Iridium/Copper Co-catalyzed Anti-Stereoselective Ring Opening of Oxabenzonorbornadienes with Grignard Reagents

Article abstract of DOI:10.1021/acs.joc.6b01479

Cooperative catalysis has been widely considered as one of the most powerful strategies to improve synthetic efficiency. A new iridium/copper cocatalyst was developed for the ring-opening reaction of oxabenzonorbornadienes with a wide variety of Grignard reagents, which afforded the corresponding anti-2-substituted 1,2-dihydronaphthalen-1-ols in high yields (up to 99% yield) under mild conditions. The effects of catalyst loading, Lewis acid, Grignard reagent loading, and reaction temperature on the yield were investigated. To the best of our knowledge, it represents the first example of ring-opening reactions of oxabicyclic alkenes with Grignard reagent nucleophiles in a trans-stereoselective manner.

Full text of DOI:10.1021/acs.joc.6b01479

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Article
Iridium/Copper Co-Catalyzed anti-Stereoselective Ring-
Opening of Oxabenzonorbornadienes with Grignard Reagents
Guo Cheng, Wen Yang, Yue Li, and Dingqiao Yang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01479 • Publication Date (Web): 25 Jul 2016
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Iridium/Copper CoꢀCatalyzed antiꢀStereoselective RingꢀOpening
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of Oxabenzonorbornadienes with Grignard Reagents
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Guo Cheng, Wen Yang, Yue Li, and Dingqiao Yang*
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry
and Environment, South China Normal University, Guangzhou 510006, People’s Republic of China
*Eꢀmail: yangdq@scnu.edu.cn (D.Y.). Phone: +86 20 31040403; Fax: +86 20 31040403.
ABSTRACT: Cooperative catalysis has been widely considered as one of the most
powerful strategy to improve the synthetic efficiency. A new iridium/copper coꢀcatalyst
was developed for the ringꢀopening reaction of oxabenzonorbornadienes with a wide
variety
of
Grignard
reagents,
which
afforded
the
corresponding
antiꢀ2ꢀsubstitutedꢀ1,2ꢀdihydronaphthalenꢀ1ꢀols in high yields (up to 99% yield) under
mild conditions. The effects of catalyst loading, Lewis acid, Grignard reagent loading
and reaction temperature on the yield were investigated. To the best of our knowledge,
it represents the first example in ringꢀopening reactions of oxabicyclic alkenes with
Grignard reagent nucleophiles in a transꢀstereoselective manner.
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KEYWORDS: Iridium/copper coꢀcatalyst; Oxabenzonorbornadienes; Grignard
reagents; Ringꢀopening reaction; transꢀStereoselective
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INTRODUCTION
Development of new methods and efficient strategies for carbon–carbon
bondꢀforming processes that can create multiple stereocenters is one of the challenges
in synthetic organic chemistry. The transition metalꢀcatalyzed ringꢀopening reaction
of oxaꢀ and azabicyclic alkenes have provided an important method to construct C–C
and C–X bond formation.1 This process may afford valuable hydronaphthalene
scaffolds of a wide range of natural products and bioactive molecules.2 In the past
several decades, a large variety of carbanion nucleophiles have been used to perform
this transformation. Initially, organolithium reagents3, organozincs4, and
organocuprates5 showed limited success in affording synꢀaddition ringꢀopening
products in moderate to good yields. In sharp contrast, Grignard reagent, which is the
most accessible organometallic reagent, has limited applications in catalytic reactions.
The main limitations of Grignard reagent are its high reactivity, which results in a
rapid, and its sensitivity to reaction conditions.6 Prior to 1996, Lautens et al. reported
the nickelꢀcatalyzed ringꢀopening of [2.2.1]oxabicyclic alkenes, in which a large
excess of Grignard reagents was used to generate mainly synꢀstereoselective
ringꢀopening products.7 Later on, copperꢀcatalyzed antiꢀstereoselective ringꢀopening
of oxabicyclic alkenes with Grignard reagents was gradually reported in succession
by Carretero’s group8, Zhou’s group9, and Alexakis’s group10, respectively. In addition,
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Nakamura’s group has also described that ironꢀcatalyzed synꢀstereoselective ring
opening of [2.2.1] and [3.2.1]oxabicyclic alkenes with Grignard reagents.11 More
recently, our group has reported a new platinumꢀcatalyzed antiꢀstereoselective
ringꢀopening of oxabicyclic alkenes with various Grignard reagents, which affords the
corresponding antiꢀ2ꢀsubstitutedꢀ1,2ꢀdihydronaphthalenꢀ1ꢀols with moderate to good
yields.12 Furthermore, our group has been committed to the iridiumꢀcatalyzed
antiꢀstereoselective ringꢀopening of benzoꢀ and alkylꢀsubstituted oxaꢀ and azabicyclic
alkenes, using amines13, phenols14, alcohols15, or carboxylic acids16 as nucleophiles.
While this monoꢀcatalysis strategy has successfully delivered vast numbers of new
reactions over many decades, multiꢀcatalysis concepts have recently began to emerge,
which can allow access to many difficult or unattainable transformations. In particular,
synergistic catalysis, wherein two catalysts and two catalytic cycles work in concert to
create a single new bond, has emerged as a powerful new mechanistic approach to
reaction engineering. Therefore, cooperative catalysis has been widely considered as
one of the most powerful strategy to improve the synthetic efficiency, in many cases
enabling chemical reactions that are impossible or inefficient using traditional single
catalyst method.17 On the other hand, the cooperative effect of multicatalyst might be
expected to improve the reactivity and selectivity. The use of multiple catalyst
systems can enlarge the substrate and reaction scope for the reaction design, improve
the reactivity, and benefit the control of selectivity.18 Recently, Fan’s group has
reported a transition metal/Lewis acid cooperative catalysis for asymmetric
ringꢀopening reaction of oxaꢀ and azabenzonorbornadienes with terminal alkynes19a,
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phenols19b or amines19c, 19d. To the best of our knowledge, however, iridium/copper
coꢀcatalyzed ring opening of oxabicyclic alkenes with Grignard reagents remains in
demand. So our continuous interest in developing ringꢀopening of oxaꢀ and
azabicyclic alkenes prompted us to further explore and expand the scope of this type
of reaction in the presence of a new iridium/copper coꢀcatalyst. Against the above
background, we report [Ir(COD)Cl]2 and Lewis acid CuI coꢀcatalyst for ring opening
of oxabenzonorbornadienes with Grignard reagents, we have afforded the biologically
corresponding 2ꢀsubstitutedꢀ1,2ꢀdihydronaphthalenꢀ1ꢀols in high yields (up to 99%
yield). According to our laboratory previous work of iridium catalytic system, we
have obtained transꢀconfiguration of the product rather than cis by Xꢀray diffraction
analysis.13ꢀ16 Furthermore, the effects of catalyst loading, Lewis acid, Grignard
reagent and temperature on the yield were investigated. It represents the first example
in ringꢀopening reactions of oxabicyclic alkenes with Grignard reagent nucleophiles
in a transꢀstereoselective manner.
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Results and discussion
To explore the ringꢀopening reactions and optimize the reaction conditions, an achiral
ligand 1,3ꢀbis(diphenylphosphino)propane (DPPP) was first chosen to validate the
catalytic activity of the iridium complex in the ringꢀopening reactions of
oxabenzonorbornadiene 1a with phenyl magnesium bromide 2a (2.5 equiv) as
benchmark substrates in 1,2ꢀdichloroethane (DCE) at 40 °C. The desired ringꢀopening
product 3a was achieved in poor yield (anti/syn > 99/1, 15%) (Table 1, entry 1),
implying that [Ir(COD)Cl]2 may be used the catalyst precursor. Further optimization
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of the reaction conditions, many Lewis acids were added, such as ZnCl2, ZnI2 and
AgSbF6 as additives in this reaction, and the yields of this reaction were only slightly
improved (Table 1, entries 2ꢀ5). When silver(I) triflate (AgOTf) was employed in the
presence of [Ir(COD)Cl]2 with DPPP, the yield was increased to 65% (Table 1, entry
5). On the other hand, we have tried CuCl2 and Cu(OAc)2 as Lewis catalysts, which
still afforded excellent yields (Table 1, entry 6ꢀ7). Fortunately, when [Ir(COD)Cl]2
and CuI were used as coꢀcatalyst, the yield of this reaction can be significantly
improved, reaching 94% (Table 1, entry 8). However, when the reaction was carried
out with only CuI as catalyst in the absence of [Ir(COD)Cl]2, merely 50% yield were
obtained in 10 h (Table 1, entry 9). Meanwhile, the amount of catalyst loading also
had a significant impact on the yield (Table 1, entries 10−12).
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Table 1. Optimization of Reaction Conditionsa
OH
Ph
Catalyst, Lewis acid
O
+ PhMgBr
DCE, 40 o
C
(2.5 equiv)
1a
2a
3a
catalyst
(mol%)
Lewis acid
(mol%)
time
(h)
entry
1
yield (%)
15
[Ir(COD)CI]2
ꢀ
24
10
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
2
ZnCl2 (10.0)
35
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
3
4
5
ZnI2 (10.0)
AgSbF6 (10.0)
AgOTf (10.0)
16
16
10
30
28
65
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
(2.5)/DPPP (5.0)
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[Ir(COD)CI]2
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CuCl2 (5.0)
4
4
89
80
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
Cu(OAc)2 (5.0)
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
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CuI (5.0)
CuI (5.0)
CuI (1.0)
4
10
4
94
50
81
(2.5)/DPPP (5.0)
DPPP (5.0)
[Ir(COD)CI]2
10
(1.0)/DPPP (2.0)
[Ir(COD)CI]2
(2.5)/DPPP (5.0)
[Ir(COD)CI]2
11
CuI (2.5)
4
95
12
CuI (1.0)
4
72
(2.5)/DPPP (5.0)
aReaction conditions: [Ir(COD)Cl]2, CuI and DPPP in DCE (2 mL) was
stirred for 30 min under N2 atm. Then, 1a (28.8 mg, 0.2 mmol) with 2a
(2.5 equiv) were added, and the reaction mixture was stirred at room
temperature for indicating period of time.
To further optimize reaction conditions, we then investigated the impact on
temperature and Grignard reagent loading for the reaction (Table 2). By examining
the effect of temperature, we observed that the best result was at 25 °C (99% yield)
(Table 2, entries 1−3). Furthermore, the effect of an amount of Grignard reagent
loading on the reactivity was also investigated (Table 2, entries 1, 4 and 5). When the
loading of Grignard reagent was decreased to 1.5 equiv, the yield of 3a was decreased
to 82% (Table 2, entry 4). Consequently, the optimum reaction conditions were
determined as follows: 2.5 mol% [Ir(COD)Cl]2, 5.0 mol% DPPP, and 2.5 mol% CuI
was stirred for 30 min in DCE under N2 atmosphere; then, 1a with 2.5 equivalent of
Grignard reagent 2a were added, and the reaction mixture was stirred for 4 h at 25 oC.
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Table 2. Effect of Temperature and Grignard Reagent Loadinga
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entry
temp (oC)
2a (equiv.)
2.5
3a yield (%)
1
25
99
2
40
2.5
95
3
4
5
55
25
25
2.5
1.5
2.0
98
82
97
aReaction conditions: [Ir(COD)Cl]2 (2.5 mol%), CuI (2.5 mol%)
and DPPP (5 mol%) in DCE (2 mL) was stirred for 30 min under N2
atm. 1a (28.8 mg, 0.2 mmol) with 2a were added, and the reaction
mixture was stirred for 4 h.
With the optimized reaction conditions in hand, we further examined ringꢀopening
of 1a with various Grignard reagents 2, and the results are listed in Table 3. It is
obvious that the reactivity of aryl Grignard reagents was better than the alkyl
Grignard reagents in terms of yields, because the carbanion nucleophilic of aryl group
is greater than that of alkyl group (Table 3, entries 1−7 and entries 8−9 ). Furthermore,
the results indicated that the positional property of the methyl on the phenyl ring in
aryl Grignard reagents had little effect on reactivity; whatever the substituents in
orthoꢀ, metaꢀ or paraꢀpositions, high yields were obtained (Table 3, entries 2−4) (up
to 98% yield). When the ringꢀopening of 1a reacted with aryl Grignard reagents
which have electronꢀwithdrawing substituents in para-position, the reaction still
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offered high yields (Table 3, entry 5). However, the ringꢀopening addition of
4ꢀmethoxyphenyl to 1a lowered the yield to 80% (Table 3, entry 6). Meanwhile,
3ꢀfluorophenyl magnesium bromide as nucleophile for the ringꢀopening was found to
give moderate yield (Table 3, entry 7). Unsuccessfully, 2,4,6ꢀtrimethylphenyl
magnesium bromide failed to provide the expected product 3j due to steric hindrance
(Table 3, entry 10).
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Table 3. RingꢀOpening of Oxabenzonorbornadienes with Various Grignard
Reagentsa
entry
R3
product
yield (%)
1
2
3
4
5
6
7
8
C6H5
99
98
96
97
91
80
71
22
3a
3b
3c
3d
3e
3f
2ꢀCH3C6H4
3ꢀCH3C6H4
4ꢀCH3C6H4
4ꢀClC6H4
4ꢀCH3OC6H4
3ꢀFC6H4
CH3
3g
3h
9
35
ꢀ
3i
3j
10
2,4,6ꢀ(CH3)3C6H2
aReaction conditions: [Ir(COD)Cl]2 (2.5 mol%), CuI (2.5
mol%) and DPPP (5 mol%) in DCE (2 mL) was stirred for 30
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min under N2 atm. 1a (28.8 mg, 0.2 mmol) with 2a (2.5 equiv)
5
6
7
were added, and the reaction mixture was stirred for 4 h.
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To extend the scope of this reaction, several types of oxabenzonorbornadienes 1b–e
with various Grignard reagents were also investigated under the standard reaction
conditions and the results were summarized in Table 4. The electronꢀrich substrate 1b
containing 3,6ꢀdimethoxy on the phenyl ring with aryl Grignard reagents afforded
high yields (Table 4, entries 1–6). The substrate 1b with 2ꢀmethylphenyl magnesium
bromide, owing to its steric hindrance, gave product 4b in slightly lower yield (67%).
On the other hand, electronꢀrich substrate 1c containing 4,5ꢀdimethoxy with any aryl
Grignard reagents afforded high yields (Table 4, entries 7–11). When compared with
electronꢀdeficient 1d (Table 4, entries 12–17), electronꢀrich substrate 1c displayed
more reactive than electronꢀdeficient substrate 1d, and 3ꢀfluorophenyl magnesium
bromide for the ringꢀopening were found to give low yield (45 %) (Table 4, entry 17).
Furthermore, substrate 1e with Grignard reagents showed slightly lower reactivity due
to steric hindrance (Table 4, entries 18ꢀ21).
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Table 4.
RingꢀOpening of Oxabenzonorbornadienes 1bꢀe with Various
Grignard Reagentsa
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entry substrate
R3
product
yield (%)
96
1
2
C6H5
1b
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1d
1d
1d
1d
1d
1d
1e
1e
1e
1e
4a
4b
4c
4d
4e
4f
2ꢀCH3C6H4
3ꢀCH3C6H4
4ꢀCH3C6H4
4ꢀClC6H4
3ꢀFC6H4
67
3
97
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4
97
5
80
6
95
7
C6H5
95
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
6f
8
2ꢀCH3C6H4
3ꢀCH3C6H4
4ꢀCH3C6H4
4ꢀClC6H4
C6H5
90
9
94
10
11
12
13
14
15
16
17
18
19
20
21
95
91
88
2ꢀCH3C6H4
3ꢀCH3C6H4
4ꢀCH3C6H4
4ꢀClC6H4
3ꢀFC6H4
78
75
78
75
45
C6H5
85
7a
7b
7c
7d
2ꢀCH3C6H4
3ꢀCH3C6H4
4ꢀClC6H4
88
80
89
aReaction conditions: [Ir(COD)Cl]2 (2.5 mol%), CuI (2.5
mol%) and DPPP (5 mol%) in DCE (2 mL) was stirred for 30
min under N2 atm. Oxabenzonorbornadiene 1 (0.2 mmol) with 2
(2.5 equiv) were added, and the reaction mixture was stirred for
4 h.
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CONCLUSIONS
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In summary, we have developed a simple, facile, and straightforward access to an
extensive array of antiꢀstereoselective ringꢀopening of oxabicyclic alkenes with
various Grignard reagents in the presence of iridium/copper coꢀcatalyst, which can
afford the corresponding antiꢀ2ꢀsubstitutedꢀ1,2ꢀdihydronaphthalenꢀ1ꢀols with good to
excellent yields (up to 99% yield). The reaction is wide in scope for both the Grignard
reagent and the oxabicyclic alkene. This protocol has the characteristic of mild
reaction conditions and excellent yields. To the best of our knowledge, it represents
the first example in ringꢀopening reaction of oxabenzonorbornadienes with
carbanionꢀbased nucleophiles giving exclusive transꢀring opening product. Further
investigations are underway to clarify the mechanism of this transformation and to
explore the scope of the coꢀcatalyst system in asymmetric ring opening (ARO)
reactions.
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EXPERIMENT SECTION
General Procedure for Iridium/Copper CoꢀCatalyzed antiꢀStereoselective
RingꢀOpening Reactions of Oxabenzonorbornadienes 1a–e with Grignard
Reagents. A 10.0 mL twoꢀneck roundꢀbottom flask was flameꢀdried under a stream of
nitrogen and cooled to room temperature. [Ir(COD)Cl]2 (3.4 mg, 2.5 mol%), DPPP
(4.1 mg, 5 mol%) and CuI (1.0 mg, 2.5 mol%) were simultaneously added followed
by the addition of anhydrous DCE (2.0 mL). After the mixture was stirred for about
30 min at room temperature, oxabenzonorbornadiene 1a (28.8 mg, 0.2 mmol) was
added and then the Grignard reagent (0.5 mmol) was added gradually and dropped by
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a syringe pump. The mixed solution was stirred at room temperature for 4 h until it
was completed as judged by thinꢀlayer chromatography. The reaction was quenched
by addition of aqueous 1 M NH4Cl (2.0 mL). The mixture was extracted three times
with CH2Cl2 (3 × 10 mL). The organic layers were combined, dried over anhydrous
MgSO4, filtered. After vacuum evaporation of the solvent and then concentrated to
give a crude product which was purified by column chromatography (200–300 mesh
silica gels) to give the target product.
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(1S*,2S*)-2-Phenyl-1,2-dihydronaphthalen-1-ol (3a).12 Prepared according to
general procedure. A white solid (44.0 mg, 99% yield). m.p. 86–87 °C. Rf = 0.21 on
silica gel (ethyl acetate/petroleum ether 1:10, v/v). 1H NMR (500 MHz, CDCl3) δ 7.39
(d, J = 7.1 Hz, 1H), 7.29–7.22 (m, 7H), 7.17–7.14 (m, 1H), 6.64 (dd, J = 9.6, 1.8 Hz,
1H), 6.01 (dd, J = 9.6, 3.8 Hz, 1H), 4.81 (d, J = 7.9 Hz, 1H), 3.78 (ddd, J = 7.8, 3.6,
2.2 Hz, 1H), 1.97 (d, J = 7.0 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 140.9,
135.6, 132.6, 129.9, 129.3, 128.7, 128.7, 128.4, 128.2, 128.2, 127.7, 127.2, 126.4,
126.4, 74.4, 50.1. MS (EI) m/z: [M − 3H]− calcd for C16H11O, 219.10; found, 219.04.
(1S*,2S*)-2-(2-Methylphenyl)-1,2-dihydronaphthalen-1-ol
(3b).
Prepared
according to general procedure. Colorless oil (46.3 mg, 98% yield). Rf = 0.25 on silica
gel (ethyl acetate/petroleum ether 1:10, v/v). 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J
= 7.3 Hz, 1H), 7.30–7.07 (m, 7H), 6.68 (dd, J = 9.6, 1.8 Hz, 1H), 5.98 (dd, J = 9.6, 4.0
Hz, 1H), 4.90–4.78 (m, 1H), 4.18–4.07 (m, 1H), 2.47 (s, 3H), 1.58 (s, 1H). 13C{1H}
NMR (100 MHz, CDCl3) δ 138.5, 136.8, 135.6, 132.6, 130.7, 130.1, 128.3, 128.1,
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127.6, 127.6, 127.0, 126.7, 126.4, 126.4, 73.8, 45.6, 20.0. HRMS (APCIꢀion trap) m/z:
[M − 3H]− calcd for C17H13O, 233.0966; found, 233.0966.
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(1S*,2S*)-2-(3-Methylphenyl)-1,2-dihydronaphthalen-1-ol (3c). Prepared according
to general procedure. A white solid (45.3 mg, 96% yield). m.p. 69–70 °C. Rf = 0.19
on silica gel (ethyl acetate/petroleum ether 1:20, v/v). 1H NMR (400 MHz, CDCl3) δ
7.42 (dd, J = 8.2, 6.4 Hz, 1H), 7.26 (ddd, J = 7.6, 5.3, 1.7 Hz, 2H), 7.21–7.13 (m, 2H),
7.10–7.02 (m, 3H), 6.63 (dd, J = 9.6, 2.1 Hz, 1H), 6.00 (dd, J = 9.6, 3.6 Hz, 1H), 4.83
(d, J = 8.4 Hz, 1H), 3.74 (ddd, J = 8.4, 3.3, 2.4 Hz, 1H), 2.32 (s, 3H), 2.05–1.76 (m,
1H). 13C{1H} NMR (100 MHz, CDCl3) δ 141.0, 138.4, 135.8, 132.6, 130.0, 129.2,
128.7, 128.3, 128.0, 127.9, 127.6, 126.3, 126.1, 125.4, 74.4, 50.2, 21.5. HRMS
(APCIꢀion trap) m/z: [M − 3H]− calcd for C17H13O, 233.0966; found, 233.0966.
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(1S*,2S*)-2-(4-Methylphenyl)-1,2-dihydronaphthalen-1-ol
(3d).
Prepared
according to general procedure. A white solid (45.8 mg, 97% yield). m.p. 105–106 °C.
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Rf = 0.21 on silica gel (ethyl acetate/petroleum ether 1:20, v/v). H NMR (500 MHz,
CDCl3) δ 7.47–7.42 (m, 1H), 7.34–7.28 (m, 2H), 7.22–7.14 (m, 5H), 6.68 (dd, J = 9.6,
2.1 Hz, 1H), 6.06 (dd, J = 9.6, 3.8 Hz, 1H), 4.84 (dd, J = 7.8, 5.0 Hz, 1H), 3.79 (ddd,
J = 7.9, 3.7, 2.1 Hz, 1H), 2.36 (s, 3H), 2.03 (d, J = 3.6 Hz, 1H). 13C{1H} NMR (125
MHz, CDCl3) δ 137.8, 136.9, 135.7, 132.7, 130.1, 129.5, 128.4, 128.2, 128.0, 127.5,
126.4, 126.4, 74.4, 49.7, 21.1. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for
C17H13O, 233.0966; found, 233.0966.
(1S*,2S*)-2-(4-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
(3e).12
Prepared
according to general procedure. A white solid (46.6 mg, 91% yield). m.p. 134–135 oC.
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Rf = 0.25 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (400 MHz,
CDCl3) δ 7.40–7.34 (m, 1H), 7.26 (ddt, J = 7.3, 4.4, 1.9 Hz, 4H), 7.20–7.12 (m, 3H),
6.67 (dd, J = 9.6, 1.8 Hz, 1H), 5.99 (dd, J = 9.6, 4.0 Hz, 1H), 4.75 (t, J = 6.4 Hz, 1H),
3.82–3.75 (m, 1H), 1.97 (d, J = 5.8 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ
139.2, 135.2, 133.0, 132.4, 129.7, 129.1, 128.9, 128.5, 128.3, 127.9, 126.6, 126.6,
74.2, 49.4. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C16H10ClO, 253.0420;
found, 253.0421.
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(1S*,2S*)-2-(4-Methoxyphenyl)-1,2-dihydronaphthalen-1-ol
(3f).12
Prepared
o
according to general procedure. A white solid (40.3 mg, 80% yield). m.p. 84–85 C.
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Rf = 0.24 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (400 MHz,
CDCl3) δ 7.40 (d, J = 7.2 Hz, 1H), 7.26 (ddd, J = 8.8, 5.7, 1.2 Hz, 2H), 7.16 (d, J =
8.5 Hz, 3H), 6.83 (d, J = 8.6 Hz, 2H), 6.64 (dd, J = 9.6, 1.7 Hz, 1H), 6.01 (dd, J = 9.6,
3.9 Hz, 1H), 4.78 (dd, J = 7.2, 4.4 Hz, 1H), 3.77 (s, 3H), 3.74 (dd, J = 5.4, 3.8 Hz,
1H), 1.61 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 158.8, 135.6, 132.6, 130.2,
129.4, 128.1, 128.1, 127.4, 126.4, 126.4, 116.0, 114.8, 114.2, 74.5, 55.3, 49.2. HRMS
(APCIꢀion trap) m/z: [M − 3H]− calcd for C17H13O2, 249.0916; found, 249.0917.
(1S*,2S*)-2-(3-Fluorophenyl)-1,2-dihydronaphthalen-1-ol
(3g).
Prepared
according to general procedure. A white solid (34.1 mg, 71% yield). m.p. 100–101 oC.
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Rf = 0.20 on silica gel (ethyl acetate/petroleum ether 1:20, v/v). H NMR (400 MHz,
CDCl3) δ 7.38 (d, J = 7.1 Hz, 1H), 7.26 (ddd, J = 14.4, 10.1, 8.2 Hz, 3H), 7.17 (d, J =
7.2 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H), 6.99–6.87 (m, 2H), 6.73–6.62 (m, 1H), 5.99 (dd,
J = 9.6, 3.9 Hz, 1H), 4.78 (d, J = 7.4 Hz, 1H), 3.79 (dd, J = 4.6, 2.3 Hz, 1H), 1.99 (s,
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1H). 13C{1H} NMR (100 MHz, CDCl3) δ 164.2 (d, 1JCꢀF = 243.8 Hz), 143.4 (d, 3JCꢀF
=
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6.9 Hz), 135.3, 132.4, 130.2 (d, JCꢀF = 8.3 Hz), 128.9, 128.5, 128.3, 128.0, 126.6,
126.6, 124.1 (d, 4JCꢀF = 2.7 Hz), 115.3 (d, 2JCꢀF = 21.3 Hz), 114.2 (d, 2JCꢀF = 21.3 Hz),
74.1, 49.7. 19F NMR (376 MHz, CDCl3) δ ꢀ112.6. HRMS (APCIꢀion trap) m/z: [M −
3H]− calcd for C16H10FO, 237.0716; found, 237.0716.
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(1S*,2R*)-2-Methyl-1,2-dihydronaphthalen-1-ol (3h).12 Prepared according to
o
general procedure. A white solid (7.1 mg, 22% yield). m.p. 63–64 C. Rf = 0.18 on
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silica gel (ethyl acetate/petroleum ether 1:20, v/v). H NMR (400 MHz, CDCl3) δ
7.42–7.38 (m, 1H), 7.31–7.21 (m, 3H), 7.13–7.09 (m, 1H), 6.46 (d, J = 9.5 Hz, 1H),
5.93 (dd, J = 9.6, 4.4 Hz, 1H), 4.47 (d, J = 5.9 Hz, 1H), 2.64 (ddd, J = 11.7, 5.9, 1.3
Hz, 1H), 1.07 (d, J = 7.2 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 136.6, 132.5,
128.4, 127.6, 127.6, 127.3, 126.5, 126.5, 71.7, 35.3, 14.1. MS (EI) m/z: [M − 3H]−
calcd for C11H9O, 157.09; found, 157.08.
(1S*,2R*)-2-Cyclohexyl-1,2-dihydronaphthalen-1-ol (3i).12 Prepared according to
o
general procedure. A white solid (16.0 mg, 35% yield). m.p. 81–82 C. Rf = 0.22 on
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silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (400 MHz, CDCl3) δ
7.36–7.21 (m, 3H), 7.13 (t, J = 9.0 Hz, 1H), 6.58 (dd, J = 9.7, 2.8 Hz, 1H), 5.98 (d, J
= 9.7 Hz, 1H), 4.78–4.64 (m, 1H), 2.20–2.01 (m, 3H), 1.82–1.68 (m, 4H), 1.38–1.14
(m, 5H), 1.05–0.96 (m, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 137.0, 132.8, 129.2,
128.6, 127.6, 127.6, 127.1, 126.5, 68.9, 46.1, 36.5, 31.0, 31.0, 26.6, 26.4. MS (EI) m/z:
[M − 3H]− calcd for C16H17O, 225.15; found, 225.14.
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(1S*,2S*)-5,8-Dimethoxy-2-phenyl-1,2-dihydronaphthalen-1-ol (4a).12 Prepared
according to general procedure. Colorless oil (54.2 mg, 96% yield). Rf = 0.22 on silica
gel (ethyl acetate/petroleum ether 1:5, v/v). 1H NMR (400 MHz, CDCl3) δ 7.24–7.13
(m, 5H), 7.11 (dd, J = 9.9, 1.2 Hz, 1H), 6.80 (d, J = 9.0 Hz, 1H), 6.72 (d, J = 9.0 Hz,
1H), 6.11 (ddd, J = 9.9, 5.5, 1.0 Hz, 1H), 5.16 (s, 1H), 3.90 (d, J = 5.5 Hz, 1H), 3.83
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(s, 3H), 3.72 (s, 3H), 2.43 (s, 1H). C{1H} NMR (100 MHz, CDCl3) δ 151.3, 149.6,
140.1, 128.5, 128.2, 128.0, 126.8, 123.3, 122.4, 120.5, 111.3, 110.6, 67.5, 56.2, 55.9,
48.2. MS (EI) m/z: [M − 3H]− calcd for C18H15O3, 279.13; found, 279.12.
(1S*,2S*)-5,8-Dimethoxy-2-(2-methylphenyl)-1,2-dihydronaphthalen-1-ol
(4b).
Prepared according to general procedure. Colorless oil (39.7 mg, 67% yield). Rf =
0.23 on silica gel (ethyl acetate/petroleum ether 1:5, v/v). 1H NMR (400 MHz, CDCl3)
δ 7.20–7.11 (m, 2H), 7.07 (td, J = 7.4, 1.1 Hz, 1H), 6.99–6.86 (m, 2H), 6.82–6.70 (m,
2H), 6.06 (dd, J = 9.8, 5.5 Hz, 1H), 5.10 (s, 1H), 4.14 (d, J = 5.4 Hz, 1H), 3.84 (s, 3H),
3.72 (s, 3H), 2.54 (s, 3H), 1.63 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 151.3,
149.6, 137.8, 136.3, 130.6, 128.2, 127.1, 126.7, 126.0, 123.2, 122.4, 120.7, 111.3,
110.4, 66.3, 56.2, 55.8, 44.0, 19.8. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for
C19H17O3, 293.1178; found, 293.1175.
(1S*,2S*)-5,8-Dimethoxy-2-(3-methylphenyl)-1,2-dihydronaphthalen-1-ol
(4c).
Prepared according to general procedure. Colorless oil (57.5 mg, 97% yield). Rf =
0.19 on silica gel (ethyl acetate/petroleum ether 1:5, v/v). 1H NMR (400 MHz, CDCl3)
δ 7.10 (dd, J = 13.8, 9.3 Hz, 2H), 7.04–6.86 (m, 3H), 6.82–6.70 (m, 2H), 6.08 (dt, J =
12.0, 6.0 Hz, 1H), 5.16 (d, J = 8.8 Hz, 1H), 3.85 (s, 1H), 3.83 (s, 3H), 3.73 (s, 3H),
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2.45 (s, 1H), 2.27 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 151.4, 149.6, 140.2,
138.1, 128.9, 128.4, 128.4, 127.6, 124.9, 123.4, 122.5, 120.3, 111.4, 110.6, 67.7, 56.3,
55.9, 48.2, 21.5. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C19H17O3,
293.1178; found, 293.1178.
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(1S*,2S*)-5,8-Dimethoxy-2-(4-methylphenyl)-1,2-dihydronaphthalen-1-ol
(4d).
Prepared according to general procedure. Colorless oil (57.5 mg, 97% yield). Rf =
0.23 on silica gel (ethyl acetate/petroleum ether 1:5, v/v). 1H NMR (500 MHz, CDCl3)
δ 7.15–7.04 (m, 5H), 6.85–6.81 (m, 1H), 6.77–6.74 (m, 1H), 6.14 (ddd, J = 9.8, 5.5,
1.0 Hz, 1H), 5.19 (s, 1H), 3.93–3.90 (m, 1H), 3.87 (s, 3H), 3.76 (s, 3H), 2.45 (d, J =
6.1 Hz, 1H), 2.30 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 151.4, 149.5, 137.0,
136.4, 129.2, 128.5, 127.9, 123.3, 122.5, 120.3, 111.3, 110.5, 67.5, 56.2, 55.9, 47.8,
21.0. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C19H17O3, 293.1178; found,
293.1179.
(1S*,2S*)-5,8-Dimethoxy-2-(4-chlorophenyl)-1,2-dihydronaphthalen-1-ol
(4e).
Prepared according to general procedure. A white solid (50.6 mg, 80% yield). m.p.
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97–98 C. Rf = 0.21 on silica gel (ethyl acetate/petroleum ether 1:5, v/v). H NMR
(400 MHz, CDCl3) δ 7.12 (ddd, J = 17.4, 16.4, 8.4 Hz, 5H), 6.81 (d, J = 9.0 Hz, 1H),
6.74 (d, J = 9.0 Hz, 1H), 6.08 (dd, J = 9.8, 5.5 Hz, 1H), 5.10 (s, 1H), 3.87 (d, J = 4.6
Hz, 1H), 3.84 (s, 3H), 3.73 (s, 3H), 2.41 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ
151.3, 149.6, 138.4, 132.5, 129.4, 128.6, 127.6, 122.9, 122.2, 120.9, 111.4, 110.8,
67.4, 56.2, 55.9, 47.4. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C18H14ClO3,
313.0631; found, 313.0635.
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(1S*,2S*)-5,8-Dimethoxy-2-(3-fluorophenyl)-1,2-dihydronaphthalen-1-ol
(4f).
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Prepared according to general procedure. Colorless oil (57.0 mg, 95% yield). Rf =
0.25 on silica gel (ethyl acetate/petroleum ether 1:5, v/v). 1H NMR (400 MHz, CDCl3)
δ 7.50–7.35 (m, 1H), 7.14 (ddd, J = 10.9, 8.7, 3.6 Hz, 2H), 6.97 (d, J = 7.7 Hz, 1H),
6.84–6.78 (m, 2H), 6.72 (s, 1H), 6.12–6.04 (m, 1H), 5.14 (d, J = 1.2 Hz, 1H), 3.90 (d,
J = 4.6 Hz, 1H), 3.83 (s, 3H), 3.73 (s, 3H), 1.68 (s, 1H). 13C{1H} NMR (100 MHz,
CDCl3) δ 164.1 (d, 1JCꢀF = 243.8 Hz), 151.3, 149.6, 142.7 (d, 4JCꢀF = 7.0 Hz), 129.9 (d,
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3JCꢀF = 8.2 Hz), 127.4, 125.0, 123.8, 123.8, 121.0 (d, JCꢀF = 16.6 Hz), 114.9, 114.7,
111.5, 110.8, 67.3, 56.2, 56.0, 47.8. 19F NMR (376 MHz, CDCl3) δ ꢀ113.2 (d, J = 17.1
Hz). HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C18H14FO3, 297.0927; found,
297.0927.
(1S*,2S*)-6,7-Dimethoxy-2-phenyl-1,2-dihydronaphthalen-1-ol (5a).12 Prepared
according to general procedure. Colorless oil (53.6 mg, 95% yield). Rf = 0.23 on silica
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gel (ethyl acetate/petroleum ether 1:3, v/v). H NMR (400 MHz, CDCl3) δ 7.30–7.22
(m, 5H), 6.96 (s, 1H), 6.72 (s, 1H), 6.58 (dd, J = 9.6, 1.7 Hz, 1H), 5.94 (dd, J = 9.6,
4.0 Hz, 1H), 4.74 (d, J = 6.5 Hz, 1H), 3.90 (s, 3H), 3.87 (s, 3H), 3.79–3.73 (m, 1H),
1.97 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 148.7, 148.7, 140.9, 128.7, 128.4,
128.1, 127.8, 127.1, 127.1, 125.6, 110.4, 110.0, 74.4, 56.0, 56.0, 50.2. HRMS
(APCIꢀion trap) m/z: [M − 3H]− calcd for C18H15O3, 279.1021; found, 279.1023.
(1S*,2S*)-6,7-Dimethoxy-2-(2-methylphenyl)-1,2-dihydronaphthalen-1-ol
(5b).
Prepared according to general procedure. A white solid (53.3 mg, 90% yield). m. p.
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(500 MHz, CDCl3) δ 7.19 (d, J = 7.4 Hz, 1H), 7.15–7.03 (m, 3H), 6.91 (s, 1H), 6.72 (s,
1H), 6.60 (dd, J = 9.6, 1.8 Hz, 1H), 5.88 (dd, J = 9.5, 4.2 Hz, 1H), 4.74 (d, J = 3.8 Hz,
1H), 4.08 (ddd, J = 6.3, 4.2, 1.9 Hz, 1H), 3.90 (s, 3H), 3.86 (s, 3H), 2.48 (s, 3H), 2.01
(s, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 148.6, 148.6, 138.5, 136.8, 130.7, 128.0,
128.0, 127.5, 127.1, 126.9, 126.3, 125.5, 110.6, 109.9, 73.7, 56.0, 56.0, 45.6, 20.0.
HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C19H17O3, 293.1178; found,
293.1179.
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(1S*,2S*)-6,7-Dimethoxy-2-(3-methylphenyl)-1,2-dihydronaphthalen-1-ol
(5c).
Prepared according to general procedure. Yellow oil (55.7 mg, 94% yield). Rf = 0.22
1
on silica gel (ethyl acetate/petroleum ether 1:3, v/v). H NMR (400 MHz, CDCl3) δ
7.24–6.99 (m, 5H), 6.71 (s, 1H), 6.55 (dd, J = 9.6, 1.9 Hz, 1H), 5.91 (dt, J = 14.2, 7.1
Hz, 1H), 4.76 (d, J = 7.8 Hz, 1H), 4.01 (s, 1H), 3.90 (s, 3H), 3.87 (s, 3H), 2.32 (s, 3H),
1.62 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 148.6, 148.6, 141.0, 138.4, 129.2,
128.6, 128.4, 128.0, 128.0, 127.0, 125.6, 125.4, 110.2, 110.0, 74.4, 56.0, 56.0, 50.3,
21.5. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C19H17O3, 293.1178; found,
293.1179.
(1S*,2S*)-6,7-Dimethoxy-2-(4-methylphenyl)-1,2-dihydronaphthalen-1-ol
(5d).
Prepared according to general procedure. Colorless oil (56.3 mg, 95% yield). Rf =
0.23 on silica gel (ethyl acetate/petroleum ether 1:3, v/v). 1H NMR (400 MHz, CDCl3)
δ 7.14–7.10 (m, 4H), 6.95 (s, 1H), 6.71 (s, 1H), 6.56 (d, J = 9.6 Hz, 1H), 5.93 (dd, J =
9.5, 4.0 Hz, 1H), 4.72 (d, J = 7.3 Hz, 1H), 3.90 (s, 3H), 3.87 (s, 3H), 3.75–3.70 (m,
1H), 2.31 (s, 3H), 1.66 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.5, 148.5,
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138.5, 137.7, 129.5, 128.3, 127.1, 125.6, 124.1, 123.8, 110.3, 109.8, 74.4, 56.0, 56.0,
49.8, 21.1. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C19H17O3, 293.1178;
found, 293.1179.
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(1S*,2R*)-6,7-Dimethoxy-2-(4-chlorophenyl)-1,2-dihydronaphthalen-1-ol
(5e).
Prepared according to general procedure. Yellow oil (57.5 mg, 91% yield). Rf = 0.25
1
on silica gel (ethyl acetate/petroleum ether 1:3, v/v). H NMR (400 MHz, CDCl3) δ
7.26–7.23 (m, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 6.5 Hz, 1H), 6.72 (s, 1H),
6.59 (dd, J = 9.6, 1.5 Hz, 1H), 5.90 (dd, J = 9.6, 4.2 Hz, 1H), 4.67 (d, J = 6.3 Hz, 1H),
3.90 (s, 3H), 3.86 (s, 3H), 3.74 (ddd, J = 8.7, 5.2, 3.1 Hz, 1H), 1.99 (s, 1H). C{1H}
13
NMR (100 MHz, CDCl3) δ 148.8, 148.8, 139.2, 132.9, 129.7, 128.8, 127.7, 127.4,
127.1, 125.4, 110.6, 110.1, 74.2, 56.0, 56.0, 49.4. HRMS (APCIꢀion trap) m/z: [M −
3H]− calcd for C18H14ClO3 , 313.0631; found, 313.0632.
(1S*,2S*)-6,7-Dibromo-2-phenyl-1,2-dihydrotriphenylen-1-ol (6a).12 Prepared
according to general procedure. Colorless oil (66.5 mg, 88% yield). Rf = 0.23 on silica
1
gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (400 MHz, CDCl3) δ 7.70 (s,
1H), 7.40 (s, 1H), 7.32 (ddd, J = 10.5, 5.3, 3.4 Hz, 3H), 7.28 – 7.25 (m, 2H), 6.59 –
6.49 (m, 1H), 6.07 (ddd, J = 12.7, 8.6, 3.8 Hz, 1H), 4.82 – 4.72 (m, 1H), 3.74 (ddd, J
= 9.3, 6.0, 3.3 Hz, 1H), 2.05 (d, J = 3.3 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ
140.3, 136.6, 133.4, 132.1, 131.2, 130.9, 129.0, 128.5, 127.6, 126.0, 124.0, 123.6,
73.6, 50.0. MS (EI) m/z: [M − 3H]− calcd for C16H9Br2O, 376.93; found, 376.90.
(1S*,2R*)-6,7-Dibromo-2-(2-methylphenyl)-1,2-dihydrotriphenylen-1-ol
(6b).
Prepared according to general procedure. Colorless oil (61.1 mg, 78% yield). Rf =
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0.22 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
CDCl3) δ 7.69 (s, 1H), 7.47–7.41 (m, 1H), 7.26–7.14 (m, 4H), 6.64–6.53 (m, 1H),
6.12–6.01 (m, 1H), 4.89–4.78 (m, 1H), 4.13–4.08 (m, 1H), 2.48 (d, J = 5.1 Hz, 3H),
2.15–2.05 (m, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 138.1, 137.0, 136.6, 133.5,
132.6, 131.4, 130.9, 130.9, 127.5, 127.3, 126.6, 126.0, 124.1, 123.5, 73.3, 45.4, 20.0.
HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C17H11Br2O, 390.9157; found,
390.9154.
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(1S*,2R*)-6,7-Dibromo-2-(3-methylphenyl)-1,2-dihydrotriphenylen-1-ol
(6c).
Prepared according to general procedure. Colorless oil (58.8 mg, 75% yield). Rf =
1
0.25 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
CDCl3) δ 7.74 (s, 1H), 7.42 (s, 1H), 7.29–7.26 (m, 1H), 7.15–7.07 (m, 3H), 6.57 (ddd,
J = 12.0, 9.0, 2.3 Hz, 1H), 6.09 (td, J = 9.6, 3.1 Hz, 1H), 4.83–4.77 (m, 1H), 3.71 (dt,
J = 9.7, 2.8 Hz, 1H), 2.38 (s, 3H), 2.08–2.01 (m, 1H). 13C{1H} NMR (125 MHz,
CDCl3) δ 140.3, 138.8, 136.7, 133.4, 132.3, 131.0, 130.8, 129.2, 128.9, 128.4, 126.0,
125.5, 124.0, 123.6, 73.6, 50.0, 21.5. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd
for C17H11Br2O, 390.9157; found, 390.9155.
(1S*,2S*)-6,7-Dibromo-2-(4-methylphenyl)-1,2-dihydrotriphenylen-1-ol
(6d).
Prepared according to general procedure. A white solid (61.1 mg, 78% yield). m.p.
108–109 oC. Rf = 0.24 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). 1H NMR
(500 MHz, CDCl3) δ 7.72 (d, J = 4.5 Hz, 1H), 7.45–7.39 (m, 1H), 7.16 (dd, J = 7.7,
1.8 Hz, 4H), 6.60–6.51 (m, 1H), 6.09 (td, J = 9.4, 3.3 Hz, 1H), 4.79–4.73 (m, 1H),
3.75–3.68 (m, 1H), 2.37 (s, 3H), 2.06 (t, J = 9.3 Hz, 1H). 13C{1H} NMR (125 MHz,
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CDCl3) δ 137.3, 137.1, 136.6, 133.4, 132.4, 131.2, 130.8, 129.7, 128.3, 125.9, 124.0,
123.5, 73.6, 49.5, 21.1. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C17H11Br2O,
390.9157; found, 390.9156.
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(1S*,2R*)-6,7-Dibromo-2-(4-chlorophenyl)-1,2-dihydrotriphenylen-1-ol
(6e).
Prepared according to general procedure. Colorless oil (61.8 mg, 75% yield). Rf =
1
0.23 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (400 MHz,
CDCl3) δ 7.69 (s, 1H), 7.47–7.39 (m, 1H), 7.32 (t, J = 6.5 Hz, 2H), 7.23–7.18 (m, 2H),
6.64–6.54 (m, 1H), 6.05 (ddd, J = 17.9, 9.6, 3.6 Hz, 1H), 4.85–4.61 (m, 1H),
3.80–3.71 (m, 1H), 2.20–2.02 (m, 1H). 13C{1H} NMR (100 MHz, CDCl3) δ 138.6,
136.2, 133.4, 133.2, 131.4, 131.0, 129.8, 129.1, 126.3, 124.3, 123.8, 116.7, 73.5, 49.3.
HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C16H8Br2ClO, 410.8609; found,
410.8604.
(1S*,2S*)-6,7-Dibromo-2-(3-fluorophenyl)-1,2-dihydrotriphenylen-1-ol
(6f).
Prepared according to general procedure. Colorless oil (35.6 mg, 45% yield). Rf =
1
0.25 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
CDCl3) δ 7.61 (s, 1H), 7.34 (d, J = 6.3 Hz, 1H), 7.23 (tt, J = 11.5, 5.7 Hz, 1H), 6.92
(dddd, J = 11.5, 9.9, 7.6, 3.3 Hz, 3H), 6.51 (ddd, J = 11.9, 7.5, 2.7 Hz, 1H), 6.05–5.94
(m, 1H), 4.75–4.61 (m, 1H), 3.71–3.65 (m, 1H), 2.00–1.92 (m, 1H). 13C{1H} NMR
1
3
(125 MHz, CDCl3) δ 164.0 (d, JC−F = 246.3 Hz), 142.8 (d, JC−F = 6.9 Hz), 136.2,
133.1, 131.2, 131.2, 131.0, 130.5 (d, 3JC−F = 8.3 Hz), 126.4, 124.4 (d, 4JC−F = 2.5 Hz),
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124.0, 123.8, 115.4 (d, JC−F = 21.3 Hz), 114.6 (d, JC−F = 20 Hz), 73.4, 49.6. 19F
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NMR (376 MHz, CDCl3) δ ꢀ112.0. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for
C16H8Br2FO, 394.8906; found, 394.8909.
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(1S*,2S*)-2-Phenyl-1,2-dihydrotriphenylen-1-ol (7a).12 Prepared according to
general procedure. A white solid (54.8 mg, 85% yield). m.p. 80–81 °C. Rf = 0.23 on
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silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz, CDCl3) δ
8.76–8.67 (m, 2H), 8.43–8.37 (m, 1H), 8.24–8.18 (m, 1H), 7.72–7.56 (m, 5H),
7.19–7.08 (m, 5H), 6.48 (ddd, J = 9.8, 5.9, 1.1 Hz, 1H), 5.56 (d, J = 7.4 Hz, 1H), 4.13
(t, J = 8.6 Hz, 1H), 2.15 (d, J = 7.6 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ
138.7, 130.8, 130.6, 130.2, 129.9, 128.7, 128.7, 127.8, 127.4, 127.4, 127.2, 127.0,
126.9, 126.5, 126.5, 123.9, 123.7, 123.1, 123.1, 122.4, 69.5, 48.8. MS (EI) m/z: [M −
3H]− calcd for C24H15O, 319.14; found, 319.11.
(1S*,2S*)-2-(2-Methylphenyl)-1,2-dihydrotriphenylen-1-ol
(7b).
Prepared
o
according to general procedure. A white solid (59.2 mg, 88% yield). m.p. 71–72 C.
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Rf = 0.22 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
CDCl3) δ 8.73–8.65 (m, 2H), 8.41–8.34 (m, 1H), 8.22–8.18 (m, 1H), 7.71–7.56 (m,
5H), 7.17 (d, J = 7.5 Hz, 1H), 7.00 (td, J = 7.3, 1.6 Hz, 1H), 6.84–6.73 (m, 2H), 6.41
(ddd, J = 9.8, 5.9, 1.0 Hz, 1H), 5.49 (s, 1H), 4.36 (d, J = 5.9 Hz, 1H), 2.62 (d, J = 6.6
Hz, 3H), 2.28–2.10 (m, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 136.6, 136.0, 131.0,
130.8, 130.6, 130.2, 129.8, 128.7, 127.4, 127.4, 127.1, 127.4, 126.7, 126.5, 126.5,
126.3, 123.9, 123.6, 123.2, 123.2, 122.5, 68.2, 44.7, 19.9. HRMS (APCIꢀion trap) m/z:
[M − 3H]− calcd for C25H17O, 333.1279, found, 333.1278.
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(1S*,2R*)-2-(3-Methylphenyl)-1,2-dihydrotriphenylen-1-ol
(7c).
Prepared
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6
7
according to general procedure. A white solid (53.8 mg, 80% yield). m.p. 99–100 oC.
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Rf = 0.25 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
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CDCl3) δ 8.77–8.69 (m, 2H), 8.44–8.38 (m, 1H), 8.27–8.21 (m, 1H), 7.73–7.59 (m,
5H), 7.25 (s, 1H), 7.02 (d, J = 4.0 Hz, 1H), 6.95–6.91 (m, 2H), 6.48 (ddd, J = 9.8, 5.9,
0.9 Hz, 1H), 5.57 (s, 1H), 4.13 (d, J = 4.6 Hz, 1H), 2.20 (s, 3H), 1.56 (s, 1H). 13C{1H}
NMR (125 MHz, CDCl3) δ 138.7, 138.3, 130.8, 130.6, 130.2, 130.0, 128.7, 128.7,
127.9, 127.4, 127.4, 127.0, 127.0, 126.4, 126.4, 124.7, 123.9, 123.7, 123.1, 123.1,
122.2, 69.5, 48.9, 21.4. HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C25H17O,
333.1279, found, 333.1277.
(1S*,2R*)-2-(4-Chlorophenyl)-1,2-dihydrotriphenylen-1-ol
(7d).
Prepared
according to general procedure. A white solid (63.4 mg, 89% yield). m.p. 123–124 oC
1
Rf = 0.20 on silica gel (ethyl acetate/petroleum ether 1:10, v/v). H NMR (500 MHz,
CDCl3) δ 8.72 (ddd, J = 17.6, 6.9, 4.8 Hz, 2H), 8.38 (dd, J = 5.5, 4.0 Hz, 1H),
8.23–8.14 (m, 1H), 7.74–7.57 (m, 5H), 7.07 (s, 4H), 6.56–6.34 (m, 1H), 5.48 (d, J =
7.4 Hz, 1H), 4.10 (d, J = 5.8 Hz, 1H), 2.16 (d, J = 7.6 Hz, 1H). 13C{1H} NMR (125
MHz, CDCl3) δ 137.0, 132.8, 130.8, 130.7, 130.0, 129.4, 129.2, 128.8, 128.5, 127.5,
127.2, 127.2, 127.1, 126.6, 126.4, 123.9, 123.5, 123.2, 123.2, 122.8, 69.4, 48.1.
HRMS (APCIꢀion trap) m/z: [M − 3H]− calcd for C24H14ClO, 353.0733, found,
353.0732.
AUTHOR INFORMATION
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Corresponding Authors
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*Eꢀmail: yangdq@scnu.edu.cn. Phone: +86 20 39310068.
Fax: +86 20 31040403
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We gratefully thank the National Natural Science Foundation of China (21172081,
21372090), the Natural Science Foundation of Guangdong Province
(S2013020013091), the City of Guangzhou Science and Technology Plan Projects
(156300018), and Graduate Student Research and Innovation Foundation of South
China Normal University (2015lkxm32) for financial support.
ASSOCIATED CONTENT
Supporting Information
General experimental remarks; copies of 1H and 13C{1H} spectra for compounds 3a
−i,
4a f, 5a e, 6a f and 7a
−
−
−
−
d, and 19F NMR for compounds 3g, 4f and 6f. This material
is available free of charge via the Internet at http://pubs.acs.org.
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