 (m, 4H), 7.08−7.03 (m, 1H), 2.70 (s, 3H); C NMR
−1
(
100 MHz, CDCl ) δ 199.9, 140.4, 138.2, 137.2, 136.1, 134.2, 133.1,
701.1, 639.4, 618.3, 550.5, 479.7 cm . MS (MALDI/DHB): m/z
3
131.7, 130.9, 129.6, 129.5, 128.4, 128.3, 128.2, 127.4, 126.9, 126.2
486.0, 485.0, 484.1, 467.0. HRMS (MALDI/DHB) calcd for
(
2C), 124.3, 19.7.
C H N ONa [M + Na]: 489.1683; Found: 489.1683.
31 22 4
General Procedure for the Preparation of Product 6a−y. The
1-Benzoyl-10-(p-tolyl)-1,4-ethanonaphthalene-2,2,3,3(1H,4H)-
corresponding enynals/enynones (1.0 equiv, 0.25 mmol) and styrene
(
tetracarbonitrile (6e). Eluent petroleum ether/ethyl acetate (8/1),
1
5.0 equiv) were added to a solution of olefins (2.0 equiv) (one of
these olefins, including 1,4-benzoquinone, tetracyanoethlene, etc.) and
the catalyst combination of [AuCl(IMes)] (5% equiv) and Selectfluor
orange solid (mp 222−223 °C), yield (102 mg, 90%). H NMR (400
MHz, CDCl ) δ 7.64−7.57 (m, 2H), 7.40−7.34 (m, 1H), 7.30 (d, J =
3
7.8 Hz, 1H), 7.23 (dt, J = 8.5, 1.1 Hz, 1H), 7.07 (dd, J = 8.5, 1.1 Hz,
2H), 6.87 (t, J = 8.0 Hz, 2H), 6.62 (d, J = 8.0 Hz, 2H), 6.35 (d, J = 8.2
Hz, 2H), 4.09−4.04 (m, 1H), 3.91 (dd, J = 10.5, 5.6 Hz, 1H), 3.06
(ddd, J = 15.2, 10.5, 2.4 Hz, 1H), 2.43 (ddd, J = 15.3, 5.6, 3.7 Hz, 1H),
(
10% equiv) in DCE (2.5 mL). The reaction mixture was stirred under
a nitrogen atmosphere at 80 °C for 24 h. After the reaction was
finished, the mixture was filtered by short silica, then the solvent was
evaporated under reduced pressure, and the residue was purified by
flash chromatography on silica gel to afford the desired products 6
2.07 (s, 3H); 13C NMR (100 MHz, CDCl
) δ 195.9, 138.7, 136.6,
3
136.1, 134.9, 132.6, 131.3, 130.9, 130.8, 130.5 129.9, 129.5, 129.4,
127.5, 127.3, 111.9, 111.6, 111.0, 110.8, 68.3, 49.1, 47.1, 45.3, 42.5,
30.6, 20.8. IR (KBr) νmax 2927.5, 2854.6, 2026.9, 1660.6, 1596.7,
(
except 6a, by crystallization).
9
-Benzoyl-12-phenyl-4a,9,9a,10-tetrahydro-9,10-ethanoanthra-
−1
cene-1,4-dione (6a). By crystallization (petroleum ether/ethyl
1267.5, 1089.3, 1017.5, 735.4, 696.3, 560.3 cm . MS (MALDI/DHB):
m/z 474.9, 471.0, 470.1, 453.1, 382.0. HRMS (MALDI/DHB) calcd
for C H N O [M + H]: 453.1724; Found: 453.1723.
1
acetate), yellow solid (mp 175−176 °C), yield (65 mg, 62%). H
NMR (400 MHz, CDCl ) δ 7.38 (d, J = 7.8 Hz, 1H), 7.29 (t, J = 7.4
3
30 21
4
Hz, 1H), 7.18−6.97 (m, 10H), 6.58 (d, J = 7.0 Hz, 2H), 6.36 (d, J =
1-Benzoyl-10-[4-(tert-butyl)phenyl]-4-methyl-1,4-ethanonaph-
1
3
1
1
1
4
1
8
0.3 Hz, 1H), 6.22 (d, J = 10.3 Hz, 1H), 4.54 (d, J = 10.1 Hz, 1H),
thalene-2,2,3,3(1H,4H)-tetracarbonitrile (6f). Eluent petroleum
.81−3.71 (m, 2H), 3.45 (d, J = 10.0 Hz, 1H), 2.72−2.63 (m, 1H),
ether/ethyl acetate (8/1), purple solid (mp 232−233 °C), yield
13
1
.88−1.80 (m, 1H); C NMR (100 MHz, CDCl ) δ 204.1, 197.7,
(126 mg, 99%). H NMR (400 MHz, CDCl
) δ 7.64 (q, J = 7.2 Hz,
3
3
96.1, 142.4, 141.9, 141.3, 140.6, 139.6, 136.3, 130.1, 129.2, 128.5,
28.3, 127.8, 127.6, 127.3, 127.2, 127.0, 124.8, 59.7, 55.1, 49.2, 46.4,
0.9, 38.6. IR (KBr) νmax 2926.6, 2853.5, 1597.0, 1596.9, 1595.3,
2H), 7.40−7.31 (m, 2H), 7.16 (d, J = 7.4 Hz, 1H), 7.09 (d, J = 7.8 Hz,
2H), 6.83 (dd, J = 14.7, 7.8 Hz, 4H), 6.36 (d, J = 8.2 Hz, 2H), 3.93
(dd, J = 10.3, 5.6 Hz, 1H), 2.90 (dd, J = 15.2, 10.6 Hz, 1H), 2.23 (dd, J
−1
13
235.7, 1088.3, 893.1, 754.2, 650.1 cm . MS (MALDI/DHB): m/z
= 15.2, 5.5 Hz, 1H), 2.00 (s, 3H), 1.08 (s, 9H); C NMR (100 MHz,
60.2, 859.2, 441.0, 420.0, 419.0. HRMS (MALDI/DHB) calcd for
CDCl ) δ 196.0, 151.8, 137.1, 136.7, 136.1, 132.8, 131.3, 130.9, 130.7,
3
C H O Na [M + Na]: 441.1471; Found: 441.1472.
129.5, 129.2, 127.3, 125.7, 124.9, 112.2, 111.2, 111.1, 110.4, 67.8, 52.8,
50.1, 45.4, 43.2, 37.6, 34.4, 31.1, 20.3. IR (KBr) νmax 2962.9, 2867.7,
2027.5, 1660.7, 1596.6, 1444.9, 1259.3, 1113.5, 834.1, 700.2, 573.9
29
22
3
1
-Benzoyl-4-methyl-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
(
1H,4H)-tetracarbonitrile (6b). Eluent petroleum ether/ethyl acetate
1
−1
(
(
4
6
8/1), purple solid (mp 230−232 °C), yield (105 mg, 93%). H NMR
cm . MS (MALDI/DHB): m/z 531.1, 527.2, 526.2, 509.0. HRMS
400 MHz, CDCl ) δ 7.69−7.60 (m, 2H), 7.36 (ddd, J = 18.8, 10.2,
(MALDI/DHB) calcd for C H N ONa [M + Na]: 531.2167;
3
34 28
4
.7 Hz, 2H), 7.19 (dd, J = 9.7, 5.0 Hz, 1H), 7.09 (d, J = 7.6 Hz, 2H),
.94 (t, J = 7.4 Hz, 1H), 6.83 (dt, J = 22.0, 7.7 Hz, 4H), 6.44 (d, J = 7.6
Found: 531.2166.
1-Benzoyl-10-(2,5-dimethylphenyl)-4-methyl-1,4-ethanonaph-
thalene-2,2,3,3(1H,4H)-tetracarbonitrile (6g). Eluent petroleum
ether/ethyl acetate (8/1), purple solid (mp 279−280 °C), yield (38
Hz, 2H), 3.94 (dd, J = 10.4, 5.5 Hz, 1H), 2.92 (dd, J = 15.3, 10.5 Hz,
1
3
1H), 2.24 (dd, J = 15.3, 5.6 Hz, 1H), 2.01 (s, 3H); C NMR (100
1
MHz, CDCl ) δ 195.9, 139.9, 137.1, 136.0, 132.9, 131.3, 130.8, 130.7,
mg, 32%). H NMR (400 MHz, DMSO) δ 7.96−7.72 (m, 2H), 7.57
3
1
1
2
6
30.6, 129.6, 129.5, 128.7, 128.6, 127.4, 124.9, 112.1, 111.2, 111.1,
10.4, 67.8, 52.8, 50.1, 45.3, 43.7, 37.6, 20.2. IR (KBr) νmax 2924.0,
852.4, 2025.8, 1655.9, 1385.0, 1134.3, 1098.6, 736.2, 698.0, 639.1,
(t, J = 7.4 Hz, 1H), 7.35 (t, J = 7.1 Hz, 2H), 7.24 (d, J = 7.8 Hz, 2H),
7.03 (t, J = 7.7 Hz, 2H), 6.67 (d, J = 7.6 Hz, 1H), 6.36 (d, J = 7.7 Hz,
1H), 6.27 (s, 1H), 4.22 (dd, J = 10.0, 6.7 Hz, 1H), 2.88 (dd, J = 15.2,
10.6 Hz, 1H), 2.41 (dd, J = 15.2, 6.5 Hz, 1H), 2.04 (d, J = 9.9 Hz, 6H),
1.83 (s, 3H); 13C NMR (100 MHz, DMSO) δ 196.7, 138.2, 137.0,
135.6, 134.6, 134.0, 133.1, 131.0, 130.6, 130.4, 129.8, 129.7, 129.2,
128.9, 128.6, 126.9, 125.5, 112.3, 111.7, 111.6, 111.1, 67.7, 52.4, 50.3,
45.4, 37.1, 36.8, 20.6, 19.5, 18.9. IR (KBr) νmax 2923.6, 2851.7, 2026.5,
−1
18.5 cm . MS (MALDI/DHB): m/z 475.9, 475.0, 471.0, 470.1,
3
18.1, 274.0. HRMS (MALDI/DHB) calcd for C H N ONa [M +
30
20
4
Na]: 475.1542; Found: 475.1543.
1
-Benzoyl-10-phenyl-1,4-ethanonaphthalene-2,2,3,3(1H,4H)-tet-
racarbonitrile (6c). Eluent petroleum ether/ethyl acetate (8/1),
1
−1
orange solid (mp 226−227 °C), yield (103 mg, 94%). H NMR
1659.5, 1596.9, 1451.9, 1296.7, 1070.9, 732.6, 696.9 cm . MS
(
(
400 MHz, CDCl ) δ 7.67−7.56 (m, 2H), 7.40−7.35 (m, 1H), 7.30
(MALDI/DHB): m/z 503.0, 499.1, 498.0, 481.0. HRMS (MALDI/
3
d, J = 7.8 Hz, 1H), 7.20 (dd, J = 12.1, 4.6 Hz, 1H), 7.08 (d, J = 7.5
DHB) calcd for C H N ONa [M + Na]: 503.1856; Found:
3
2
24
4
Hz, 2H), 6.96 (t, J = 7.4 Hz, 1H), 6.85 (dt, J = 15.6, 7.6 Hz, 4H), 6.48
d, J = 7.5 Hz, 2H), 4.09 (t, J = 2.9 Hz, 1H), 3.93 (dd, J = 10.5, 5.6 Hz,
H), 3.07 (ddd, J = 15.2, 10.5, 2.3 Hz, 1H), 2.46 (ddd, J = 15.3, 5.5,
503.1856.
(
1
1-Benzoyl-10-mesityl-4-methyl-1,4-ethanonaphthalene-2,2,3,3-
(1H,4H)-tetracarbonitrile (6h). Eluent petroleum ether/ethyl acetate
G
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1
−1
(
(
7
6
=
8/1), purple solid (mp 192−193 °C), yield (36 mg, 29%). H NMR
772.8, 733.7, 697.4 cm . MS (MALDI/DHB): m/z 543.0, 540.0,
400 MHz, CDCl ) δ 7.67−7.62 (m, 1H), 7.59 (d, J = 7.7 Hz, 1H),
.47−7.41 (m, 4H), 7.17 (d, J = 7.4 Hz, 1H), 6.89 (t, J = 7.8 Hz, 2H),
.45 (s, 1H), 6.13 (s, 1H), 4.37 (dd, J = 10.7, 8.5 Hz, 1H), 2.69 (dd, J
15.1, 10.9 Hz, 1H), 2.46 (dd, J = 15.0, 8.3 Hz, 1H), 1.99 (s, 3H),
.97 (s, 3H), 1.88 (s, 3H), 1.50 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 196.4 139.3 137.8, 136.4, 136.1, 133.2, 132.7, 132.3, 131.4, 130.5,
30.0, 129.9, 128.7, 126.9, 125.2, 112.3, 111.4, 111.2, 110.6, 68.1, 52.0,
5.3, 37.7, 34.2, 22.4, 22.2, 20.3, 20.2. IR (KBr) νmax 2924.8, 2853.3,
024.9, 1660.6, 1597.0, 1452.5, 1245.7, 1095.5, 769.5, 645.7, 620.2
539.1, 538.1. HRMS (MALDI/DHB) calcd for C H F N ONa [M +
Na]: 543.1406; Found: 543.1405.
1-Benzoyl-4-methyl-10-(perfluorophenyl)-1,4-ethanonaphtha-
lene-2,2,3,3(1H,4H)-tetracarbonitrile (6m). Eluent petroleum ether/
ethyl acetate (8/1), yellow solid (mp 261−262 °C), yield (16 mg,
12%). H NMR (400 MHz, CDCl
7.8 Hz, 1H), 7.67−7.58 (m, 4H), 7.47 (t, J = 7.3 Hz, 1H), 7.21 (t, J =
7.5 Hz, 2H), 4.39−4.30 (m, 1H), 2.92 (dd, J = 14.4, 11.1 Hz, 1H),
2.38 (dd, J = 14.8, 7.6 Hz, 1H), 2.10 (s, 3H); 13C NMR (100 MHz,
3
31 19
3
4
1
1
) δ 7.83−7.76 (m, 1H), 7.71 (d, J =
3
1
4
2
−1
cm . MS (MALDI/DHB): m/z 517.0, 513.2, 512.2, 495.0. HRMS
MALDI/DHB) calcd for C H N ONa [M + Na]: 517.2001;
CDCl
= 6.3 Hz), 129.0, 127.7, 125.0, 111.2, 111.0, 110.5, 110.1, 66.4, 52.0,
50.7, 45.4, 34.4, 31.7, 20.0; 19F NMR (376 MHz, CDCl
3
) δ 194.7, 136.4 (d, J = 23.2 Hz), 133.8, 131.9, 130.5, 130.0 (d, J
(
33 26 4
Found: 517.1999.
3
) δ −136.8
1
-Benzoyl-10-(4-fluorophenyl)-4-methyl-1,4-ethanonaphtha-
lene-2,2,3,3(1H,4H)-tetracarbonitrile (6i). Eluent petroleum ether/
(dd, J = 105.5, 22.5 Hz, 2H), −151.8 (t, J = 21.0 Hz, 1H), −160.8 (m,
2H). IR (KBr) νmax 2923.7, 2025.6, 1638.8, 1522.4, 1384.8, 1096.9,
954.6, 700.7, 639.1, 618.1, 569.3 cm . MS (MALDI/DHB): m/z
565.9, 564.9, 561.0, 560.0. HRMS (MALDI/DHB) calcd for
C H F N ONa [M + Na]: 565.1050; Found: 565.1049.
10-Benzoyl-5-methyl-5,10,10a,11-tetrahydro-4bH-5,10-
ethanobenzo[b]fluorene-12,12,13,13-tetracarbonitrile (6n). Eluent
petroleum ether/ethyl acetate (8/1), purple solid (mp 240−241 °C),
yield (115 mg, 99%). H NMR (400 MHz, CDCl ) δ 7.55−7.48 (m,
H), 7.32 (t, J = 7.4 Hz, 1H), 7.27 (d, J = 7.0 Hz, 2H), 7.21 (t, J = 6.3
Hz, 2H), 6.95 (dt, J = 15.1, 7.5 Hz, 4H), 6.40 (t, J = 7.4 Hz, 1H), 6.19
d, J = 7.7 Hz, 1H), 4.09 (d, J = 9.3 Hz, 1H), 3.59 (q, J = 9.1 Hz, 1H),
.01 (dd, J = 16.1, 8.9 Hz, 1H), 2.55 (dd, J = 16.1, 9.1 Hz, 1H), 2.05
s, 3H); 13C NMR (100 MHz, CDCl ) δ 193.7, 141.6, 138.8, 135.1,
34.8, 134.2, 132.5, 132.1, 131.4, 131.3, 129.2, 128.9 (2C), 127.4,
25.9, 124.9, 112.2, 111.3, 110.8, 110.5, 66.1, 52.2, 51.6, 48.9, 48.0,
5.8, 35.6, 19.2. IR (KBr) νmax 2925.3, 2852.2, 2026.0, 1660.9, 1596.5,
1389.4, 1242.6, 1149.4, 745.6, 697.5 cm . MS (MALDI/DHB): m/z
487.1, 483.1, 482.1. HRMS (MALDI/DHB) calcd for C31
−1
ethyl acetate (8/1), purple solid (mp 227−228 °C), yield (73 mg,
1
6
=
6
2%). H NMR (400 MHz, CDCl ) δ 7.75−7.56 (m, 2H), 7.41 (dt, J
3
15.1, 4.8 Hz, 2H), 7.26 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 7.5 Hz, 2H),
.94 (t, J = 7.9 Hz, 2H), 6.50 (t, J = 8.5 Hz, 2H), 6.39 (dd, J = 8.7, 5.2
Hz, 2H), 3.94 (dd, J = 10.5, 5.7 Hz, 1H), 2.94 (dd, J = 15.4, 10.5 Hz,
30 15 5 4
13
1
H), 2.16 (dd, J = 15.4, 5.7 Hz, 1H), 2.01 (s, 3H); C NMR (100
MHz, CDCl ) δ 195.7, 162.6 (d, J = 249.4 Hz), 137.0, 136.0, 135.7,
1
3
3
2
1
1
4
33.1, 131.5, 131.2 (d, J = 8.3 Hz), 130.8, 130.7, 129.7, 127.5, 125.0,
15.6 (d, J = 22.5 Hz), 112.0, 111.1, 110.3 (2C), 67.8, 52.7, 50.1, 45.3,
2.7, 37.9, 20.2; 19F NMR (376 MHz, CDCl ) δ −112.7. IR (KBr)
(
3
3
νmax 2924.7, 2853.5, 2026.3, 1660.6, 1596.5, 1512.0, 1232.6, 1152.2,
−1
(
7
4
60.7, 759.0, 645.3, 620.1, 560.5 cm . MS (MALDI/DHB): m/z
93.0, 489.1, 488.0, 471.0. HRMS (MALDI/DHB) calcd for
3
1
1
4
C H FN ONa [M + Na]: 493.1454; Found: 493.1459.
30
19
4
1
-Benzoyl-10-(4-chlorophenyl)-4-methyl-1,4-ethanonaphtha-
lene-2,2,3,3(1H,4H)-tetracarbonitrile (6j). Eluent petroleum ether/
−1
ethyl acetate (8/1), purple solid (mp 258−259 °C), yield (88 mg,
H N ONa
20 4
1
7
7
3%). H NMR (400 MHz, CDCl ) δ 7.72−7.62 (m, 2H), 7.41 (q, J =
[M + Na]: 487.1546; Found: 487.1543.
1-Benzoyl-10-(cyclohexylmethyl)-4-methyl-1,4-ethanonaphtha-
lene-2,2,3,3(1H,4H)-tetracarbonitrile (6o). Eluent petroleum ether/
3
.3 Hz, 2H), 7.28 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 7.6 Hz, 2H), 6.93 (t,
J = 7.9 Hz, 2H), 6.75 (d, J = 8.5 Hz, 2H), 6.33 (d, J = 8.4 Hz, 2H),
.91 (dd, J = 10.4, 5.6 Hz, 1H), 2.94 (dd, J = 15.4, 10.5 Hz, 1H), 2.14
dd, J = 15.4, 5.6 Hz, 1H), 2.01 (s, 3H); C NMR (100 MHz, CDCl3)
δ 195.7, 138.4, 136.9, 136.0, 134.7, 133.0, 131.5, 130.8 (2C), 130.7,
30.4, 129.7, 128.8, 127.6, 125.0, 112.0, 111.0 (2C), 110.2, 67.8, 52.7,
0.0, 45.2, 42.8, 37.7, 20.2. IR (KBr) νmax 2925.6, 2854.3, 2026.7,
661.2, 1596.8, 1384.7, 1098.9, 825.3, 749.8, 630.5, 570.6 cm . MS
MALDI/DHB): m/z 507.0, 505.1, 504.0. HRMS (MALDI/DHB)
ethyl acetate (8/1), brown solid (mp 222−224 °C), yield (52 mg,
3
(
1
13
4
7
2
4%). H NMR (400 MHz, CDCl ) δ 7.92 (d, J = 8.1 Hz, 2H), 7.60−
3
.51 (m, 2H), 7.48−7.36 (m, 5H), 2.88 (dd, J = 17.6, 8.8 Hz, 1H),
.58 (dd, J = 14.2, 9.2 Hz, 1H), 1.91 (s, 3H), 1.52−1.39 (m, 5H), 1.24
1
5
1
(
d, J = 19.3 Hz, 2H), 1.01 (t, J = 12.1 Hz, 3H), 0.81 (t, J = 6.9 Hz,
−1
1H), 0.70 (t, J = 10.6 Hz, 1H), 0.46 (ddd, J = 31.9, 21.9, 10.0 Hz, 2H);
C NMR (100 MHz, CDCl ) δ 195.7, 137.2, 136.8, 134.1, 131.5,
13
(
3
calcd for C H ClN ONa [M + Na]: 509.1155; Found: 509.1153.
131.1, 130.8, 130.3, 129.3, 128.2, 124.3, 112.1, 111.2, 110.8, 110.4,
65.5, 51.7, 50.5, 44.6, 44.3, 36.9, 34.5, 34.4, 33.6, 31.0, 26.2, 26.0, 25.8,
20.3. IR (KBr) νmax 2924.0, 2852.1, 1661.4, 1448.4, 1402.1, 1384.6,
30
19
4
1
-Benzoyl-10-(4-bromophenyl)-4-methyl-1,4-ethanonaphtha-
lene-2,2,3,3(1H,4H)-tetracarbonitrile (6k). Eluent petroleum ether/
−1
ethyl acetate (8/1), purple solid (mp 238−239 °C), yield (89 mg,
1239.1, 1184.9, 1105.3, 764.6, 736.2, 710.0, 660.8, 619.5, 479.8 cm .
MS (MALDI/DHB): m/z 495.0, 491.1, 490.1. HRMS (MALDI/
DHB) calcd for C H N ONa [M + Na]: 495.2150; Found:
1
6
(
7%). H NMR (400 MHz, CDCl ) δ 7.82−7.70 (m, 2H), 7.56−7.48
3
m, 2H), 7.39 (t, J = 7.0 Hz, 1H), 7.22 (d, J = 7.3 Hz, 2H), 7.02 (dd, J
3
1
28
4
=
15.6, 7.4 Hz, 4H), 6.36 (d, J = 6.7 Hz, 2H), 3.99 (dd, J = 10.0, 5.3
495.2153.
13
Hz, 1H), 3.08−2.96 (m, 1H), 2.28−2.18 (m, 1H), 2.11 (s, 3H);
NMR (100 MHz, CDCl ) δ 195.7, 138.9, 136.9, 136.0, 133.0, 131.7,
C
1-(4-Methylbenzoyl)-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
(1H,4H)-tetracarbonitrile (6p). Eluent petroleum ether/ethyl acetate
(8/1), orange solid (mp 199−200 °C), yield (112 mg, 99%). H NMR
(400 MHz, CDCl ) δ 7.60 (d, J = 4.1 Hz, 2H), 7.34 (dt, J = 8.7, 4.4
3
1
1
1
2
7
5
31.5, 131.1, 130.7, 130.6, 130.4, 129.8, 127.6, 125.0, 122.8, 112.0,
11.0 (2C), 110.2, 67.8, 52.7, 50.0, 45.2, 42.9, 37.7, 20.2. IR (KBr) νmax
924.9, 2853.4, 2026.9, 1660.4, 1596.5, 1240.1, 1151.4, 1011.5, 825.7,
71.8, 733.4, 697.9, 603.4 cm . MS (MALDI/DHB): m/z 571.0,
52.9, 550.0, 549.0, 548.0. HRMS (MALDI/DHB) calcd for
3
Hz, 1H), 7.28 (d, J = 7.8 Hz, 1H), 6.96 (t, J = 8.7 Hz, 3H), 6.83 (t, J =
7.7 Hz, 2H), 6.65 (d, J = 8.2 Hz, 2H), 6.47 (d, J = 7.6 Hz, 2H), 4.08 (t,
J = 2.7 Hz, 1H), 3.91 (dd, J = 10.4, 5.5 Hz, 1H), 3.04 (ddd, J = 15.2,
10.5, 2.2 Hz, 1H), 2.46 (ddd, J = 15.3, 5.1, 3.9 Hz, 1H), 2.17 (s, 3H);
−1
C H BrN ONa [M + Na]: 553.0654; Found: 553.0659.
30
19
4
13
1
-Benzoyl-4-methyl-10-[4-(trifluoromethyl)phenyl]-1,4-ethano-
C NMR (100 MHz, CDCl ) δ 195.1, 144.4, 139.9, 134.9, 133.3,
3
naphthalene-2,2,3,3(1H,4H)-tetracarbonitrile (6l). Eluent petroleum
ether/ethyl acetate (8/1), purple solid (mp 244−245 °C), yield (69
mg, 53%). H NMR (400 MHz, CDCl ) δ 7.69 (ddd, J = 13.6, 9.9, 4.2
131.4, 131.0 (2C), 130.4, 129.9, 129.8, 128.8, 128.5, 128.1, 127.5,
112.1, 111.7, 111.2, 110.9, 68.2, 49.2, 47.2, 45.1, 43.0, 30.5, 21.6. IR
(KBr) νmax 2926.5, 2853.6, 2025.5, 1658.6, 1598.0, 1240.8, 1179.2,
1
3
−1
Hz, 2H), 7.45 (dt, J = 15.0, 4.7 Hz, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.06
1021.1, 887.1, 770.3, 731.0, 703.5, 650.6 cm . MS (MALDI/DHB):
m/z 476.0, 475.0, 470.0, 454.0, 453.0. HRMS (MALDI/DHB) calcd
for C H N ONa [M + Na]: 475.1539; Found: 475.1540.
(
dd, J = 26.5, 7.9 Hz, 4H), 6.86 (t, J = 7.9 Hz, 2H), 6.51 (d, J = 8.2 Hz,
2
2
H), 3.97 (dd, J = 10.5, 5.5 Hz, 1H), 2.97 (dd, J = 15.4, 10.5 Hz, 1H),
30
20
4
.18 (dd, J = 15.4, 5.5 Hz, 1H), 2.02 (s, 3H); 13C NMR (100 MHz,
1-(4-Methoxybenzoyl)-10-phenyl-1,4-ethanonaphthalene-
2,2,3,3(1H,4H)-tetracarbonitrile (6q). Eluent petroleum ether/ethyl
CDCl ) δ 195.5, 144.0, 136.9, 136.1, 133.2, 131.7, 130.6, 130.5, 130.3,
3
1
1
30.0, 129.9, 127.6, 125.5 (q, J = 3.8 Hz), 125.1, 111.9, 111.0, 110.9,
acetate (8/1), purple solid (mp 258−259 °C), yield (104 mg, 89%).
10.2, 67.8, 52.8, 50.0, 45.2, 43.0, 37.7, 20.2; 19F NMR (376 MHz,
1
H NMR (400 MHz, CDCl ) δ 7.60 (d, J = 4.0 Hz, 2H), 7.39−7.29
3
CDCl ) δ −63.1. IR (KBr) ν
2926.5, 2854.6, 2026.6, 1660.7,
(m, 2H), 7.08 (d, J = 8.6 Hz, 2H), 6.98 (t, J = 7.3 Hz, 1H), 6.86 (t, J =
7.6 Hz, 2H), 6.50 (d, J = 7.7 Hz, 2H), 6.32 (d, J = 8.7 Hz, 2H), 4.09 (s,
3
max
1594.4, 1457.8, 1325.2, 1238.3, 1171.4, 1128.3, 1067.8, 1012.5, 842.9,
H
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1
1
1
H), 3.92 (dd, J = 10.4, 5.3 Hz, 1H), 3.69 (s, 3H), 3.05 (dd, J = 14.3,
1.6 Hz, 1H), 2.48 (dt, J = 15.3, 4.3 Hz, 1H); 13C NMR (100 MHz,
(8/1), orange solid (mp 180−181 °C), yield (63 mg, 55%). H NMR
(400 MHz, CDCl ) δ 7.35 (dd, J = 7.2, 1.5 Hz, 1H), 7.31−7.21 (m,
3
CDCl ) δ 193.1, 163.4, 140.1, 134.9, 133.6, 131.3, 131.0, 129.9, 129.8,
2H), 7.10−6.97 (m, 4H), 6.88 (q, J = 7.6 Hz, 4H), 6.51 (d, J = 7.8 Hz,
2H), 4.08 (s, 1H), 3.96 (dd, J = 10.4, 5.5 Hz, 1H), 3.14−3.02 (m, 1H),
3
1
4
1
28.8, 128.6, 128.3, 127.5, 112.7, 112.2, 111.7, 111.2, 110.9, 68.2, 55.5,
9.2, 47.2, 45.2, 43.0, 30.3. IR (KBr) νmax 2924.7, 2853.8, 2026.1,
13
2.51−2.41 (m, 1H); C NMR (100 MHz, CDCl ) δ 195.4, 163.8 (d, J
3
−1
598.2, 1506.9, 1311.9, 1259.0, 1174.1, 1020.9, 840.2, 770.1 cm . MS
= 255.5 Hz), 139.4, 137.2 (d, J = 8.4 Hz), 135.8, 133.1 (d, J = 8.7 Hz),
133.0, 130.6, 129.7, 128.9, 127.6, 126.1 (d, J = 3.6 Hz), 117.3 (d, J =
22.0 Hz), 115.1 (d, J = 23.0 Hz), 111.8, 111.3, 111.0, 110.6, 67.7, 49.2,
(
MALDI/DHB): m/z 491.0, 471.0, 470.0, 469.0. HRMS (MALDI/
DHB) calcd for C H N O [M + H]: 469.1677; Found: 469.1673.
30
21
4
2
46.9, 45.2, 42.9, 30.2; 19F NMR (376 MHz, CDCl
) δ −106.1. IR
3
1
-(3-Fluorobenzoyl)-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
(1H,4H)-tetracarbonitrile (6r). Eluent petroleum ether/ethyl acetate
(KBr) νmax 2927.7, 2856.3, 2033.5, 1660.9, 1598.2, 1491.8, 1128.4,
1
−1
(
8/1), orange solid (mp 235−236 °C), yield (111 mg, 97%). H NMR
1101.1, 989.6, 878.6, 744.6, 696.0, 623.9, 612.2, 550.5 cm . MS
(MALDI/DHB): m/z 480.0, 475.0, 474.0, 457.0. HRMS (MALDI/
(
400 MHz, CDCl ) δ 7.71−7.57 (m, 2H), 7.41 (t, J = 7.2 Hz, 1H),
3
7
.28 (d, J = 7.8 Hz, 1H), 6.93 (ddt, J = 21.9, 15.0, 7.5 Hz, 6H), 6.70 (d,
DHB) calcd for C29
479.1289.
H17FN ONa [M + Na]: 479.1289; Found:
4
J = 10.0 Hz, 1H), 6.49 (d, J = 7.7 Hz, 2H), 4.10 (s, 1H), 3.91 (dd, J =
13
1
0.4, 5.6 Hz, 1H), 3.13−3.02 (m, 1H), 2.50−2.39 (m, 1H); C NMR
1-Heptanoyl-10-phenyl-1,4-ethanonaphthalene-2,2,3,3(1H,4H)-
tetracarbonitrile (6w). Eluent petroleum ether/ethyl acetate (8/1),
yellow solid (mp 170−171 °C), yield (110 mg, 99%). H NMR (400
MHz, CDCl ) δ 7.63 (t, J = 7.5 Hz, 1H), 7.55 (dd, J = 18.0, 7.6 Hz,
(
100 MHz, CDCl ) δ 195.0, 161.2 (d, J = 247.4 Hz), 139.5, 137.9,
3
1
134.8, 131.7, 130.6, 130.2, 130.0, 129.6, 129.1 (d, J = 7.6 Hz), 128.9,
127.7, 126.5 (d, J = 2.9 Hz), 120.3 (d, J = 21.2 Hz), 117.5 (d, J = 24.3
3
19
2H), 7.20 (t, J = 7.9 Hz, 2H), 7.13 (t, J = 7.5 Hz, 2H), 6.52 (d, J = 7.4
Hz, 2H), 3.99 (s, 1H), 3.64 (dd, J = 10.2, 5.9 Hz, 1H), 3.14−2.99 (m,
Hz), 111.8, 111.5, 110.9, 110.8, 68.3, 49.2, 47.1, 45.1, 42.7, 30.7;
NMR (376 MHz, CDCl ) δ −111.9. IR (KBr) ν 2924.3, 2852.7,
2
F
3
max
1
H), 1.98 (td, J = 15.2, 4.9 Hz, 2H), 1.47−1.31 (m, 3H), 1.12 (dt, J =
025.9, 1661.5, 1596.8, 1230.4, 1159.3, 767.9, 754.2, 650.1, 623.0
−1
14.1, 7.0 Hz, 2H), 0.97 (m, 3H), 0.86 (dd, J = 8.7, 6.1 Hz, 1H), 0.76 (t,
cm . MS (MALDI/DHB): m/z 480.0, 479.0, 475.0, 474.0. HRMS
J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 206.0, 140.5, 134.5,
(
MALDI/DHB) calcd for C H FN ONa [M + Na]: 479.1298;
3
29
17
4
1
1
2
2
1
31.4, 130.8, 130.5, 129.3, 128.9, 128.7, 127.9, 127.7, 111.5 (2C),
11.1, 110.7, 67.2, 47.4, 46.2, 44.6, 43.5, 41.5, 33.4, 31.1, 28.5, 24.2,
2.3, 14.0. IR (KBr) νmax 3065.8, 3033.2, 2958.6, 2929.9, 2872.5,
854.9, 2251.3, 2026.1, 1702.1, 1603.1, 1494.4, 1461.8, 1381.8, 1214.7,
088.7, 910.5, 765.7, 702.0, 618.6, 548.2, 525.7, 477.4, 427.7 cm . MS
MALDI/DHB): m/z 470.1, 469.0, 465.1, 464.1. HRMS (MALDI/
DHB) calcd for C H N ONa [M + Na]: 469.2009; Found:
469.2010.
-(Cyclohex-1-enecarbonyl)-10-phenyl-1,4-ethanonaphthalene-
,2,3,3(1H,4H)-tetracarbonitrile (6x). Eluent petroleum ether/ethyl
Found: 479.1303.
1
-(4-Chlorobenzoyl)-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
(1H,4H)-tetracarbonitrile (6s). Eluent petroleum ether/ethyl acetate
1
(
8/1), orange solid (mp 228−229 °C), yield (117 mg, 99%). H NMR
−1
(
400 MHz, CDCl ) δ 7.67−7.59 (m, 2H), 7.37 (td, J = 8.1, 4.2 Hz,
3
(
1
1
1
H), 7.24 (d, J = 7.8 Hz, 1H), 7.02 (d, J = 8.2 Hz, 3H), 6.85 (dd, J =
3.2, 7.8 Hz, 4H), 6.47 (d, J = 7.8 Hz, 2H), 4.10 (s, 1H), 3.90 (dd, J =
0.3, 5.5 Hz, 1H), 3.10−3.00 (m, 1H), 2.50−2.37 (m, 1H); C NMR
29 26
4
13
1
(
100 MHz, CDCl ) δ 194.8, 139.9, 139.7, 134.9, 134.2, 132.1, 131.7,
3
2
1
1
2
30.6, 130.1, 129.8, 129.0, 128.8, 127.8, 127.7, 111.9, 111.6, 111.0,
10.8, 68.2, 49.1, 47.1, 45.0, 42.8, 30.5. IR (KBr) νmax 2927.7, 2856.3,
033.8, 1660.8, 1595.9, 1578.9, 1233.3, 1089.0, 1017.2, 899.2, 735.2,
1
acetate (8/1), orange solid (mp 215−216 °C), yield (62 mg, 56%). H
NMR (400 MHz, CDCl ) δ 7.63−7.51 (m, 2H), 7.49−7.39 (m, 2H),
3
−1
7.12 (d, J = 5.6 Hz, 3H), 6.73−6.50 (m, 2H), 5.69 (s, 1H), 4.02 (d, J =
696.8, 555.8 cm . MS (ESI): m/z 495.0, 493.0, 492.0, 490.0, 473.0,
2
(
.8 Hz, 1H), 3.78 (dd, J = 10.2, 6.4 Hz, 1H), 3.08−2.96 (m, 1H), 2.39
358.9, 354.0, 274.2. HRMS (ESI) calcd for C H ClN ONa [M +
29
17
4
ddd, J = 15.2, 6.3, 3.4 Hz, 1H), 2.28 (d, J = 17.1 Hz, 1H), 1.98 (d, J =
Na]: 495.0989; Found: 495.0983.
1
1
7.5 Hz, 1H), 1.72 (d, J = 18.6 Hz, 1H), 1.40 (d, J = 4.8 Hz, 1H),
.36−1.23 (m, 2H), 1.17−1.07 (m, 2H); C NMR (100 MHz,
CDCl ) δ 194.0, 150.3, 141.1, 137.3, 134.9, 131.2, 130.9, 129.9, 129.7,
29.1, 128.6, 127.3, 112.1, 111.7, 111.1, 110.9, 68.6, 49.6, 46.8, 45.1,
2.6, 30.8, 26.5, 24.2, 21.8, 20.4. IR (KBr) νmax 2926.4, 2855.1, 2026.1,
623.0, 1460.3, 1384.6, 1269.5, 1095.4, 765.3, 737.0, 700.5, 639.3,
18.5, 560.1 cm . MS (MALDI/DHB): m/z 465.0, 460.0, 451.0,
O [M + H]:
1
-Benzoyl-7-methyl-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
13
(1H,4H)-tetracarbonitrile (6t). Eluent petroleum ether/ethyl acetate
1
3
(
8/1), orange solid (mp 211−212 °C), yield (112 mg, 99%). H NMR
1
4
1
6
(
400 MHz, CDCl ) δ 7.49 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 7.7 Hz,
3
1
H), 7.20 (t, J = 7.3 Hz, 1H), 7.09 (d, J = 6.7 Hz, 3H), 6.94 (t, J = 7.3
Hz, 1H), 6.84 (dt, J = 18.4, 7.5 Hz, 4H), 6.46 (d, J = 7.7 Hz, 2H), 4.06
s, 1H), 3.88 (dd, J = 10.3, 5.4 Hz, 1H), 3.09−2.96 (m, 1H), 2.42 (dt, J
−1
(
=
15.2, 4.0 Hz, 1H), 2.18 (s, 3H); 1 C NMR (100 MHz, CDCl ) δ
3
444.0, 443.0. HRMS (MALDI/DHB) calcd for C29
H N
23 4
3
4
43.1877; Found: 443.1880.
4
1
1
4
1
96.1, 140.3, 139.9, 136.0, 133.0, 132.1, 131.7, 131.4, 130.7, 130.1,
29.8, 128.8, 128.6, 127.4 (2C), 112.1, 111.8, 111.2, 111.0, 68.3, 49.2,
7.3, 44.8, 42.8, 30.8, 21.7. IR (KBr) νmax 2927.9, 2855.3, 2033.4,
-Benzoyl-2,9-dimethyl-11-phenyl-3a,4,9,9a-tetrahydro-1H-4,9-
ethanobenzo[f]isoindole-1,3(2H)-dione (6y). Eluent petroleum
ether/ethyl acetate (8/1), yellow solid (mp 179−180 °C), yield (87
mg, 80%). H NMR (400 MHz, CDCl ) δ 7.28 (t, J = 7.4 Hz, 2H),
.24−7.11 (m, 5H), 7.10−6.95 (m, 5H), 6.51 (d, J = 7.3 Hz, 2H), 4.31
d, J = 8.6 Hz, 1H), 3.72 (dd, J = 10.7, 6.0 Hz, 1H), 2.94 (d, J = 8.6
Hz, 1H), 2.42 (dd, J = 13.5, 10.8 Hz, 1H), 2.32 (s, 3H), 1.74 (s, 3H),
−1
660.6, 1596.4, 1128.0, 1100.6, 989.5, 831.6, 743.1, 693.7, 621.4 cm .
1
3
MS (MALDI/DHB): m/z 475.1, 474.9, 471.1, 470.1, 453.0. HRMS
7
(
(
MALDI/DHB) calcd for C H N O [M + H]: 453.1726; Found:
30 21 4
4
53.1723.
-Benzoyl-6-methoxy-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
1H,4H)-tetracarbonitrile (6u). Eluent petroleum ether/ethyl acetate
1
13
1
1
1
3
1
.65 (dd, J = 13.5, 5.9 Hz, 1H); C NMR (100 MHz, CDCl ) δ 204.6,
3
(
76.6, 176.4, 142.4, 142.2, 140.5, 133.8, 130.2, 129.5, 128.9, 128.6,
27.8, 127.7, 127.6, 127.4, 126.9, 122.4, 58.3, 50.2, 48.9, 47.8, 45.1,
9.1, 24.1, 20.7. IR (KBr) νmax 2928.9, 2854.3, 2030.0, 1769.9, 1699.1,
441.9, 1379.4, 1291.6, 1233.6, 1125.6, 957.9, 843.5, 761.6, 700.3
cm . MS (MALDI/DHB): m/z 894.2, 893.3, 458.0, 437.0, 436.1.
1
(8/1), orange solid (mp 211−212 °C), yield (115 mg, 98%). H NMR
(400 MHz, CDCl ) δ 7.21 (d, J = 7.4 Hz, 1H), 7.15 (d, J = 8.7 Hz,
3
1
H), 7.10 (d, J = 1.6 Hz, 1H), 7.06 (d, J = 8.0 Hz, 2H), 6.96 (t, J = 7.3
Hz, 1H), 6.93−6.69 (m, 5H), 6.51 (d, J = 7.7 Hz, 2H), 4.03 (s, 1H),
−1
3
2
1
1
4
1
6
4
.90 (dd, J = 10.3, 5.5 Hz, 1H), 3.84 (s, 3H), 3.10−2.94 (m, 1H),
HRMS (MALDI/DHB) calcd for C H NO [M + H]: 436.1908;
13
29 26
3
.53−2.35 (m, 1H); C NMR (100 MHz, CDCl ) δ 196.1, 161.6,
3
Found: 436.1907.
39.8, 136.3, 135.9, 133.0, 132.2, 130.7, 129.8, 128.8, 128.6, 127.4,
21.3, 115.1, 113.1, 112.1, 111.7, 111.3, 110.9, 68.0, 55.8, 49.4, 47.1,
5.4, 43.1, 30.5. IR (KBr) νmax 2926.5, 2854.5, 2030.3, 1660.2, 1605.9,
498.2, 1459.8, 1269.5, 1128.7, 1099.7, 989.5, 827.0, 743.8, 696.2,
ASSOCIATED CONTENT
■
*
S
Supporting Information
The copies of NMR spectral data, the crystallographic data
CIF file) of 6a, and the copy of HRMS spectrum of compound
b. This material is available free of charge via the Internet at
http://pubs.acs.org.
−1
24.2, 611.7, 552.1 cm . MS (MALDI/DHB): m/z 491.0, 488.0,
87.0, 486.0, 470.0, 469.0. HRMS (MALDI/DHB) calcd for
(
7
C H N O [M + H]: 469.1663; Found: 469.1659.
30
21
4
2
1
-Benzoyl-6-fluoro-10-phenyl-1,4-ethanonaphthalene-2,2,3,3-
(1H,4H)-tetracarbonitrile (6v). Eluent petroleum ether/ethyl acetate
I
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
AUTHOR INFORMATION
Corresponding Authors
E-mail: zhusf@scut.edu.cn.
E-mail: tongmei@scut.edu.cn.
■
*
*
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the NNSFC (21172077, 21372086), the
Program for New Century Excellent Talents in University
■
(
NCET-10-0403), The National Basic Research Program of
China (973) (2011CB808600), the Changjiang Scholars and
Innovation Team Project of Ministry of Education, SRF for
ROCS, State Education Ministry, Guangdong NSF
(
10351064101000000), and the Fundamental Research Funds
for the Central Universities, SCUT.
REFERENCES
■
(
1
1) (a) Asao, N.; Aikawa, H.; Yamamoto, Y. J. Am. Chem. Soc. 2003,
26, 7458. (b) Asao, N.; Kasahara, T.; Yamamoto, Y. Angew. Chem.,
Int. Ed. 2003, 42, 3504. (c) Yu, S.-Y.; Zhang, H.; Gao, Y.; Mo, L.;
Wang, S.; Yao, Z.-J. J. Am. Chem. Soc. 2013, 135, 11402. (d) Barluenga,
J.; Vazquez-Villa, H.; Merino, I.; Ballesteros, A.; Gonzalez, J. M.
Chem.Eur. J. 2006, 12, 5790.
(
2) (a) Zhu, S.; Zhang, Z.; Huang, X.; Jiang, H.; Guo, Z. Chem.Eur.
J. 2013, 19, 4695. (b) Zhu, S.; Guo, Z.; Huang, Z.; Jiang, H. Chem.
Eur. J. 2014, 20, 2425. (c) Zhu, S.; Hu, L.; Jiang, H. Org. Biomol. Chem.
2
(
014, 12, 4014.
3) For general reviews on o-QDMs: (a) Segura, J. L.; Martin, N.
Chem. Rev. 1999, 99, 3199. (b) Martin, N.; Seoane, C.; Hanack, M.
Org. Prep. Proced. Int. 1991, 23, 237. (c) Zhu, S.; Zheng, R. Chin. J. Org.
Chem. 2014, DOI: 10.6023/cjoc201401006.
(
4) For our previous work on o-QDMs: (a) Zhu, S.; Liang, R.; Jiang,
H.; Wu, W. Angew. Chem., Int. Ed. 2012, 51, 10861. (b) Zhu, S.; Xiao,
Y.; Guo, Z.; Jiang, H. Org. Lett. 2013, 15, 898.
(
5) Examples using Selectfluor as the oxidant in oxidization of Au(I)
to Au(III): (a) Melhado, A. D.; Brenzovich, W. E., Jr.; Lackner, A. D.;
Toste, F. D. J. Am. Chem. Soc. 2010, 132, 8885. (b) Brenzovich, W. E.,
Jr.; Benitez, D.; Lackner, A. D.; Shunatona, H. P.; Tkatchouk, E.;
Goddard, W. A.; Toste, F. D. Angew. Chem., Int. Ed. 2010, 49, 5519.
(
c) Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010,
132, 1474. (d) Zhu, S.; Ye, L.; Wu, W.; Jiang, H. Tetrahedron 2013, 69,
10375.
(
6) Representative examples of the generation and application of
benzopyrilium ion: (a) Asao, N.; Takahashi, K.; Lee, S.; Kasahara, T.;
Yamamoto, Y. J. Am. Chem. Soc. 2002, 124, 12650. (b) Asao, N.;
Nogami, T.; Lee, S.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 10921.
(
c) Asao, N.; Nogami, T.; Takahashi, K.; Yamamoto, Y. J. Am. Chem.
Soc. 2002, 124, 764. (d) Ding, Q.; Wu, J. Org. Lett. 2007, 9, 4959.
e) Dyker, G.; Hildebrandt, D.; Liu, J.; Merz, K. Angew. Chem., Int. Ed.
003, 42, 4399. (f) Bhunia, S.; Wang, K.-C.; Liu, R.-S. Angew. Chem.,
(
2
Int. Ed. 2008, 47, 5063. (g) Tang, R.-Y.; Li, J.-H. Chem.Eur. J. 2010,
16, 4733. (h) Yue, D.; Ca, N. D.; Larock, R. C. J. Org. Chem. 2006, 71,
3381. (i) Kusama, H.; Funami, H.; Shido, M.; Hara, Y.; Takaya, J.;
Iwasawa, N. J. Am. Chem. Soc. 2005, 127, 2709. (j) Kusama, H.;
Funami, H.; Takaya, J.; Iwasawa, N. Org. Lett. 2004, 6, 605.
(
7) (a) Pena, D.; Perez, D. Eur. J. Org. Chem. 2003, 1238. (b) Wang,
Z.-Q.; Zhang, W.-W.; Gong, L.-B. Angew. Chem., Int. Ed. 2011, 50,
968. (c) Too, P.-C.; Chiba, S. Chem. Commun. 2012, 48, 7634.
d) Chen, Y.; Li, G.; Liu, Y. Adv. Synth. Catal. 2011, 353, 392.
8) Zhao, X.; Zhang, X.-G.; Tang, R.-Y.; Deng, C. L. Eur. J. Org.
Chem. 2010, 4211.
8
(
(
J
dx.doi.org/10.1021/jo500838x | J. Org. Chem. XXXX, XXX, XXX−XXX