Palladium-catalyzed syn-stereocontrolled ring opening of oxabicyclic alkenes with arylsulfonyl hydrazides

Article abstract of DOI:10.1021/acs.joc.9b01957

A novel palladium-catalyzed ring-opening reaction of oxabicyclic alkenes with arylsulfonyl hydrazides was first developed. In this work, we provide an efficient one-pot reaction to afford the corresponding cis-2-aryl-1,2-dihydronaphthalen-1-ols and 2-aryl

Full text of DOI:10.1021/acs.joc.9b01957

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Article
Palladium-catalyzed syn-stereocontrolled ring-opening
of oxabicyclic alkenes with arylsulfonyl hydrazides
Donghan Chen, Yongqi Yao, Wen Yang, Qifu Lin, Huan-
yong Li, Lin Wang, Shuqi Chen, Yun Tan, and Dingqiao Yang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01957 • Publication Date (Web): 12 Sep 2019
Downloaded from pubs.acs.org on September 13, 2019
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Page 1 of 13
The Journal of Organic Chemistry
Palladium-catalyzed syn-stereocontrolled ring-opening of oxabicyclic alkenes
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with arylsulfonyl hydrazides
†
†
†
†
‡
Donghan Chen, Yongqi Yao, Wen Yang, Qifu Lin, Huanyong Li, Lin
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†
Wang, Shuqi Chen, Yun Tan, and Dingqiao Yang*
†Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, College of Chemistry, South China
Normal University, Guangzhou 510006, People’s Republic of China
‡Analytical and Testing Center, Jinan University, Guangzhou 510632, People’s Republic of China
Supporting Information
R2
R2 OH
R2
PdCl2(PPh3)2
10 mol%)
R1
R1
R1
R1
R1
R1
Ar
Ar
(
2
- H O
O
+
ArSO2NHNH2
Cu(OAc)2 (1.5 equiv.)
DMF, 100 oC, 15 min
R2 R3
R2 R3
R2 R3
22 examples
up to 96% yield
3 examples
up to 95% yield
R1 = H, OMe, Me, Br, F
R2 = H, OMe
1. short reaction time
2. in open-air condition
R3 = H, Me
3. high regioselectivity
R1 + R2
=
, R3 = H
ABSTRACT: A novel palladium-catalyzed ring-opening of oxabicyclic alkenes with arylsulfonyl hydrazides was first
developed. In this work, we provide an efficient one-pot reaction to afford the corresponding cis-2-aryl-1,2-
dihydronaphthalen-1-ols and 2-aryl-naphthalenes in moderate to excellent yields (up to 95%) under an open-air condition.
Various types of functional groups attached to the substrates were tolerated in this method. Among them, the cis-1,2-
configuration of product 3ag was confirmed by X-ray crystallographic analysis. In addition, a plausible mechanism for the
ring-opening was also proposed.
KEYWORDS: palladium catalyst; ring-opening; oxabicyclic alkenes; arylsulfonyl hydrazides; regioselectivity
INTRODUCTION
heteroatom and carboanion nucleophiles in the presence of
3
4
5
6
7
8
9
10
catalysts including Ir, Pd, Rh, Ni, Cu, Ru, Pt, Fe,
etc.11
Transition
metal
catalyzed
ring-opening
of
oxabenzonorbornadienes has wide application value in
organic chemistry. It is an effective means of constructing
Research shows that various carboanion nucleophiles
zincs,4g,12
organoaluminums,6e,13
1
including
organic
multiple stereocenters in organic synthesis . Studies have
organolithiums,14
organoboronic
acids,15
Grignard
shown that the corresponding backbone of the ring-opening
reaction product naphthalene exists in a wide series of
reagents16 and alkyne reagents,3d,8e,17 have been widely
applied for asymmetric ring-opening of the
2
natural materials and bioactive molecules . On this basis,
oxabenzonorbornadienes. Our research group has also been
engaged in studying the ring-opening for several years. The
previous workers have developed many ring-opening
reactions of oxa(aza)bicyclic alkenes with a range of
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continuous interest in these types of reactions promoted our effective method, which employs arylsulfonyl hydrazides
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
group to further investigate the ring-opening of
oxabenzonorbornadienes with a series of heteroatom
nucleophiles. Last few years, our group have reported
asymmetric ring-opening reactions of Ir-catalyzed
oxa(aza)bicyclic alkenes with various nucleophiles
including phenols, alcohols, carboxylic acids and amines,
as aryl donors for the ring-opening of oxabicyclic alkenes
in the presence of palladium catalyst.
RESULTS AND DISCUSSION
The initial optimization of the conditions was conducted
with oxabicyclic alkenes 1a and phenylsulfonyl hydrazide
2a in 1,2-dichloroethane (DCE) at 85 °C under an air
atmosphere. According to the previously reported
literatures,22 the copper salt can promote the removal of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
resulting the compounds are excellent yields with high
enantioselectivities.5
In recent years, studies have found that aryl halides,12e,18
organometallic reagents19 and arylboronic acids3b,20 can be
used as aryl donors in ring-opening reactions to form
carbon–carbon bond. However, these arylating agents also
have some drawbacks. For example, aryl halides normally
have low activity to react with oxa(aza)bicyclic alkenes;
the organometallic reagents are generally sensitive to air
and moisture; arylboronic acids are more expensive, and so
forth. Herein, it is very important to search for a split-new
carboanion nucleophile as an aryl donor for ring-opening
with oxa(aza)bicyclic alkenes. To the best of our
knowledge, arylsulfonyl and sulfinic compounds have been
widely used in the synthesis of functional structures of
various biologically active compounds, and have become a
novel and low-cost organic synthesis reagent.21 These
compounds mainly include arylsulfonyl chloride, sodium
arylsulfinate, arylsulfonyl hydrazide and arylsulfinic acid,
which can be used as arylating agents to form C–C bonds,
respectively. Over the past few years, our group have
realized the ring-opening of oxabicyclic alkenes with
sodium arylsulfinates in the presence of Pd or Pt
catalysts.3h,9d In our continuing interest in the discovery of
new arylating reagents based on sodium arylsulfinates, we
envisioned that arylsulfonyl hydrazides could be employed
as novel aryl sources to react with oxa(aza)bicyclic alkenes.
are generally stable in air. They can be prepared in one step
from readily available arylsulfonyl chlorides and hydrazine
hydrates. Recently, there has been increasing interest in
2
SO from arylsulfonyl hydrazides. Therefore, we tried to
use copper acetate as an oxidant. We observed that the
reaction can hardly occur in the presence of palladium
catalyst or copper acetate. These control experiments
indicated that the palladium catalyst and copper salt were
essential for the desired reaction (Table 1, entries 1–2).
2 3 2
When Pd(OAc) /PPh and Cu(OAc) were simultaneously
added into the system, we succeeded in obtaining the target
product 3aa, but the yield was only 36% (Table 1, entry 3).
Encouraged by these results, we examined a range of Pd
catalysts under the same condition. The results indicated
3 2 2
Pd(PPh ) Cl is the best catalyst in this reaction (Table 1,
entries 3–6). Subsequently, various ligands were screened
under the same catalytic conditions. We found that the
yield of 3aa was improved to 54% when the system was
conducted without other ligands (Table 1, entries 7–10).
We also investigated the effect of two different chiral
bisphosphine ligands including (S)-BINAP and (R)-BINAP
on enantioselectivity. Unfortunately, we obtained the
corresponding product 3aa in low yield with poor
enantioselectivity (23% and 15% ee, respectively. Table 1,
entries 8–9). Moreover, the influence of the catalyst
loading was examined, the results showed that reducing the
catalyst loading significantly decreased the yield (39%)
(
Table 1, entry 11). In consideration of the above studies,
the catalyst loading of 10 mol% Pd(PPh Cl was
optimally selected to further optimize the reaction.
3
)
2
2
Table 1. Effects of catalysts, ligands, and catalyst loadingsa,b,c
2 2
constructing C–C bond by liberating N and SO of
OH
arylsulfonyl hydrazides in situ. However, the reaction of
oxabenzonorbornadienes with arylsulfonyl hydrazides has
not been explored so far. Herein, we first developed an
Ph
catalyst, ligand
O
+ PhSO NHNH2
2
additive, DCE
o
1
a
2a
85 C, 8 h
3
aa
2
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The Journal of Organic Chemistry
catalyst
(10 mol%)
none
ligand
(20 mol%)
none
additive
yieldc
(%)
–
ee
Table 2. Optimization of solvents, temperatures and
entry
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(1.5 equiv.)
(%)
additivesa,b
1
2
3
4
5
6
7
8
9
Cu(OAc)
none
2
OH
Pd(OAc)
Pd(OAc)
2
2
PPh
PPh
PPh
PPh
PPh
3
3
3
3
3
–
3 2 2
Pd(PPh ) Cl
Ph
(10 mol%)
O
+ PhSO NHNH2
2
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
36
40
46
37
54
34
39
35
39
additive, solvent
temp., time
1
a
2a
3aa
PdCl
Pd(PPh
Pd(CH
Pd(PPh
2
yieldb
time
(h)
8
3
)
2
Cl
2
solvent
(2 mL)
temp.
(oC)
additive
entry
3
CN)
2
Cl
2
(1.5 equiv.)
(
%)
45
40
38
47
50
56
67
70
82
79
55
93
3
)
2
Cl
2
none
(R)-BINAP
(S)-BINAP
DPPE
Cu(OAc)
2
1
2
DCE
DCE
DCE
DCE
85
85
85
85
85
85
85
CuO
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
3
)
2
2
2
2
Cl
Cl
Cl
Cl
2
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
15
23
(CF
CuCl
Cu(C
3
SO
3
)
2
Cu
8
3
3
3
)
)
)
2
2
2
2
3
2
8
1
0
2
2
4
5
H
7
O
2
)
2
8
11b
none
aUnless otherwise noted, the reaction was conducted with oxabicyclic alkene
5
CH
THF
CH CN
3
OH
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
8
1
a (0.1 mmol, 14.4 mg) and 2a (0.2 mmol, 34.4 mg) in the presence of 10
6
2
2
2
2
8
b
mol% catalyst and 20 mol% ligand in 2.0 mL of solvent in 8 h. The catalyst
7
3
4
c
loading is 5 mol%. Isolated yield.
8
1,4-dioxane
DMF
85
85
4
9
1
Next, we continued to study the influence of additives,
solvents and temperatures on the reaction. To further
optimize the reaction, several cupric salts, such as CuO,
10
11
12b
DMSO
DMF
85
Cu(OAc)2
Cu(OAc)
Cu(OAc)
1
65
2
10
0.25
DMF
100
2
aUnless otherwise noted, the reaction was conducted with oxabicyclic alkene
(
3 3 2 2 5 7 2 2
CF SO ) Cu, CuCl and Cu(C H O ) were also tested.
1
a (0.1 mmol, 14.4 mg) and 2a (0.2 mmol, 34.4 mg) in the presence of 10
Unfortunately, they led to much lower yields (Table 2,
entries 1–4). Then, we explored the effect of solvent effect
on the reaction. The results indicated the solvent effect has
a significant influence on the yield. The reaction only gave
b
mol% catalyst (7.0 mg) in 2.0 mL of solvent. Isolated yield.
With the optimized conditions in hand, we went on to
investigate the generality of the reaction with various
arylsulfonyl hydrazides, which were listed in Table 3. We
could see the structures of arylsulfonyl hydrazides 2 have a
significant impact on the reactivity from Table 3. Although
mostly arylsulfonyl hydrazides 2 proceeded smoothly with
substrate 1a, it is apparent that the arylsulfonyl hydrazides
2 with an electron donating group on the phenyl ring gave
higher yield than those having an electron withdrawing
group (Table 3, entries 2–7). Considering the effect of the
group position properties of the mono-substituted
arylsulfonyl hydrazides on the reactivity, we noted that
they had significant effect on the reactivity. For example,
when 4-chlorobenzenesulfonyl hydrazide 2e acted as the
nucleophilic reagent, the yield of target product 3ae was as
high as 91% (Table 3, entry 5). In contrast, when 2-
chlorobenzenesulfonyl hydrazide 2d as a nucleophile, the
product 3ad was obtained in only 63% yield (Table 3, entry
low yields in the protic solvent CH
3
OH or the non-polar
(
aprotic) solvent tetrahydrofuran (THF) (Table 2, entries 5–
6
). Better results were obtained with moderate yields in the
CN (Table 2,
polar (aprotic) solvent 1,4-dioxane or CH
3
entries 7–8). Fortunately, high boiling dipolar (aprotic)
solvent dimethyl sulfoxide (DMSO) or dimethyl
formamide (DMF) dramatically enhanced the yield up to
79% and 82%, respectively (Table 2, entries 9–10).
However, we haven’t yet achieved the best conditions. The
effect of temperature on this reaction was also examined.
Results indicated the temperature had an obvious effect on
reaction rate too. When the temperature was 100 °C, the
product 3aa was obtained in an excellent yield (93%)
within 15 min (Table 2, entry 12). Therefore, the optimal
reaction conditions were established as 10 mol%
Pd(PPh
3
)
2
Cl
2
, 2.0 equiv of arylsulfonyl hydrazides and 1.5
o
equiv of Cu(OAc)
air atmosphere.
2
in DMF at 100 C for 0.25 h under an
4
).
In
addition
to
these,
when
2,4,6-
trimethylbenzenesulfonyl hydrazide 2h was employed in
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the reaction, the desired product 3ah was obtained in 36% reactivity due to the influence of steric hindrance (Table 4,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
yield due to the influence of steric hindrance (Table 3,
entry 8).
entry 17).
Table
4.
Palladium-catalyzed
ring-opening
of
Table
3.
Palladium-catalyzed
ring-opening
of
oxabenzonorbornadiene 1b–1h with various arylsulfonyl
hydrazides 2a,b
oxabenzonorbornadiene 1a with various arylsulfonyl
hydrazides 2 a,b
R2
R2 OH
R1
R1
PdCl2(PPh3)2
10 mol%)
R1
R1
Ar
(
OH
O
+
ArSO2NHNH2
Pd(PPh3)2Cl2
Cu(OAc)2 (1.5 equiv.)
DMF, 100 oC, 15 min
Ar
2
(10 mol%)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
O
+ ArSO NHNH
R2
1b-1h
R3
R2
R3
2
2
Cu(OAc)2 (1.5 equiv.)
DMF, 100 oC, 15 min
3ba-3ha
1a
2a-2h
1b: R1 = R3 = H , R2 = OCH3
3
aa-3ah
- H2O
c: R1 = OCH3, R2 = R3 = H
d: R1 = Br, R2 = R3 = H
e: R1 = R2 = H, R3 = Me
1
1
1
b
R2
entry
Ar
product
3aa
yield (%)
R1
R1
Ar
1
2
3
4
5
6
7
8
C
6
H
5
93
94
90
63
91
89
85
36
1f : R1 = Me, R2 = R3 = H
g: R1 = F, R2 = R3 = H
1
4-CH
3
C
6
H
4
3ab
3ac
R2
R3
4ca-4ce
1h: R1 + R2
, R3 = H
=
4-CH OC H
3
6 4
2-ClC
6
6
H
4
4
3ad
3ae
yieldb
b
entry
Ar
substrate
prod. 3 yield (%) prod. 4
4-ClC
H
(%)
4-FC
4-O NC
2,4,6-(CH
6
H
4
3af
1
2
3
4
5
6
7
8
9
C H
1b
1b
1b
1c
1c
1c
1d
1d
1d
1e
1e
1e
1f
3ba
3bb
3be
96
91
70
6
5
2
6
H
4
3ag
3 6
4-CH C H
4
4
4
4
4
3
)
3
C
6
H
2
3ah
4-ClC H
6
4
aUnless otherwise noted, the reaction was conducted with oxabicyclic alkene
C H
6
5
4ca
4cb
4ce
95
94
62
1
a (0.1 mmol, 14.4 mg) and 2a–2h (0.2 mmol) in the presence of 10 mol%
4-CH
3
C
6
H
b
catalyst (7.0 mg) in 2.0 mL of solvent. Isolated yield.
4-ClC
6
H
4
C
6
H
5
3da
3db
3de
3ea
3eb
3ee
3fa
3fb
3fe
75
71
65
83
70
67
88
81
71
91
57
4-CH
3
C
6
H
Furthermore, the range of the ring-opening was further
surveyed by various oxabenzonorbornadienes 1b–1h,
which were summarized in Table 4. As shown in Table 4,
apart from substrate 1h, the ring-opening of other
oxabicyclic alkenes with phenylsulfonyl hydrazide 2a
proceeded smoothly to give the desired products in
moderate to excellent yields under the optimized condition.
Compared with electron-defect substrates, electron-rich
substrates reacted better with various arylsulfonyl
hydrazides. Interestingly, we could obtain the
corresponding further dehydrated products 2-aryl-
naphthalenes 4ca–4ce in high yields, but could not obtain
the expected ring-opening products 3 when we employed
methoxy substituted oxabenzonorbornadiene 1c to react
with arylsulfonyl hydrazides 2 (Table 4, entries 4–6). It's
worth noting that the asymmetric substrate 1e bearing a
methyl substituent at the position of oxo-bridge carbon
reacted well with arylsulfonyl hydrazides 2, affording the
4-ClC
6
H
4
1
1
0
1
6 5
C H
4-CH
3
C
6
H
12
13
14
4-ClC H
6
4
6 5
C H
4-CH
3
C
6
H
1f
1
1
1
5
6
7
4-ClC
6
H
4
1f
C
6
6
H
5
1g
1h
3ga
3ha
C
H
5
aUnless otherwise noted, the reaction was conducted with oxabicyclic alkene
1
b-1h (0.1 mmol) and 2a-2e (0.2 mmol) in the presence of 10 mol% catalyst
b
(7.0 mg) in 2.0 mL of solvent. Isolated yield.
To further evaluate the reaction efficiency at the
preparative scale, a scaled-up reaction was then carried out.
The desired product 3aa was obtained in 64% (0.286 g)
yields under the standard conditions, implying its possible
applications of this method in synthetic chemistry (Scheme
1
).
Scheme 1. Scaled-up experiment of 3aa
target products
3
in moderate yield with high
regioselectivity (Table 4, entries 10–12). Moreover,
substrate 1h with arylsulfonyl hydrazides 2 showed low
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arylsulfonyl hydrazides as aryl sources under mild
OH
Pd(PPh3)2Cl2
10 mol%)
1
2
3
4
5
Ph
(
O
+ PhSO NHNH
conditions. Arylsulfonyl hydrazides were first used as
carboanion nucleophiles in the ring-opening by liberating
2
2
Cu(OAc)2 (3.0 mmol)
DMF, 100 oC, 15 min
1
(
a, 0.288g
2.0 mmol)
2a, 0.689g
(4.0 mmol)
3aa, 0.286g
64% yield
2 2
N and SO in situ. This protocol offers a facile means for
Scheme 2. Plausible Mechanism
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
synthesizing cis-2-aryl-1,2-dihydronaphthalen-1-ols 3 and
2-arylnaphthalenes 4 with moderate to excellent yields. Our
laboratory is further investigating the applications of
palladium catalysts in other ring-opening reactions.
HOAc Ph3P
Cl
Cl
ArSO2NHNH2
HCl, Cu(OAc)2
Pd
2
Ph3P
HCl
Ph3P
Ph3P
Ph3P
NHNHSO2Ar
Cl
Pd(0)
Pd
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
OH
Ph3P
H2O
A
Ar
Ph3P
Ph3P
H
HCl
Pd
3
4
PPh3
Pd
Cl
ArSO2N NH
Ph3P
Ph3P
HCl
Cl
Cl
Cl
EXPERIMENTAL SECTION
B
Pd
-H2O
Ph3P
O
Ar
Ar
General Methods. Unless otherwise indicated, all reagents
and solvents were purchased from commercial sources and
used without further purification. Oxabicyclic alkenes (1a–
1h) were prepared according to literature procedures, and
the corresponding spectral and physical data were
consistent with the literature data.23 Flash column
chromatography was performed using the indicated solvent
system on Qingdao-Haiyang silica gel (200−300 mesh).
The products were separated by Anhui-Liangchen thin-
layer chromatography silica gel. All of the compounds
Ph3P
Ph3P
Cl
N
F
Pd
Ar
O
NSO2Ar
C
Cl
Pd
E
Ph3P
Ph3P
Cl
PPh3
Ph3P
Pd
SO2+N2
Ar
D
O
1a
According to our experimental results and the general
mechanism of desulfurization cross-coupling reactions, we
proposed the following plausible mechanism for the Pd-
catalyzed ring-opening of oxabicyclic alkene 1a with
arylsulfonyl hydrazides 2 (Scheme 2). Displacement of
were determined and characterized by 1H, 13C and 19F
NMR. Peaks recorded are relative to the internal standards:
3 2 2
Pd(PPh ) Cl catalyst by arylsulfonyl hydrazide 2 results in
the formation of complex A which undergoes β-hydride
elimination to give sulfonyl diazene B and meanwhile
1
TMS (δ = 0.00) for H NMR and CDCl
3
(δ = 77.00) for
C{ H} NMR spectra. H and C{ H} NMR spectra were
recorded at 600 MHz and 150 MHz at 25 °C in CDCl
respectively. 19F NMR spectra were recorded at 565 MHz
at 25 °C in CDCl . Spectral data are reported as follows:
1
3
1
1
13
1
release HPd(PPh
HPd(PPh Cl followed by oxidation with Cu(OAc)
regenerates Pd(II) catalyst. Displacement of Pd(PPh
3
)
2
Cl. Reductive elimination of
/HCl
Cl
2
3
,
3
)
2
2
3
)
2
3
with sulfonyl diazene B gives complex C. Successive
extrusion of nitrogen and sulfur dioxide from complex C
leads to the formation of arylpalladium D, which undergoes
exo-1,2-addition with substrate 1a to form intermediate E,
then eliminated the β-oxygen atom to afford a new Pd
intermediate F. Protonation of the last species F by water
affords cis-2-aryl-1,2-dihydronaphthalen-1-ol product 3
chemical shift (δ, ppm); multiplicity (s-singlet, d-doublet, t-
triplet, q-quadruplet, and m-multiplet); coupling constants
(J, Hz) and number of protons. HRMS (ion trap) spectra
were obtained using a mass spectrometer (ESI) and MS
spectra were recorded using EI at 70 eV. Enantiomeric
excesses were determined with a Chiralcel AD-H column
eluted with a mixture of hexane and i-propanol (hexane/i-
propanol 92:8 (v/v), 1.0 mL/min, λ = 254 nm) Melting
points were uncorrected. The crystal structure
determination was carried out by X-ray diffraction
apparatus.
3 2
and a HPd(PPh ) Cl. Further dehydration of ring-opened
product 3 gives the 2-aryl-naphthalene 4.
CONCLUSIONS
In conclusion, we have demonstrated an unprecedented
General Procedure. All experiments were carried out
under an open-air condition. Oxabicyclic alkenes 1 (0.1
Pd-catalyzed
ring-opening
with
reaction
readily
of
oxabenzonorbornadienes
available
mmol), arylsulfonyl hydrazides 2 (2.0 equiv., 0.2 mmol),
5
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The Journal of Organic Chemistry
Page 6 of 13
Cu(OAc)
2 3 2 2
(27.2mg, 1.5 equiv., 0.15 mmol), Pd(PPh ) Cl
1H), 7.23 (d, J = 7.3 Hz, 1H), 7.21 – 7.09 (m, 3H), 6.90 –
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(10 mol%, 7.0mg) and DMF (2.0 mL) were simultaneously
6.79 (m, 2H), 6.68 (dd, J = 9.6, 1.6 Hz, 1H), 6.10 (dd, J =
9.6, 4.3 Hz, 1H), 4.93 (d, J = 6.1 Hz, 1H), 3.83 – 3.80 (m,
added into a 10.0 mL round-bottomed flask. The mixed
solution was stirred at 100 °C in oil bath for 15 min. After
cooling to room temperature, the reaction mixture was
added 20 mL water and then extracted by ethyl acetate (10
mL×3), The organic layers were combined, dried with
1
3
1
1H), 3.76 (d, J = 12.6 Hz, 3H), 1.57 (s, 1H). C{ H} NMR
(150 MHz, CDCl ) δ 159.0, 136.3, 132.7, 130.3, 130.0,
3
129.1, 128.2, 128.0, 128.0, 126.5, 126.3, 114.1, 71.3, 55.2,
-
46.4. HRMS m/z (ESI-ion trap) [M - H
: 249.0916, found: 249.0916.
(1S*,2R*)-2-(2-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
2
- H] calcd for
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
anhydrous Na
2
SO
4
, and then filtered. The filtrate was
17 13 2
C H O
concentrated under vacuum, and the resulting residue was
purified by column chromatography on silica gel (200–300
mesh) using ethyl acetate/petroleum ether as eluent to
afford the desired product 3 and 4.
(3ad). Following the general procedure, 3ad was obtained
1
as a colorless oil (16.1 mg, 63%). H NMR (600 MHz,
CDCl
3
) δ 7.39 – 7.34 (m, 1H), 7.34 – 7.25 (m, 3H), 7.23 –
7
9
1
.15 (m, 4H), 6.68 (dd, J = 9.6, 2.7 Hz, 1H), 5.98 (ddd, J =
(1S*,2R*)-2-Phenyl-1,2-dihydronaphthalen-1-ol
(3aa).
.6, 2.9, 0.9 Hz, 1H), 4.83 (s, 1H), 4.42 (dt, J = 5.3, 2.9 Hz,
Following the general procedure, 3aa was obtained as a
H), 1.46 (s, 1H). 13C{ H} NMR (150MHz, CDCl
1
) δ
1
3
colorless oil (20.7 mg, 93%). H NMR (600 MHz, CDCl
3
)
136.9, 135.2, 134.2, 132.1, 131.0, 129.6, 129.0, 128.8,
δ 7.29 – 7.20 (m, 6H), 7.19 – 7.16 (m, 2H), 7.10 (dd, J =
7.4, 1.0 Hz, 1H), 6.64 (dd, J = 9.6, 2.1 Hz, 1H), 6.06 (dd, J
1
28.5, 128.3, 128.1, 128.0, 127.0, 126.7, 69.2, 44.0. HRMS
-
m/z (ESI-ion trap) [M - H] calcd for C16
H
12ClO: 255.0577,
=
9.6, 4.0 Hz, 1H), 4.86 (d, J = 5.1 Hz, 1H), 3.80 (ddd, J =
found: 255.0587.
1
3
1
6
.0, 4.0, 2.1 Hz, 1H), 1.49 (s, 1H). C{ H} NMR
150MHz, CDCl ) δ 137.7, 136.1, 132.6, 129.7, 129.3,
28.7, 128.3, 128.2, 128.0, 127.42, 126.7, 126.4, 71.3, 47.3.
(
3
(1S*,2R*)-2-(4-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
1
(3ae). Following the general procedure, 3ae was obtained
-
HRMS m/z (ESI-ion trap) [M - H
2
- H] calcd for C16
H
11O:
o
1
as a white solid (23.3 mg, 91%). m.p. 113.0–114.0 C. H
NMR (600 MHz, CDCl ) δ 7.35 – 7.29 (m, 2H), 7.28 –
.24 (m, 3H), 7.21 – 7.15 (m, 3H), 6.71 (dd, J = 9.6, 2.0 Hz,
H), 6.08 (dd, J = 9.6, 4.1 Hz, 1H), 4.92 (d, J = 5.9 Hz, 1H),
2
19.0811, found: 219.0814.
3
7
1
3
(1S*,2R*)-2-(p-Tolyl)-1,2-dihydronaphthalen-1-ol (3ab).
Following the general procedure, 3ab was obtained as a
.83 (ddd, J = 6.0, 4.1, 2.0 Hz, 1H), 1.47 (s, 1H). 13C{ H}
1
1
colorless oil (22.2mg, 94%). H NMR (600 MHz, CDCl
3
) δ
3
NMR (150 MHz, CDCl ) δ 136.3, 135.9, 133.2, 132.4,
7.27 (dd, J = 7.3, 0.6 Hz, 1H), 7.21 (td, J = 7.4, 1.3 Hz, 1H),
.16 (dd, J = 7.4, 1.4 Hz, 1H), 7.12 – 7.02 (m, 5H), 6.62
(dd, J = 9.6, 2.0 Hz, 1H), 6.04 (dd, J = 9.6, 4.1 Hz, 1H),
130.6, 129.2, 128.7, 128.5, 128.4, 128.2, 126.5, 126.5, 71.2,
7
-
4
6.7. HRMS m/z (ESI-ion trap) [M - H
10ClO: 253.0421, found: 253.0423.
2
- H] calcd for
16
C H
4
1
.85 (d, J = 5.7 Hz, 1H), 3.76 (ddd, J = 6.1, 4.1, 2.0 Hz,
H), 2.25 (s, 3H), 1.48 (s, 1H). 13C{ H} NMR (150 MHz,
1
(1S*,2R*)-2-(4-Fluorophenyl)-1,2-dihydronaphthalen-1-ol
CDCl
3
) δ 137.1, 136.2, 134.4, 132.7, 129.9, 129.4, 129.1,
(3af). Following the general procedure, 3af was obtained as
1
28.2, 128.1, 128.0, 126.6, 126.3, 71.3, 46.9, 21.0. HRMS
o
1
a white solid (21.4mg, 89%). m.p. 100.0–101.0 C. H
NMR (600 MHz, CDCl ) δ 7.39 – 7.31 (m), 7.30 – 7.28
(m), 7.27 – 7.22 (m), 7.20 (d, J = 7.4 Hz), 7.13 – 6.93 (m),
-
2
m/z (ESI-ion trap) [M - H - H] calcd for C17H13O:
3
2
33.0967, found: 233.0971.
6
.73 (dd, J = 9.6, 1.8 Hz), 6.12 (dd, J = 9.6, 4.1 Hz), 4.95
(1S*,2R*)-2-(4-Methoxyphenyl)-1,2-dihydronaphthalen-
(d, J = 5.9 Hz), 3.95 – 3.76 (m), 1.50 (s). 13C{ H} NMR
1
1
-ol (3ac). Following the general procedure, 3ac was
1
3
(150 MHz, CDCl ) δ 163.0, 161.3, 136.0, 133.3 (d, J = 3.2
obtained as a colorless oil (22.7mg, 90%). H NMR (600
Hz), 132.5, 130.8 (d, J = 7.8 Hz), 129.6, 128.3 (d, J = 9.0
3
MHz, CDCl ) δ 7.35 (d, J = 7.3 Hz, 1H), 7.28 (t, J = 7.3 Hz,
Hz), 128.1, 126.5 (d, J = 15.1 Hz), 115.5, 115.3, 71.2, 46.5.
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19F NMR (565 MHz, CDCl
The Journal of Organic Chemistry
dihydronaphthalen-1-ol (3bb). Following the general
procedure, 3bb was obtained as a white solid (26.9mg,
3
) δ -115.4 (s). HRMS m/z (ESI-
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
-
ion trap) [M - H] calcd for C16
239.0873.
H12FO: 239.0871, found:
o
1
91%). m.p. 101.0–102.0 C. H NMR (600 MHz, CDCl
.32 (d, J = 7.9 Hz, 2H), 7.21 (d, J = 7.8 Hz, 2H), 7.08 (dd,
J = 9.8, 3.2 Hz, 1H), 6.81 (q, J = 8.9 Hz, 2H), 6.28 – 6.00
3
) δ
7
(
1S*,2R*)-2-(4-Nitrophenyl)-1,2-dihydronaphthalen-1-ol
3ag). Following the general procedure, 3ag was obtained
(
(m, 1H), 5.06 (d, J = 4.1 Hz, 1H), 3.83 (t, J = 14.7 Hz, 6H),
as a pale-yellow solid (22.7 mg, 85%). m.p. 122.3–123.6
.78 – 3.75 (m, 1H), 2.36 (s, 3H), 1.59 (s, 1H). 13C{ H}
1
3
o
1
C. H NMR (600 MHz, CDCl
7.44 (d, J = 8.6 Hz), 7.35 – 7.27 (m), 7.21 (d, J = 7.3 Hz),
.77 (dd, J = 9.6, 2.0 Hz), 6.08 (dd, J = 9.6, 3.8 Hz), 4.93
3
) δ 8.15 (d, J = 8.7 Hz),
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
NMR (150 MHz, CDCl
3
) δ 150.8, 149.7, 137.2, 136.6,
1
5
29.3, 129.1, 128.9, 124.3, 122.6, 122.0, 111.4, 110.9, 64.3,
6
2
6.2, 56.2, 46.8, 21.1. HRMS m/z (ESI-ion trap) [M - H -
1
3
1
(s), 3.95 (t, J = 5.7 Hz), 1.60 (s). C{ H} NMR (150 MHz,
CDCl ) δ 147.2, 146.4, 135.5, 132.1, 130.2, 129.0, 128.8,
28.4, 128.1, 126.8, 126.6, 123.5, 71.1, 47.2. HRMS m/z
-
H] calcd for C19
H
17O3: 293.1178, found: 293.1177.
3
1
(1S*,2R*)-2-(4-Chlorophenyl)-5,8-dimethoxy-1,2-
-
(
ESI-ion trap) [M - H] calcd for C16
H
12NO
3
: 266.0816,
dihydronaphthalen-1-ol (3be). Following the general
procedure, 3be was obtained as a white solid (22.1mg,
found: 266.0813.
o
1
7
0%). m.p. 114.0–116.0 C. H NMR (600 MHz, CDCl
3
) δ
(1S*,2R*)-2-Mesityl-1,2-dihydronaphthalen-1-ol (3ah).
Following the general procedure, 3ah was obtained as a
7
.38 – 7.31 (m, 4H), 7.08 (dd, J = 9.8, 3.2 Hz, 1H), 6.81 (q,
J = 9.0 Hz, 2H), 6.06 (ddd, J = 9.8, 2.3, 1.5 Hz, 1H), 5.06
o
1
white solid (9.5mg, 36%). m.p. 122.0–124.0 C. H NMR
(s, 1H), 3.82 (d, J = 8.6 Hz, 6H), 3.76 – 3.73 (m, 1H), 1.62
(600 MHz, CDCl
3
) δ 7.35 (ddd, J = 8.8, 6.8, 3.0 Hz), 7.27
(d, J = 14.7 Hz, 1H). 13C{ H} NMR (150 MHz, CDCl
1
) δ
3
(
dd, J = 7.4, 1.2 Hz), 7.21 (d, J = 7.5 Hz), 6.92 (s), 6.60 (dd,
1
1
50.6, 149.7, 139.1, 132.7, 130.5, 128.5, 128.4, 124.2,
22.3, 111.5, 111.0, 64.3, 56.2, 56.1, 46.6. HRMS m/z
J = 9.6, 3.3 Hz), 6.25 – 6.11 (m), 4.74 (d, J = 4.9 Hz), 4.21
(
dt, J = 5.3, 2.8 Hz), 2.50 (s), 2.35 (s), 2.28 (s), 1.56 (s).
-
(
ESI-ion trap) [M - H
2
3
- H] calcd for C18H14ClO :
1
3
1
3
C{ H} NMR (150 MHz, CDCl ) δ 139.0, 137.0, 136.3,
3
13.0632, found: 313.0624.
1
1
35.1, 132.8, 132.6, 132.2, 131.0, 129.3, 129.1, 129.0,
2
,3-Dimethoxy-6-phenylnaphthalene (4ca). Following the
27.3, 126.8, 124.0, 70.0, 43.2, 21.5, 21.0, 20.7. HRMS
general procedure, 4ca was obtained as a white solid
-
m/z (ESI-ion trap) [M - H
61.1280, found: 261.1277.
1S*,2R*)-5,8-Dimethoxy-2-phenyl-1,2-
2
- H] calcd for C19
H
17O:
o
1
(
25.1mg, 95%). m.p. 121.0–122.0 C. H NMR (600 MHz,
CDCl ) δ 7.89 (s, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.71 – 7.67
(m, 2H), 7.60 (dd, J = 8.4, 1.8 Hz, 1H), 7.46 (t, J = 7.7 Hz,
H), 7.35 (t, J = 7.4 Hz, 1H), 7.15 (d, J = 23.6 Hz, 2H),
2
3
(
dihydronaphthalen-1-ol (3ba). Following the general
2
procedure, 3ba was obtained as a colorless oil (27.1 mg,
1
3
1
4.00 (d, J = 1.7 Hz, 6H). C{ H} NMR (150 MHz, CDCl
3
)
1
9
6%). H NMR (600 MHz, CDCl
3
) δ 7.41 (dt, J = 13.3, 7.5
δ 149.8, 149.6, 141.3, 137.0, 129.4, 128.8, 128.4, 127.2,
Hz, 4H), 7.31 (t, J = 7.3 Hz, 1H), 7.09 (dd, J = 9.8, 3.2 Hz,
H), 6.82 (q, J = 9.0 Hz, 2H), 6.24 – 6.07 (m, 1H), 5.09 (dd,
1
27.0, 126.8, 124.3, 123.8, 106.6, 106.0, 55.8. HRMS m/z
1
+
(
ESI-ion trap) [M + H] calcd for C18
H
17
O
2
: 265.1228,
J = 4.6, 1.2 Hz, 1H), 3.83 (d, J = 6.7 Hz, 6H), 3.81 – 3.79
found: 265.1225.
m, 1H), 1.59 (s, 1H). 13C{ H} NMR (150 MHz, CDCl
1
) δ
(
3
150.7, 149.7, 140.4, 129.1, 128.9, 128.6, 127.0, 124.3,
2,3-Dimethoxy-6-(p-tolyl)naphthalene (4cb). Following the
general procedure , 4cb was obtained as a white solid
1
22.5, 122.1, 111.5, 110.9, 64.3, 56.2, 56.2, 47.3. HRMS
-
o
1
m/z (ESI-ion trap) [M - H
2
- H] calcd for C18
H
15
O
3
:
(26.1mg, 94%). m.p. 136.2–137.2 C. H NMR (600 MHz,
2
79.1022, found: 279.1026.
CDCl ) δ 7.88 (s, 1H), 7.73 (d, J = 8.4 Hz, 1H), 7.63 – 7.52
3
(m, 3H), 7.27 (d, J = 7.7 Hz, 2H), 7.16 (s, 1H), 7.13 (s, 1H),
(
1S*,2R*)-5,8-Dimethoxy-2-(p-tolyl)-1,2-
13
1
4
.00 (d, J = 2.3 Hz, 6H), 2.41 (s, 3H). C{ H} NMR (150
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The Journal of Organic Chemistry
) δ 149.7, 149.4, 138.4, 136.9, 136.7, 129.5, 1H), 7.27 – 7.25 (m, 2H), 7.15 – 7.08 (m, 2H), 6.60 (dd, J =
3
Page 8 of 13
MHz, CDCl
29.4, 128.2, 127.0, 126.7, 124.0, 123.8, 106.5, 106.1, 55.8,
21.1. HRMS m/z (ESI-ion trap) [M + H]+ calcd for
: 279.1385, found: 279.1383.
6-(4-Chlorophenyl)-2,3-dimethoxynaphthalene
Following the general procedure, 4ce was obtained as a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
9.7, 1.4 Hz, 1H), 6.16 (dd, J = 9.6, 4.8 Hz, 1H), 4.95 (t, J =
7.3 Hz, 1H), 3.82 – 3.76 (m, 1H), 1.58 (s, 1H). 13C{ H}
1
C
19
H
19
O
2
3
NMR (150 MHz, CDCl ) δ 136.8, 134.2, 133.8, 133.3,
(4ce).
131.4, 131.3, 130.9, 130.6, 128.9, 126.7, 124.2, 123.8, 70.2,
-
46.1. HRMS m/z (ESI-ion trap) [M - H
2
- H] calcd for
o
1
white solid (18.5mg, 94%). m.p. 139.0–140.0 C. H NMR
600 MHz, CDCl ) δ 7.84 (d, J = 1.5 Hz, 1H), 7.72 (d, J =
.4 Hz, 1H), 7.62 – 7.56 (m, 2H), 7.52 (dd, J = 8.4, 1.8 Hz,
C
16
H
8
Br ClO: 408.8631, found: 408.8634.
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
3
(1S*,2R*)-4-Methyl-2-phenyl-1,2-dihydronaphthalen-1-ol
8
1
6
(3ea). Following the general procedure, 3ea was obtained
1
H), 7.44 – 7.37 (m, 2H), 7.13 (d, J = 19.5 Hz, 2H), 4.00 (s,
as a pale-yellow oil (19.6mg, 83%). H NMR (600 MHz,
CDCl ) δ 7.37 – 7.33 (m), 7.31 – 7.28 (m), 7.28 – 7.23 (m),
H). 13C{ H} NMR (150 MHz, CDCl
1
) δ 149.9, 149.7,
3
3
139.8, 135.6, 133.0, 129.3, 128.9, 128.5, 128.4, 126.9,
5.94 (dd, J = 3.9, 1.2 Hz), 4.89 (d, J = 5.7 Hz), 3.83 (ddd, J
= 5.9, 4.1, 1.9 Hz), 2.19 (t, J = 1.6 Hz), 1.53 (s). 13C{ H}
1
1
24.2, 123.4, 106.5, 106.0, 55.8. HRMS m/z (ESI-ion trap)
+
[M + H] calcd for C18
H
16ClO
2
: 299.0839, found: 299.0835.
NMR (150 MHz, CDCl
3
) δ 138.2, 136.5, 134.2, 132.9,
1
4
29.2, 128.6, 128.2, 127.8, 127.3, 126.5, 126.3, 123.3, 71.5,
(1S*,2R*)-6,7-Dibromo-2-phenyl-1,2-dihydronaphthalen-
-
2
7.2, 19.2. HRMS m/z (ESI-ion trap) [M - H - H] calcd
1
-ol (3da). Following the general procedure, 3da was
for C17H13O: 233.0967, found: 233.0970.
1
obtained as a colorless oil (28.3mg, 75%). H NMR (600
MHz, CDCl
3
) δ 7.56 (s, 1H), 7.40 (s, 1H), 7.30 – 7.25 (m,
(1S*,2R*)-4-Methyl-2-(p-tolyl)-1,2-dihydronaphthalen-1-ol
3H), 7.21 – 7.12 (m, 2H), 6.59 (dd, J = 9.6, 1.3 Hz, 1H),
(3eb). Following the general procedure, 3eb was obtained
1
6
1
1
1
.20 (dd, J = 9.6, 4.8 Hz, 1H), 4.95 (s, 1H), 3.93 – 3.73 (m,
as a pale-yellow oil (17.5mg, 70%). H NMR (600 MHz,
H), 1.55 (s, 1H). 13C{ H} NMR (150 MHz, CDCl
1
) δ
3
3
CDCl ) δ 7.42 – 7.29 (m, 3H), 7.26 (dd, J = 6.8, 2.1 Hz,
37.1, 135.6, 133.5, 131.8, 131.4, 130.8, 129.3, 128.9,
1H), 7.17 – 7.02 (m, 4H), 5.93 (d, J = 3.1 Hz, 1H), 4.88 (d,
27.9, 126.4, 124.0, 123.6, 70.2, 46.7. HRMS m/z (ESI-ion
J = 5.4 Hz, 1H), 3.98 – 3.68 (m, 1H), 2.31 (s, 3H), 2.18 (s,
-
3H), 1.56 (s, 1H). 13C{ H} NMR (150 MHz, CDCl
1
trap) [M - H
74.9022.
2
- H] calcd for C16
H
9
Br
2
O: 374.9021, found:
3
) δ
3
136.9, 136.7, 134.9, 134.3, 132.7, 129.3, 129.1, 128.1,
127.7, 126.6, 126.5, 123.2, 71.5, 46.8, 21.0, 19.2. HRMS
(1S*,2R*)-6,7-Dibromo-2-(p-tolyl)-1,2-
-
m/z (ESI-ion trap) [M - H
2
- H] calcd for C18
H
16O:
dihydronaphthalen-1-ol (3db). Following the general
procedure, 3db was obtained as a colorless oil (27.8mg,
2
47.1124, found: 247.1121.
1
7
1
1%). H NMR (600 MHz, CDCl
3
) δ 7.58 (s, 1H), 7.39 (s,
(1S*,2R*)-2-(4-Chlorophenyl)-4-methyl-1,2-
H), 7.08 (dd, J = 35.4, 8.0 Hz, 4H), 6.58 (dd, J = 9.7, 1.4
dihydronaphthalen-1-ol (3ee). Following the general
Hz, 1H), 6.19 (dd, J = 9.6, 4.9 Hz, 1H), 4.96 (d, J = 6.2 Hz,
procedure, 3ee was obtained as a pale-yellow oil (18.1mg,
1
3
1
1
1
H), 3.91 – 3.56 (m, 1H), 2.31 (s, 3H), 1.51 (s, 1H). C{ H}
67%). H NMR (600 MHz, CDCl
3
) δ 7.38 – 7.32 (m, 3H),
NMR (150 MHz, CDCl
3
) δ 137.7, 137.3, 133.6, 132.2,
7.29 – 7.26 (m, 1H), 7.26 (d, J = 2.7 Hz, 1H), 7.25 – 7.24
(m, 1H), 7.19 – 7.11 (m, 2H), 5.89 (dd, J = 4.1, 1.4 Hz, 1H),
4.87 (s, 1H), 3.79 (ddd, J = 5.9, 4.1, 1.9 Hz, 1H), 2.18 (t, J
1
4
32.0, 131.4, 130.7, 129.6, 129.1, 126.2, 123.9, 123.6, 70.2,
-
2
6.2, 21.0. HRMS m/z (ESI-ion trap) [M - H - H] calcd
= 1.6 Hz, 3H), 1.57 (s, 1H). 13C{ H} NMR (150 MHz,
1
for C17
H
11Br
2
O: 388.9177, found: 388.9179.
CDCl ) δ 136.8, 136.4, 134.0, 133.3, 133.0, 130.6, 128.6,
3
(1S*,2R*)-6,7-Dibromo-2-(4-chlorophenyl)-1,2-
128.3, 128.0, 126.4, 125.8, 123.4, 71.5, 46.6, 19.2. HRMS
dihydronaphthalen-1-ol (3de). Following the general
procedure, 3de was obtained as a colorless oil (22.7mg,
-
m/z (ESI-ion trap) [M - H
2
- H] calcd for C17
H
12ClO:
1
267.0577, found: 267.0574.
6
3
5%). H NMR (600 MHz, CDCl ) δ 7.57 (s, 1H), 7.40 (s,
8
ACS Paragon Plus Environment

Page 9 of 13
The Journal of Organic Chemistry
(
1S*,2R*)-6,7-Dimethyl-2-phenyl-1,2-dihydronaphthalen-
J = 10.5, 7.6 Hz), 6.59 (dd, J = 9.7, 1.7 Hz), 6.15 (dd, J =
1
2
1
-ol (3fa). Following the general procedure, 3fa was
9.6, 4.5 Hz), 4.92 (t, J = 6.9 Hz), 3.82 (dd, J = 7.7, 3.0 Hz),
1
1.56 (d, J = 5.6 Hz). 13C{ H} NMR (150 MHz, CDCl
1
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
obtained as a pale-yellow oil (22.0mg, 88%). H NMR (600
) δ
3
MHz, CDCl
3
) δ 7.27 – 7.23 (m, 2H), 7.22 – 7.18 (m, 3H),
150.6 (dd, J = 27.6, 13.1 Hz), 149.0 (dd, J = 29.7, 12.8 Hz),
136.2, 133.3 – 133.0 (m), 130.4 (d, J = 2.6 Hz), 129.5 (dd,
J = 6.3, 4.0 Hz), 129.2, 128.8, 127.8, 126.5, 115.9 (d, J =
7.04 (s, 1H), 6.88 (s, 1H), 6.58 (dd, J = 9.6, 2.1 Hz, 1H),
5
1
.97 (dd, J = 9.6, 3.8 Hz, 1H), 4.77 (s, 1H), 3.81 – 3.73 (m,
H), 2.18 (d, J = 8.5 Hz, 6H), 1.50 (s, 1H). 13C{ H} NMR
1
19
18.5 Hz), 115.0 (d, J = 18.1 Hz), 70.3, 46.6. F NMR (565
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(150 MHz, CDCl
3
) δ 138.4, 136.5, 136.3, 133.5, 130.2,
MHz, CDCl
3
) δ -138.3 (d, J = 20.9 Hz), -139.7 (d, J = 21.5
-
1
1
29.3, 128.6, 128.5, 128.3, 128.0, 127.9, 127.3, 71.3, 47.6,
Hz). HRMS m/z (ESI-ion trap) [M - H
16 9 2
C H F O: 255.0622, found: 255.0625.
2
- H] calcd for
-
9.6, 19.5. HRMS m/z (ESI-ion trap) [M - H
2
- H] calcd
for C18
H
15O: 247.1124, found: 247.1124.
(1S*,2R*)-2-Phenyl-1,2-dihydrotriphenylen-1-ol
(3ha).
(1S*,2R*)-6,7-Dimethyl-2-(p-tolyl)-1,2-dihydronaphthalen-
Following the general procedure, 3ha was obtained as a
o
1
1
-ol (3fb). Following the general procedure, 3fb was
white solid (18.4mg, 57%). m.p. 156.0–158.0 C. H NMR
(600 MHz, CDCl ) δ 8.79 – 8.70 (m, 2H), 8.35 – 8.23 (m,
1
obtained as a pale-yellow oil (21.4mg, 81%). H NMR (600
3
MHz, CDCl
H), 6.95 (s, 1H), 6.63 (dd, J = 9.6, 2.1 Hz, 1H), 6.03 (dd, J
= 9.6, 3.8 Hz, 1H), 4.83 (d, J = 5.7 Hz, 1H), 3.80 (ddd, J =
3
) δ 7.17 (d, J = 8.1 Hz, 2H), 7.15 – 7.09 (m,
2H), 7.73 – 7.66 (m, 2H), 7.66 – 7.57 (m, 3H), 7.54 (dd, J
= 8.0, 0.9 Hz, 2H), 7.47 (dt, J = 7.8, 3.4 Hz, 2H), 7.41 –
7.35 (m, 1H), 6.48 (ddd, J = 9.8, 2.3, 1.5 Hz, 1H), 5.43 (s,
3
1
3
1
5
.9, 3.7, 2.4 Hz, 1H), 2.32 (s, 3H), 2.25 (d, J = 8.7 Hz, 6H),
1H), 4.16 – 3.93 (m, 1H), 1.55 (s, 1H). C{ H} NMR (150
MHz, CDCl ) δ 140.1, 130.8, 130.7, 130.6, 129.9, 129.2,
1.56 (s, 1H). 13C{ H} NMR (150 MHz, CDCl
1
) δ 136.9,
3
3
1
36.4, 136.3, 135.1, 133.6, 130.3, 129.3, 129.1, 128.8,
28.3, 127.9, 127.8, 71.2, 47.2, 21.0, 19.6, 19.5. HRMS
128.8, 128.7, 128.6, 127.3, 127.2, 126.9, 126.9 , 126.5,
126.4, 124.1, 123.9, 123.8, 123.1, 123.1, 67.6, 48.0. HRMS
1
-
-
m/z (ESI-ion trap) [M - H
2
- H] calcd for C19
H
17O:
2
m/z (ESI-ion trap) [M - H - H] calcd for C24H15O:
2
61.1280, found: 261.1278.
319.1124, found: 319.1122.
(1S*,2R*)-2-(4-Chlorophenyl)-6,7-dimethyl-1,2-
ASSOCIATED CONTENT
Supporting Information
dihydronaphthalen-1-ol (3fe). Following the general
procedure, 3fe was obtained as a colorless oil (20.2mg,
The Supporting Information is available free of charge on
the ACS Publications website at DOI:
1
7
7
1%). H NMR (600 MHz, CDCl
3
) δ 7.29 – 7.25 (m, 2H),
.22 – 7.18 (m, 2H), 7.09 (s, 1H), 6.95 (s, 1H), 6.64 (dd, J
Copies of 1H, 19F and C{ H} NMR spectra for all
13
1
=
=
9.6, 2.1 Hz, 1H), 5.99 (dd, J = 9.6, 3.9 Hz, 1H), 4.82 (t, J
compounds and X-ray crystal data of 3ag (PDF).
6.1 Hz, 1H), 3.78 (ddd, J = 5.9, 3.8, 2.2 Hz, 1H), 2.25 (d,
Accession Codes
J = 8.7 Hz, 6H), 1.42 (d, J = 7.6 Hz, 1H). 13C{ H} NMR
1
CCDC
crystallographic data for this paper. These data can be
obtained free of charge via
1910703
contains
the
supplementary
3
(150 MHz, CDCl ) δ 136.9, 136.6, 136.5, 133.3, 133.0,
130.6, 130.0, 128.6, 128.3, 128.1, 127.9, 71.1, 47.0, 19.6,
-
1
9.5. HRMS m/z (ESI-ion trap) [M - H
14ClO: 281.0734, found: 281.0732.
2
- H] calcd for
www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
18
C H
(1S*,2R*)-6,7-Difluoro-2-phenyl-1,2-dihydronaphthalen-1-
ol (3ga). Following the general procedure, 3ga was
1
obtained as a yellow oil (23.5mg, 91%). H NMR (600
AUTHOR INFORMATION
3
MHz, CDCl ) δ 7.33 – 7.25 (m), 7.22 – 7.12 (m), 6.97 (dd,
9
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The Journal of Organic Chemistry
Page 10 of 13
Corresponding Author
E-mail: yangdq@scnu.edu.cn (Dingqiao Yang)
Cycloheptenols. Temperature Effects in the Asymmetric Reductive
Ring Opening of [3.2.1] Oxabicycloalkenes. J. Am. Chem. Soc. 1997,
19, 11090−11091. (e) Lautens, M.; Fagnou, K.; Taylor, M.; Rovis,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
*
1
T. Rhodium-catalysed Asymmetric Ring Opening of Oxabicyclic
ORCID
Alkenes with Heteroatom Nucleophiles. J. Organomet. Chem. 2001,
Dingqiao Yang: 0000-0002-5226-7722
6
24, 259−270. (f) Lautens, M.; Fagnou, K.; Zunic, V. An Expedient
Enantioselective Route to Diaminotetralins: Application in the
Notes
The authors declare no competing financial interest.
Preparation of Analgesic Compounds. Org. Lett. 2002, 4, 3465−3468.
(g) Tsoung, J.; Krämer, K.; Zajdlik, A.; Liébert, C.; Lautens, M.
0
1
2
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7
8
9
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6
7
8
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5
6
7
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3
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5
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7
8
9
0
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6
7
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9
0
Diastereoselective Friedel-Crafts Alkylation of Hydronaphthalenes. J.
Org. Chem. 2011, 76, 9031−9045.
ACKNOWLEDGMENT
3
(a) Yang, D.-Q.; Long, Y.-H.; Wang, H.; Zhang, Z.-M. Iridium-
We gratefully thank the National Natural Science
Foundation of China (21172081, 21372090), the Natural
Catalyzed Asymmetric Ring-Opening Reactions of N-Boc-
azabenzonorbornadiene with Secondary Amine Nucleophiles. Org.
Lett. 2008, 10, 4723−4726. (b) Long, Y.-H.; Yang, D.-Q.; Zhang, Z.-
M.; Wu, Y.-J.; Zeng, H.-P.; Chen, Y. Iridium-Catalyzed Asymmetric
Ring Opening of Azabicyclic Alkenes by Amines. J. Org. Chem.
Science
Foundation
of
Guangdong
Province
(S2013020013091) and the City of Guangzhou Science and
Technology Plan Projects (201510010054) for financial
support.
2
010, 75, 7291−7299. (c) Yang, D.-Q.; Long, Y.-H.; Zhang, J.-F.;
Zeng, H.-P.; Wang, S.-Y.; Li, C.-R. Iridium-Catalyzed Asymmetric
Ring-Opening Reactions of Oxabenzonorbornadienes with Amine
Nucleophiles. Organometallics 2010, 29, 3477−3480. (d) Yang, D.-
Q.; Long, Y.-H.; Wu, Y.-J.; Zuo, X.-J.; Tu, Q.-Q.; Fang, S.; Jiang, L.-
S.; Wang, S.-Y.; Li, C.-R. Iridium-Catalyzed Anti-Stereocontrolled
Asymmetric Ring Opening of Azabicyclic Alkenes with Primary
Aromatic Amines. Organometallics 2010, 29, 5936−5940. (e) Fang,
S.; Liang, X.-L.; Long, Y.-H.; Li, X.-L.; Yang, D.-Q.; Wang, S.-Y.;
Li, C.-R. Iridium-Catalyzed Asymmetric Ring-Opening of
Azabicyclic Alkenes with Phenols. Organometallics 2012, 31,
3113−3118. (f) Cheng, H.-C.; Yang, D.-Q. Iridium-Catalyzed
Asymmetric Ring-Opening of Oxabenzonorbornadienes with Phenols.
J. Org. Chem. 2012, 77, 9756−9765. (g) Yang, D.-Q.; Xia, J.-Y.;
Long, Y.-H.; Zeng, Z.-Y.; Zuo, X.-J.; Wang, S.-Y.; Li, C.-R. Iridium-
Catalyzed Asymmetric Ring-opening of Azabicyclic Alkenes with
Alcohols. Org. Biomol. Chem. 2013, 11, 4871−4881. (h) Yang, W.;
Luo, R.-S.; Yang, D.-Q. Iridium-Catalyzed Asymmetric Ring-
Opening of Oxabenzonorbornadienes with N-Substituted Piperazine
Nucleophiles. Molecules 2015, 20, 21103−21124.
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