Asymmetric Ring-Opening Reactions of Aza- and Oxa-bicyclic Alkenes with Boronic Acids Using a Palladium/Zinc Co-catalytic System

Article abstract of DOI:10.1021/acs.joc.6b03038

The asymmetric ring opening reactions of bicyclic alkenes with boronic acids were accomplished by using a highly active palladium/zinc co-catalytic system that was suitable for both azabenzonorbornadienes and oxabenzonorbornadienes, which were transformed to the corresponding chiral hydronaphthalene products in high yields (up to 99%) and high optical purities (up to 98% ee). The reaction protocol is general and mild and displays good functional group tolerance.

Full text of DOI:10.1021/acs.joc.6b03038

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Article
Asymmetric Ring Opening Reactions of Aza- and Oxa-bicyclic Alkenes
with Boronic Acids Using a Palladium/Zinc Co-catalytic System
Wei Zhang, Jingchao Chen, Guangzhi Zeng, Fan Yang, Jianbin
Xu, Weiqing Sun, Madhuri Vikas Shinde, and Baomin Fan
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b03038 • Publication Date (Web): 23 Jan 2017
Downloaded from http://pubs.acs.org on January 25, 2017
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The Journal of Organic Chemistry
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Asymmetric Ring Opening Reactions of Aza- and Oxa-bicyclic
Alkenes with Boronic Acids Using a Palladium/Zinc Co-
catalytic System
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†
Wei Zhang,† Jingchao Chen,*, Guangzhi Zeng,† Fan Yang,† Jianbin Xu,† Weiqing Sun,† Madhuri
Vikas Shinde,† and Baomin Fan*, ,
† ‡
†YMU-HKBU Joint Laboratory of Traditional Natural Medicine, Yunnan Minzu University, Kunming, Yunnan, Peo-
ple's Republic of China
‡Key Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu University, Kunming, Yunnan 650500,
People's Republic of China
ABSTRACT: The asymmetric ring opening reactions of bicyclic alkenes with boronic acids were accomplished by using a
highly active palladium/zinc co-catalytic system. And the
co-catalytic system was suitable for both azabenzonor-
bornadienes and oxabenzonorbornadienes, which were
transformed to the corresponding chiral hydronaphtha-
lenes products in high yields (up to 99%) and high optical
purities (up to 98% ee). The reaction protocol is general,
mild, and with good functional group tolerance.
oxabenzonorbornadienes,3d,6c,16 only few examples were
INTRODUCTION
given with azabenzonorbornadienes17 in asymmetric
The transition-metal-catalyzed ring opening reactions of
heterobicyclic alkenes have received intense attention in
extend the reaction scope for the asymmetric ring
fashion. In order to develop a general catalyst system and
the past decade as they represent versatile approaches for
opening reactions of azabenzonorbornadienes with
chiral hydronaphthalenes,1 which are frequently found in
boronic acids, we investigated it by using palladium/zinc
a plethora of natural products and biologically active
co-catalytic system. Moreover, this co-catalytic system
molecules.2 The group of Lautens has taken the lead in
also exhibited excellent catalytic ability on the
exploring rhodium catalyzed asymmetric ring opening
oxabenzonorbornadiene substrates.
reaction (ARO) of heterobicyclic alkenes3; and some other
groups have also achieved a lot of success by using
iridium,4 nickel,5 palladium,6 copper,7 and ruthenium
catalysts8. Our group has had long interest in this kind of
reactions by studying it by co-catalytic systems
comprising chiral transition metal complexes and Lewis
RESULTS AND DISCUSSION
According to our previous studies of the asymmetric ring
opening reactions, the selection of Lewis acid is crucial to
the reaction outcomes. Therefore, our journey
commenced by searching for a suitable Lewis acid using
the reaction of azabenzonorbornadiene 1a with
phenylboronic acid 2a in the presence of Pd(OAc)2 and
(R)-BINAP (Table 1). The initially tested ZnI2 only give the
desired product 3aa in trace amount (Table 1, entry 1), CuI
and FeCl2 also failed to promote the reaction (Table 1,
entries 2-3). We were delight to find that by using AgOTf,
3aa was obtained in 89% yield with 79% enantiomeric
acids, which was previously employed by pioneers.3c,9
.
Followed by our previous work that employing alkynes,10
amines,11 phenols,12 alcohols,13 and organic acids14 as
nucleophiles, the asymmetric ring opening reaction of
heterobicyclic alkenes by boronic acids have attracted our
attention as they offered straightforward method for the
preparation of chiral aryltetralin, which are common
substructures in bioactive natural products such as
chelidonine, corynoline, and wailupemycin D.15 Although
this kind of reactions have been studied with
excess
(Table
1,
entry
4).
Some
other
trifluoromethanesulfonic salts were next screened by
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assuming that the trifluoromethanesulfonate anion has a (Table 2, entry 10). However, the reaction performed at -
o
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2
3
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7
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unique effect in the present reaction. But the
experimental results showed that CuOTf and Cu(OTf)2
led to inferior reaction yields with similar
enantioselectivities (Table 1, entries 5-6). By switching to
Zn(OTf)2 and Fe(OTf)2, excellent yields were achieved
(Table 1, entries 7-8). The next tested Lewis acids such as
Fe(OTf)3, In(OTf)3, and Al(OTf)3 were less effective and
60 C became sluggish and only a trace amount of the
desired product was observed after 72 hours (entry 14).
The addition of water was proved to be no need, because
an improved ee was obtained with the reaction yield
unchanged by the control experiment. This result can be
explained by the undermining of Lewis acid when water
was added, and thus affected the enantioselectivity of the
reaction. Although the reaction was performed well in
other solvents such toluene and diethyl ether, but the
outcomes were inferior compared to tetrahydrofuran
(Table 2, entries 13-14).
9
Table 1. Screening of Lewis acids for the ARO
reactiona
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With the optimized conditions in hand, various boronic
acids were reacted with azabenzonorbornadiene 1a, and
the corresponding products 3aa-an were obtained
generally in high yields and excellent enantiomeric
excesses (Table 3). Among them, halogen bearing
phenylboronic acid showed good tolerance, and the
Entry Lewis acid Time [h] Yield [%] ee [%]b
1
ZnI2
48
48
48
2.5
4.5
0.5
0.4
1
trace
N.R.
N.R.
89
---
---
---
79
75
80
77
77
79
79
79
43
2
CuI
3
FeCl2
Table 2. Screening of chiral ligands and reaction
temperatures for the ARO reactiona
4
5
AgOTf
CuOTf
Cu(OTf)2
Zn(OTf)2
Fe(OTf)2
Fe(OTf)3
In(OTf)3
Al(OTf)3
---
76
6
7
79
98
8
9
10
11
12
98
12
81
14
83
13
77
60
90
aReaction conditions: 1a (0.2 mmol), 1a/2a/Pd(OAc)2/ (R)-
BINAP/Lewis acid (1:2:0.05:0.06:0.1), in tetrahydrofuran (2
o
b
mL) at 0 C under Ar for the time indicated. Determined
by HPLC with a Chiralcel OD-H column.
Time
[h]
0.5
0.5
0.5
2
T
Yield ee
[%]
Entry Ligand
[oC]
[%]b
gave inferior reaction yields (Table 1, entries 9-11). Control
experiment further established the requirement of Lewis
acid for good enantioselectivity (Table 1, entry 12).
1
(R)-BINAP
0
0
0
0
0
98
89
84
75
86
77
58
77
31
2
(R)-H8-BINAP
(R)-DM-BINAP
(R)-SEGPHOS
(R,R)-BDPP
(R)-SDP
Subsequently, the reaction conditions optimization of
present reaction was carried out by screening various
chiral ligands and reaction temperatures. As the results
summarized in table 2, the using of BINAP-derived
diphosphine ligands such as (R)-H8-BINAP and (R)-DM-
BINAP both gave reduced reaction yields (Table 2, entries
2 and 3). And the evaluation of other bidentate chiral
ligands were failed to give good reaction results (Table 2,
entries 4 and 5). The next tested chiral spiro ligand (Table
2, entry 6) and some monophosphine ligands (Table 2,
entries 7 and 8) were proved to be ineffective. In order to
improve the reaction enantioselectivity, the reaction was
carried out by lowering the reaction temperature. The
present catalytic system was proved to be highly active as
good reaction result was obtained at -20 oC (Table 2, entry
3
4
5
2
31
6
r.t. 60
trace ---
trace ---
trace ---
7
(R)-MONOPHOS r.t. 60
8
(S)-NMDPP
(R)-BINAP
(R)-BINAP
(R)-BINAP
(R)-BINAP
(R)-BINAP
(R)-BINAP
r.t. 60
-20
9
2
95
95
89
93
10
11
12c
13d
14e
-40 19
-60 72
-40 13
-40 40
-40 72
trace ---
95
95
84
94
87
80
o
9), and high enantioselectivity was achieved at -40 C
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aReaction conditions: The reaction was carried out with 1a
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93
98
99
---
1
2
3
4
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6
7
8
(0.2 mmol), 2a (0.4 mmol) and 0.1 equiv. of Zn(OTf)2 in
tetrahydrofuran (2 mL) in the presence of Pd(OAc)2 (5
mol%) and a bidentate ligand (6 mol%) or monodentate
ligand (12 mol%) under Ar for the time indicated.
bDetermined by HPLC with a Chiralcel OD-H column.
cNo water was used. dToluene was used as solvent.
eDiethyl ether was used as solvent.
26
NR
aReaction conditions: 1a (0.2 mmol), 1a/2/Pd(OAc)2/(R)-
BINAP/Zn(OTf)2 (1:2:0.05:0.06:0.1), in tetrahydrofuran (2
mL) at -40 oC under Ar for the time indicated.
bDetermined by HPLC with a Chiralcel OD-H , AD-H or
9
halogen groups were unreacted (Table 3, entries 2-4). The
electron- withdrawing groups substituted phenylboronic
acids were also suitable nucleophiles in present
transformation (Table 3, entries 5-8). However, caused by
the steric effect, meta- and ortho- substituted
phenylboronic acids exhibited lower reactivities and
10
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c
AS-H column. 10% Pd(OAc)2 and 12% (R)-BINAP were
d
o
e
o
f
used. Reacted at 0 C. Reacted at -20 C. Results in the
parentheses were obtained by using the literature
conditions (ref 15a).
enantioselectivities toward this asymmetric ring opening
reaction (Table 3, entries 9-10). The electron-rich
phenylboronic acid 2k was participated in the reaction,
albeit with relatively moderate result (Table 3, entry 11). 2-
Naphthylboronic acid was found less reactive, and a
prolonged reaction time was needed to complete full
transformation (Table 3, entry 12). In addition to
phenylboronic acids, 3-furanylboronic acid 2m and 3-
thienylboronic acid 2n also gave the corresponding ring
Table 3. Scope of the phenylboronic acidsa
Boc
HN
Boc
N
R
Pd(OAc)2, (R)-BINAP, Zn(OTf)2
THF, -40 o
R
+
B(OH)2
C
3aa-ap
1a
2a-p
Boronic acid
Time Yield
Entry
ee [%]b
[h]
[%]
2a-n
1
19
95
94
90
Table 4. Scope of the bicyclic alkenesa
2c,d
3
26
24
72
97
90(73)f 94(71)f
Bicyclic alkene
Time Yield
[h]
Entry
ee [%]b
94
4
99
98
91
[%]
1a-m
1
17
95
5
30
90
2
3
4
5
6
39
36
39
33
35
98(90)c 95(60)c
6
19
41
17
97
99
98
93
96
93
95
95
86
72
86
96
90
93
94
93
7
8
9c,d
10c,d
70
65
96(88)c 91(55)c
11e
36
72
86
93
90
82
7
8
9
53
19
41
94
95
95
91
12c,d
94
94
13c
60
91(80)f 99(78)f
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96
92
Boc
HN
3
Br
4
5
6
7
8
9
Br
11
19
17
16
96
95
95
98
3da
12
95
Figure 1. X-ray structure of 3da.
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Basis on our experience of the asymmetric ring opening
aReaction conditions: 1 (0.2 mmol), 1/2a/Pd(OAc)2/(R)-
BINAP/Zn(OTf)2 (1:2:0.05:0.06:0.1), in tetrahydrofuran (2
mL) at -40 oC under Ar for the time indicated.
bDetermined by HPLC with a Chiralcel OD-H or AD-H
column. cResults in the parentheses were obtained by
using the literature conditions (ref 15a).
reactions11c,12b and literatures of palladium catalyzed
reaction of arylboronic acids20, a plausible mechanism of
this ring opening reaction is outlined by the reaction of 1a
and 2a (Figure 2). The catalytic cycle would be initiated
opening products with excellent results (Table 3, entries
13-14). However, the present reaction was not suitable for
the alkyl and vinyl boronoic acid pinacol esters (Table 3,
entries 15-16). To illustrate the advantage of present
conditions to the reported method15a, the reactions of 2c
and 2m were also tested by using [Pd (MeCN2)Cl2], (S)-
tol-binap and Cs2CO3 in methanol at ambient
temperature (Table 3, entries 3 and 13). The results
indicated present conditions showed superior efficiency
in terms of the reaction yields and enantioselectivities.
Next, the scope of the reaction was surveyed by a range
of bicyclic alkenes, including azabenzonorbornadienes
and oxabenzonorbornadienes. As the experimental results
summarized in table 4, except for dimethoxyl-substituted
azabenzonorbornadiene (table 4, entry 3), which gave a
decreased yield due to the generation of 2,3-dimethoxy-6-
phenylnaphthalene as side-product, all of the
azabenzonorbornadienes performed well and gave the
corresponding products generally in good results (table 4,
entries 2-6). And the bromine groups remained intact
that enables further elaboration of the product (table 4,
entry 4). As expected, the reactions of 1b and 1f also gave
superior results than that of the literature conditions15a
Figure 2. Proposed mechansim for the asymmeric ring
opening reaction.
by the coordination of Pd(OAc)2 and (R)-Binap to form
the chiral palladium catalyst A. Subsequently,
transmetalation of phenylboronic acid 1a generates the
arylpalladium species B, which was followed by insertion
of 1a into the carbon-palladium bond to generated
intermediate C. Then the following β-elimination of
nitrogen opens the pyrrolidine ring and yields the ring-
opened species D. Finally, the ring opening product 3aa is
given by hydrolysis.
(table 4, entries
2
and 6). To our delight,
oxabenzonorbornadienes were also viable substrates to
give excellent results (table 4, entries 8-13). Thus, this
synthetic protocol was highly effective for both aza- and
oxa- bicyclic alkenes.
CONCLUSION
In summary, by employing the highly active co-catalytic
system comprising Pd(OAc)2, (R)-BINAP and Zn(OTf)2,
the asymmetric ring opening reactions of both
azabenzonorbornadienes and oxabenzonorbornadienes
with boronic acids were accomplished with high yields
and enantioselectivities. This approach allows for rapid
preparation of chiral arytetralin derivatives.
Finally, the absolute configurations of the ring opening
products of azabenzonorbornadienes (3aa-an & 3ba-ga)
were identified by X-ray analysis of 3da (figure 1),18 and
the ring opening products of oxabenzonorbornadienes
(3ha-ma) were assigned by comparison of the chiral
HPLC data of 3ha with that reported in the literature.19
EXPERIMENTAL SECTION
Synthesis of substrates. Bicyclic alkene 1a-l were pre-
pared according to the literature procedures.21
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0.46 cm ID), conditions: n-hexane/i-PrOH = 95/5, 0.5
mL/min, 254 nm; tmajor = 9.4 min, tminor = 13.2 min.
General Method. The reactions and manipulations
1
2
3
4
were performed under an atmosphere of argon by using
standard Schlenk techniques and Drybox. Anhydrous THF
(Tetrahydrofuran) was distilled from sodium benzophenone
tert-butyl
((1R,2S)-2-(4-chlorophenyl)-1,2-dihydro-
naphthalen-1-yl)carbamate (3ac):17 White solid, 90% yield, 94%
1
ee. [α]D27 = -213.5 (c = 1.24×10-2, CHCl3). H NMR (400 MHz,
1
ketyl prior to use. H and 13C{1H}NMR spectra were recorded
CDCl3) δ 7.29 - 7.10 (m, 6H), 7.02 (d, J = 2 Hz, 2H), 6.67 (dd, J
= 9.7, 1.0 Hz, 1H), 6.08 (dd, J = 9.6, 5.0 Hz, 1H), 5.27 (dd, J =
9.9, 7.4 Hz, 1H), 4.51 (d, J = 10.1 Hz, 1H), 3.84 (t, J = 5.7 Hz, 1H),
1.40 (s, 9H). The ee of 3ac was determined by HPLC analysis
using Daicel Chiralcel AS-H column (25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm;
at ambient temperature on 400 MHz and 75 MHz spectrome-
ters using tetramethylsilane (TMS) as internal reference. The
chemical shifts are quoted in δ units, parts per million (ppm)
5
6
7
8
1
upfield from the signal of internal TMS. H NMR data is rep-
resented as follows: Chemical shift, multiplicity (s = singlet, d
= doublet, t = triplet, m = multiplet), integration and cou-
pling constant(s) J in Hertz (Hz). The enantioselective ex-
cesses were determined by normal phase HPLC eluted with a
mixture of isopropyl alcohol and hexane. High resolution
mass spectra (HRMS) were obtained on a double-focusing
high resolution magnetic-sector mass-analyzed instrument,
operating in an electron impact (EI) mode. Column chroma-
tography was performed with silica gel (200-300 mesh) with
petroleum ether and ethyl acetate as eluents.
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t
major =9.2 min, tminor = 10.8 min.
tert-butyl ((1R,2S)-2-(4-bromophenyl)-1,2-dihydro-
naphthalen-1-yl)carbamate (3ad): White solid, 98% yield, 92%
o
1
ee. Mp 113 - 114 C. [α]D27 = -258.9 (c = 1.66×10-2, CHCl3). H
NMR (400 MHz, CDCl3) δ 7.35 (d, J = 8.0 Hz, 2H), 7.28 – 7.10
(m, 4H), 6.97 (d, J = 8.0 Hz, 2H), 6.68 (d, J = 9.6 Hz, 1H), 6.08
(dd, J = 9.6, 4.9 Hz, 1H), 5.31 - 5.20 (m, 1H), 4.50 (d, J = 10.0
Hz, 1H), 3.83 (t, J = 5.5 Hz, 1H), 1.40 (s, 9H). 13C{1H}NMR
(CDCl3, 100 MHz): δ 155.3, 136.7, 134.3, 133.2, 131.5, 130.8, 129.8,
128.7, 128.3, 127.9, 126.5, 125.5, 121.2, 79.6, 52.2, 44.2, 28.4.
HRMS (EI) calcd for C21H22BrNO2 [M]+: 399.0834. Found:
399.0837. The ee of 3ad was determined by HPLC analysis
using Daicel Chiralcel OD-H column ( 25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm;
tmajor = 8.4 min, tminor = 10.8 min.
General procedure for the asymmetric ring
opening reactions of bicyclic alkene with boronic
acids. Pd(OAc)2 (2.3 mg, 0.01 mmol), (R)-BINAP (7.5 mg,
0.012 mmol) and 1.0 mL THF were added to a Schlenk tube
under argon atmosphere. The resulting solution was stirred
at room temperature for 30 min, then Zn(OTf)2 (7.3 mg, 0.02
mmol) was added and stirred for additional 10 min, then a
solution of bicyclic alkene 1a-m (48.6 mg, 0.2 mmol) in THF
(0.7 mL) was added, and the mixture was stirred for addi-
tional 5 min. The mixture was stirred at -40 °C under argon
atmosphere for 15 min, followed by the addition of boronic
acid 2a-n (48.8 mmol, 0.4 mmol) solution in dry THF (0.5
ml). The mixture was then stirred at -40 °C under argon at-
mosphere with TLC monitoring until the complete consump-
tion of 1a-m. The reaction mixture was concentrated and the
residue was purified by chromatography on a silica gel col-
umn to afford the desired product. The enantioselective ex-
cess value of the product was determined by HPLC on a chi-
ral stationary phase.
methyl
4-((1R,2S)-1-((tert-butoxycarbonyl)amino)-1,2-
dihydronaphthalen-2-yl)benzoate (3ae): White solid, 98%
o
yield, 90% ee. Mp 144 - 146 C. [α]D27 = -292.2 (c = 1.44×10-2,
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.0 Hz, 2H),
7.28 - 7.15 (m, 6H), 6.71 (d, J = 9.6 Hz, 1H), 6.11 (dd, J = 9.6, 4.8
Hz, 1H), 5.31 (dd, J = 9.6, 7.5 Hz, 1H), 4.54 (d, J = 10.1 Hz, 1H),
3.94 (s, 1H), 3.87 (s, 3H), 1.38 (s, 9H). 13C{1H}NMR (CDCl3, 100
MHz): δ 166.9, 155.3, 143.3, 134.3, 133.1, 130.2, 129.6, 129.5, 129.1,
128.9, 128.3, 127.9, 127.3, 126.5, 125.6, 79.6, 52.2, 52.1, 44.8, 28.3.
HRMS calcd for C23H25NO4 [M]+: 379.1784. Found: 379.1783.
The ee of 3ae was determined by HPLC analysis using Daicel
Chiralcel OD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm; tmajor = 10.3 min,
tminor = 13.8 min.
Characterization Data. tert-butyl ((1R,2S)-2-phenyl-1,2-
dihydronaphthalen-1-yl)carbamate (3aa):17 White solid, 95%
tert-butyl
((1R,2S)-2-(4-cyanophenyl)-1,2,3,4-
1
yield, 94% ee. [α]D27 = -288.8 (c = 5.80×10-3, CHCl3). H NMR
tetrahydronaphthalen-1-yl)carbamate (3af): White solid, 97%
o
yield, 93% ee. Mp 124 - 127 C. [α]D27 = -233.1 (c = 1.34×10-2,
(400 MHz, CDCl3) δ 7.24 - 7.09 (m, 9H), 6.67 (d, J = 9.6 Hz,
1H), 6.13 (dd, J = 9.6, 5.0 Hz, 1H), 5.35 - 5.23 (m, 1H), 4.53 (d, J
= 9.8 Hz, 1H), 3.86 (s, 1H), 1.40 (s, 9H). The ee of 3aa was
determined by HPLC analysis using Daicel Chiralcel OD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH
= 98/2, 0.5 mL/min, 254 nm; tmajor = 7.7 min, tminor = 9.7 min.
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 7.8 Hz, 2H),
7.34 - 7.09 (m, 6H), 6.73 (d, J = 9.6 Hz, 1H), 6.07 (dd, J = 9.6,
4.4 Hz, 1H), 5.32 – 5.18 (m, 1H), 4.53 (d, J = 10.0 Hz, 1H), 3.97
(s, 1H), 1.37 (s, 9H). 13C{1H}NMR (CDCl3, 100 MHz): δ 155.0,
144.0, 134.0, 132.8, 132.1, 129.9, 129.3, 128.7, 128.5, 128.2, 126.7,
125.9, 118.8, 111.1, 79.8, 52.2, 45.1, 28.3. HRMS (EI) calcd for
C22H22N2O2 [M]+: 346.1681. Found: 346.1686. The ee of 3af was
determined by HPLC analysis using a Daicel Chiralcel OD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH
= 90/10, 1.0 mL/min, 254 nm; tmajor = 7.5 min, tminor = 10.6 min.
tert-butyl
((1R,2S)-2-(4-fluorophenyl)-1,2-dihydro-
naphthalen-1-yl)carbamate (3ab): White solid, 97% yield, 90%
o
1
ee. Mp 97 - 100 C. [α]D27 = -169.4 (c = 1.30×10-2, CHCl3). H
NMR (400 MHz, CDCl3) δ 7.27 - 7.13 (m , 4H), 7.09 - 7.00 (m,
2H), 6.91 (t, J = 8.4 Hz, 2H), 6.67 (d, J = 9.6 Hz, 1H), 6.09 (dd,
J = 9.6, 4.9 Hz, 1H), 5.30 - 5.23 (m, 1H), 4.51 (d, J = 10.0 Hz, 1H),
3.84 (dd, J = 16.2, 10.9 Hz, 1H), 1.40 (s, 9H). 13C{1H}NMR
(CDCl3, 100 MHz): δ 163.4, 160.9, 155.4, 134.5, 133.4, 133.3, 133.2,
130.6, 130.5, 130.2, 128.4, 128.2, 127.8, 126.4, 125.6, 115.3, 115.1,
79.5, 52.3, 44.0, 28.4. HRMS (EI) calcd for C21H22FNO2 [M]+:
339.1635. Found: 339.1621. The ee of 3ab was determined by
HPLC analysis using Daicel Chiralcel OD-H column (25 cm ×
tert-butyl
((1R,2S)-2-(4-nitrophenyl)-1,2-dihydro-
naphthalen-1-yl)carbamate (3ag): White solid, 99% yield, 95%
o
1
ee. Mp 115 - 117 C. [α]D27 = -280.9 (c = 1.26×10-2, CHCl3). H
NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.3 Hz, 2H), 7.32 - 7.18
(m, 6H), 6.75 (d, J = 9.6 Hz, 1H), 6.09 (dd, J = 9.6, 4.4 Hz, 1H),
5.30 - 5.26 (m, 1H), 4.55 (d, J = 9.9 Hz, 1H), 4.01 (d, J = 23.6 Hz,
1H), 1.36 (s, 9H). 13C{1H}NMR (CDCl3, 100 MHz): δ 155.0, 147.2,
146.2, 133.9, 132.8, 130.0, 129.4, 128.6, 128.6, 128.3, 126.8, 125.9,
5
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Page 6 of 9
123.5, 79.8, 52.2, 44.9, 28.3. HRMS (EI) calcd for C21H22N2O4
0.46 cm ID), conditions: n-hexane/i-PrOH = 95/5, 0.5
mL/min, 254 nm; tmajor = 8.8 min, tminor = 11.4 min.
[M]+: 366.1580. Found: 366.1574. The ee of 3ag was deter-
mined by HPLC analysis using a Daicel Chiralcel OD-H col-
umn (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
95/5, 0.5 mL/min, 254 nm; tmajor = 12.4 min, tminor = 17.2 min.
1
2
3
4
5
6
7
8
tert-butyl
((1R,2S)-1,2-dihydro-[2,2'-binaphthalen]-1-
yl)carbamate (3al): White solid, 93% yield, 82% ee. Mp 58 -
60 oC. [α]D27 = -310.1 (c = 7.2×10-3, CHCl3). 1H NMR (400 MHz,
CDCl3) δ 7.65 - 7.58 (m, 3H), 7.50 (s, 1H), 7.34 - 7.32 (m, 2H),
7.20 - 7.09 (m, 5H), 6.61 (dd, J = 24.4, 9.8 Hz, 1H), 6.12 (dd, J =
9.6, 5.0 Hz, 1H), 5.33 - 5.29 (m, 1H), 4.47 (d, J = 10.0 Hz, 1H),
3.95 (s, 1H), 1.26 (s, 9H). 13C{1H}NMR (CDCl3, 100 MHz): δ
154.5, 134.2, 133.7, 132.3, 131.7, 129.3, 127.4, 127.1, 127.0, 126.9,
126.7, 126.5, 126.1, 125.4, 124.9, 124.7, 124.4, 78.4, 51.3, 43.8, 27.3.
HRMS (EI) calcd for C25H25NO2 [M]+: 371.1885. Found:
371.1893. The ee of 3al was determined by HPLC analysis us-
ing Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm;
tert-butyl
((1R,2S)-2-(4-(trifluoromethyl)phenyl)-1,2-
dihydronaphthalen-1-yl)carbamate (3ah): White solid, 98%
yield, 95% ee. Mp 82 - 85 oC. [α]D27 = -160.2 (c = 1.72×10-2,
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.20 - 7.06 (m, 4H), 7.01
- 6.97 (m, 2H), 6.84 (t, J = 8.4 Hz, 2H), 6.60 (d, J = 9.6 Hz, 1H),
6.02 (dd, J = 9.5, 4.9 Hz, 1H), 5.21 - 5.17 (m, 1H), 4.44 (d, J =
9.9 Hz, 1H), 3.75 (d, J = 24.5 Hz, 1H), 1.32 (s, 9H). 13C{1H}NMR
(CDCl3, 100MHz): δ 162.3, 159.9, 154.3, 133.4, 132.3, 132.2, 129.6,
129.5, 129.2, 127.4, 127.2, 126.8, 125.4, 124.5, 114.3, 114.1, 78.5, 51.2,
43.0, 27.3. HRMS (EI) calcd for C22H22F3NO2 [M]+: 389.1603.
Found: 389.1606. The ee of 3ah was determined by HPLC
analysis using a Daicel Chiralcel OD-H column (25 cm × 0.46
cm ID), conditions: n-hexane/i-PrOH = 98/2, 0.5 mL/min,
254 nm; tmajor = 10.4 min, tminor = 16.3 min.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
t
minor = 9.0 min, tmajor = 11.1 min.
tert-butyl ((1R,2S)-2-(furan-3-yl)-1,2-dihydro-naphthalen-1-
27
yl)carbamate (3am): 17 Colorless oil, 91% yield, 99% ee. [α]D
= -234.7 (c = 1.02×10-2, CH2Cl2). H NMR (400 MHz, CDCl3) δ
1
tert-butyl
((1R,2S)-2-(3-(trifluoromethyl)phenyl)-1,2-
7.28 - 7.19 (m, 5H), 7.11 (d, J = 6.3 Hz, 1H), 6.59 (d, J = 9.6 Hz,
1H), 6.05 - 6.09 (m, 1H), 6.01 (s, 1H), 5.22 (dd, J = 9.6, 6.9 Hz,
1H), 4.74 (d, J = 9.8 Hz, 1H), 3.72 (t, J = 5.4 Hz, 1H), 1.45 (s,
9H). The ee of 3am was determined by HPLC analysis using
Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID), condi-
dihydronaphthalen-1-yl)carbamate (3ai): White solid, 93%
yield, 86% ee. Mp 80 - 83 oC. [α]D27 = -184.1 (c = 1.32×10-2,
1
CHCl3). H NMR (400 MHz, CDCl3) δ 7.47 (t, J = 8.1 Hz, 1H),
7.41 - 7.12 (m, 7H), 6.73 (dd, J = 9.7, 1.5 Hz, 1H), 6.10 (dd, J =
9.6, 4.7 Hz, 1H), 5.27 (dd, J = 10.0, 7.1 Hz, 1H), 4.53 (d, J = 10.1
Hz, 1H), 3.97 (t, J = 5.2 Hz, 1H), 1.37 (s, 9H). 13C{1H}NMR
(CDCl3, 100 MHz): δ 155.2, 139.1, 134.1, 133.0, 132.4, 129.3, 129.2,
128.8, 128.4, 128.1, 126.6, 126.1, 126.0, 125.8, 124.1, 124.0, 79.7,
52.2, 44.6, 28.2. HRMS (EI) calcd for C22H22F3NO2 [M]+:
389.1603. Found: 389.1607. The ee of 3ai was determined by
HPLC analysis using Daicel Chiralcel OD-H column (25 cm ×
0.46 cm ID), conditions: n-hexane/i-PrOH = 98/2, 0.5
mL/min, 254 nm; tmajor = 7.8 min, tminor = 11.3 min.
tions: n-hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm; tmajor
7.8 min, tminor = 10.0 min.
=
tert-butyl ((1R,2S)-2-(thiophen-3-yl)-1,2-dihydro-naphthalen-
1-yl)carbamate (3an):17 Colourless oil, 93% yield, 98% ee.
[α]D = -310.6 (c = 1.10×10-2, CHCl3). H NMR (400 MHz,
CDCl3) δ 7.28 - 7.10 (m, 5H), 6.97 (d, J = 1.9 Hz, 1H), 6.73 (d, J
= 4.6 Hz, 1H), 6.61 (d, J = 9.6 Hz, 1H), 6.13 (dd, J = 9.6, 5.2 Hz,
1H), 5.28 (dd, J = 9.6, 7.2 Hz, 1H), 4.64 (d, J = 9.9 Hz, 1H), 3.94
(t, J = 5.6 Hz, 1H), 1.43 (s, 9H). The ee of 3an was determined
by HPLC analysis using a Daicel Chiralcel OD-H column (25
cm × 0.46 cm ID), conditions: n-hexane/i-PrOH = 95/5, 0.5
mL/min, 254 nm; tmajor = 8.9 min, tminor = 12.5 min.
27
1
tert-butyl
((1R,2S)-2-(2-(trifluoromethyl)phenyl)-1,2-
dihydronaphthalen-1-yl)carbamate (3aj): White solid, 96%
yield, 72% ee. Mp 118 - 120 oC. [α]D27 = -75.9 (c = 5.8×10-3,
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.3 Hz, 1H),
7.45 - 7.14 (m, 6H), 7.08 (d, J = 6.8 Hz, 1H), 6.58 (d, J = 8.2 Hz,
1H), 5.93 (dd, J = 9.6, 3.3 Hz, 1H), 5.14 (dd, J = 10.0, 6.4 Hz, 1H),
4.57 (d, J = 10.1 Hz, 1H), 4.28 (d, J = 2.8 Hz, 1H), 1.20 (s, 9H).
13C{1H}NMR (CDCl3, 100 MHz): δ 154.6, 138.8, 134.7, 132.5,
132.0, 131.7, 131.4, 130.5, 130.4, 128.4, 128.3, 128.2, 127.0, 126.6,
126.0, 126.0, 79.3, 51.5, 41.4, 28.3. HRMS (EI) calcd for
C22H22F3NO2 [M]+: 389.1603. Found: 389.1609. The ee of 3aj
was determined by HPLC analysis using Daicel Chiralcel OD-
H column (25 cm × 0.46 cm ID), conditions: n-hexane/i-
tert-butyl
((1R,2R)-2-vinyl-1,2-dihydronaphthalen-1-
25
yl)carbamate (3ao): Colourless oil, 26% yield, 99% ee. [α]D
=
-179.3 (c = 7.3×10-3, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.27-
7.20 (m, 3H), 7.08-7.06 (m, 1H), 6.53-6.50 (m, 1H), 5.96 (dd, J
= 5.2, 9.6 Hz, 1H), 5.64 (dd, J = 8.4, 17.2 Hz, 1H), 5.24-4.86 (m,
4H), 3.16-3.13 (m, 1H), 1.47 (s, 9H). 13C{1H}NMR (CDCl3, 100
MHz): δ 155.7, 136.3, 134.8, 133.1, 129.3, 127.9, 127.8, 127.6, 126.4,
125.5, 118.4, 79.5, 51.3, 43.6, 28.4. HRMS (EI) calcd for
C17H21NO2Na+ [M]+: 294.1470. Found: 294.1463. The ee of 3ao
was determined by HPLC analysis using a Daicel Chiralcel
OD-H column (25 cm × 0.46 cm ID), conditions: n-hexane/i-
PrOH = 98/2, 0.5 mL/min, 254 nm; tmajor = 7.5 min.
PrOH = 98/2, 0.5 mL/min, 254 nm; tmajor = 7.4 min, tminor
8.3 min.
tert-butyl
=
((1R,2S)-2-(4-methoxyphenyl)-1,2-dihydro-
tert-butyl
((1R,2S)-6,7-dimethyl-2-phenyl-1,2-
naphthalen-1-yl)carbamate (3ak): White solid, 86% yield, 90%
dihydronaphthalen-1-yl)carbamate (3ba): White solid, 98%
ee. Mp 60 - 62 C. [α]D26 = -210.9 (c = 1.26×10-2, CHCl3). H
NMR (400 MHz, CDCl3) δ 7.25 - 7.12 (m, 4H), 6.99 (d, J = 8.5
Hz, 2H), 6.76 (d, J = 8.6 Hz, 2H), 6.65 (d, J = 9.6 Hz,1H), 6.11
(dd, J = 9.6, 5.2 Hz, 1H), 5.30 - 5.26 (m, 1H), 4.52 (d, J = 10.0
Hz, 1H), 3.84 - 3.77 (m, 1H), 3.74 (s, 3H), 1.42 (s, 9H).
13C{1H}NMR (CDCl3, 100 MHz): δ 158.9, 155.6, 134.8, 133.5,
130.8, 130.1, 129.2, 128.0, 128.0, 127.6, 126.3, 125.3, 113.9, 79.4,
55.2, 52.4, 43.9, 28.4. HRMS (EI) calcd for C22H25NO3 [M]+:
351.1834. Found: 351.1816. The ee of 3ak was determined by
HPLC analysis using Daicel Chiralcel OD-H column (25 cm ×
yield, 95% ee. Mp 165 - 167 C. [α]D27 = -260.0 (c = 1.24×10-2,
o
1
o
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.28- 7.17 (m, 3H), 7.16 -
7.05 (m, 2H), 6.93 (d, J = 10.8 Hz, 2H), 6.61 (d, J = 9.6 Hz, 1H),
6.05 (dd, J = 9.6, 4.8 Hz, 1H), 5.26 - 5.17 (m, 1H), 4.53 (d, J =
10.0 Hz, 1H), 3.91 - 3.80 (m, 1H), 2.23 (d, J = 12.2 Hz, 6H), 1.38
(s, 9H). 13C{1H}NMR (CDCl3, 100 MHz): δ 155.4, 138.2, 136.4,
135.7, 132.0, 130.9, 129.3, 129.2, 128.4, 128.2, 127.8, 127.1, 79.3,
52.1, 45.0, 28.4, 19.7, 19.4. HRMS (EI) calcd for C23H27NO2
[M]+: 349.2042. Found: 349.2047. The ee of 3ba was deter-
mined by HPLC analysis using Daicel Chiralcel OD-H col-
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The Journal of Organic Chemistry
umn (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
95/5, 0.5 mL/min, 254 nm; tmajor = 7.8 min, tminor = 10.5 min.
MHz): δ 156.1, 137.3, 136.5, 134.4, 133.3, 130.3, 129.1, 128.6, 128.4,
1
2
3
4
5
6
7
8
128.2, 128.2, 128.2, 127.9, 127.4, 126.5, 125.5, 66.8, 53.0, 44.9.
HRMS (EI) calcd for C24H21NO2 [M]+: 355.1572. Found:
355.1573. The ee of 3ga was determined by HPLC analysis
using a Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH = 95/5, 0.5 mL/min, 254 nm;
tert-butyl
((1R,2S)-6,7-dimethoxy-2-phenyl-1,2-
dihydronaphthalen-1-yl)carbamate (3ca):17 White solid, 86%
yield, 93% ee. [α]D26 = -144.9 (c = 1.09×10-2, CHCl3). H NMR
1
(400 MHz, CDCl3) δ 7.29 - 7.20 (m, 3H), 7.18 - 7.11 (m, 2H),
6.73 (d, J = 24.0 Hz, 2H), 6.58 (dd, J = 9.6, 1.6 Hz, 1H), 6.03
(dd, J = 9.6, 4.7 Hz, 1H), 5.18 (dd, J = 10.0, 7.3 Hz, 1H), 4.56 (d,
J = 10.2 Hz, 1H), 3.88 (d, J = 20.9 Hz, 7H), 1.37 (s, 9H). The ee
of 3ca was determined by HPLC analysis using a Daicel Chi-
ralcel OD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 95/5, 1.0 mL/min, 254 nm; tmajor = 5.9 min,
t
major = 14.9 min, tminor = 20.4 min.
(1R,2S)-2-phenyl-1,2-dihydronaphthalen-1-ol
(3ha):22
Colorless oil, 96% yield, 94% ee. [α]D27 = -172.9 (c = 9.2×10-3,
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.38 - 7.19 (m, 8H), 7.15
(d, J = 7.2 Hz, 1H), 6.68 (dd, J = 9.6, 1.6 Hz, 1H), 6.10 (dd, J =
9.6, 4.0 Hz, 1H), 4.89 (s, 1H), 3.87 - 3.77 (m, 1H), 1.57 (s, 1H).
The ee of 3ha was determined by HPLC analysis using Daicel
Chiralcel AD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 90/10, 1.0 mL/min, 254 nm; tmajor = 7.6 min,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
t
minor = 7.1 min.
tert-butyl
((1R,2S)-6,7-dibromo-2-phenyl-1,2-
dihydronaphthalen-1-yl)carbamate (3da): White solid, 96%
o
yield, 95% ee. Mp 124 - 127 C [α]D27 = -190.2 (c = 1.04×10-2,
t
minor = 10.6 min .
CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 7.0 Hz, 2H),
7.19 - 7.12 (m, 3H), 6.95 (s, 2H), 6.50 (d, J = 9.7 Hz, 1H), 6.16 -
6.12 (m, 1H), 5.26 - 5.16 (m, 1H), 4.36 (d, J = 10.2 Hz, 1H), 3.75
(dd, J = 15.3, 9.1 Hz, 1H), 1.36 (s, 9H). 13C{1H}NMR (CDCl3, 100
MHz): δ 155.4, 136.0, 135.6, 134.3, 132.6, 130.9, 130.6, 129.1, 129.0,
128.7, 127.7, 126.3, 123.7, 123.6, 80.0, 51.7, 44.2, 28.4. HRMS (EI)
calcd for C21H21Br2NO2Na+ [M]+: 499.9837. Found: 499.9827.
The ee of 3da was determined by HPLC analysis using a
Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID), condi-
(1R,2S)-6,7-dimethyl-2-phenyl-1,2-dihydro-naphthalen-1-ol
(3ia):22 White powder, 95% yield, 94% ee. [α]D27 = -126.7 (c =
1
7.6×10-3, CHCl3). H NMR (400 MHz, CDCl3) δ 7.36 - 7.22 (m,
5H), 7.10 (s, 1H), 6.95 (s, 1H), 6.64 (dd, J = 9.6, 1.7 Hz, 1H),
6.04 (dd, J = 9.6, 3.7 Hz, 1H), 4.83 (t, J = 6.3 Hz, 1H), 3.82 (t, J
= 5.6 Hz, 1H), 2.25 (d, J = 6.2 Hz, 6H), 1.46 (d, J = 6.6 Hz, 1H).
The ee of 3ia was determined by HPLC analysis using Daicel
Chiralcel AD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 90/10, 1.0 mL/min, 250 nm; tmajor = 7.6 min,
tminor = 12.4 min.
tions: n-hexane/i-PrOH = 98/2, 0.3 mL/min, 254 nm; tmajor
15.3 min, tminor = 16.8 min.
=
(1R,2S)-5,8-dimethoxy-2-phenyl-1,2-dihydro-naphthalen-1-ol
(3ja):22 Colorless oil, 96% yield, 92% ee. [α]D26 = +59.3 (c =
6.8×10-3, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.44 - 7.37 (m,
4H), 7.31 (t, J = 7.0 Hz, 1H), 7.09 (dd, J = 9.8, 3.1 Hz, 1H), 6.81
(q, J = 9.0 Hz, 2H), 6.14 (d, J = 9.8 Hz, 1H), 5.09 (s, 1H), 3.81
(dd, J = 11.3, 6.0 Hz, 7H), 1.59 (s, 1H). The ee of 3ja was deter-
mined by HPLC analysis using a Daicel Chiralcel AD-H col-
umn (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
80/20, 1.0 mL/min, 250 nm; tmajor = 13.1 min, tminor = 23.9 min.
(1R,2S)-6,7-dibromo-2-phenyl-1,2-dihydro-naphthalen-1-ol
(3ka):22 White solid, 96% yield, 98% ee. [α]D27 = -181.4 (c =
tert-butyl
((5R,6S)-6-phenyl-5,6-dihydronaphtho[2,3-
d][1,3]dioxol-5-yl)carbamate (3ea): White solid, 90% yield, 93%
o
1
ee. Mp 185 - 188 C. [α]D27 = -142.8 (c = 1.04×10-2, CHCl3). H
NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 13.0, 6.6 Hz, 3H), 7.13
(d, J = 6.7 Hz, 2H), 6.72 (s, 1H), 6.65 (s, 1H), 6.55 (t, J = 9.2 Hz,
1H), 6.02 (dd, J = 9.6, 4.8 Hz, 1H), 5.92 (d, J = 8.5 Hz, 2H), 5.18
(dd, J = 9.6, 7.6 Hz, 1H), 4.53 (d, J = 10.1 Hz, 1H), 3.84 - 3.74 (m,
1H), 1.38 (s, 9H). 13C{1H}NMR (CDCl3, 100 MHz): δ 155.3, 147.3,
146.9, 137.8, 129.1, 128.5, 128.4, 128.1, 127.4, 127.2, 107.1, 101.0,
79.4, 60.4, 52.4, 44.8, 28.4, 21.1, 14.2. HRMS (EI) calcd for
C22H23NO4 [M]+: 365.1627. Found: 365.1630. The ee of 3ea was
determined by HPLC analysis using Daicel Chiralcel OD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH
=95/5, 0.5 mL/min, 254 nm; tmajor =10.1 min, tminor = 10.9 min.
tert-butyl ((6R,7S)-7-phenyl-2,3,6,7-tetrahydro-naphtho[2,3-
b][1,4]dioxin-6-yl)carbamate (3fa): White solid, 96% yield, 92%
1
8.8×10-3, CHCl3). H NMR (400 MHz, CDCl3) δ 7.56 (s, 1H),
7.40 (s, 1H), 7.27 (t, J = 9.1 Hz, 3H), 7.21 – 7.10 (m, 2H), 6.59 (d,
J = 9.6 Hz, 1H), 6.19 (dd, J = 9.6, 4.7 Hz, 1H), 4.94 (d, J = 6.4
Hz, 1H), 3.81 (t, J = 5.5 Hz, 1H), 1.56 (t, J = 8.8 Hz, 1H). The ee
of 3ka was determined by HPLC analysis using a Daicel Chi-
ralcel AD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 90/10, 1.0 mL/min, 250 nm; tmajor = 7.1 min,
tminor = 8.9 min.
o
1
ee. Mp 202 - 206 C. [α]D26 = -230.4 (c = 5.4×10-3, CHCl3). H
NMR (400 MHz, CDCl3) δ 7.28 - 7.17 (m, 3H), 7.10 (d, J = 6.6
Hz, 2H), 6.68 (d, J = 10.4 Hz, 2H), 6.54 (d, J = 9.6 Hz,1H), 6.02
(dd, J = 9.6, 5.1 Hz, 1H), 5.25 - 5.14 (m, 1H), 4.45 (d, J = 10.1 Hz,
1H), 4.23 (s, 4H), 3.82 - 3.69 (m, 1H), 1.39 (s, 9H). 13C{1H}NMR
(CDCl3, 100 MHz): δ 155.4, 143.2, 142.6, 137.8, 129.2, 128.8, 128.5,
128.4, 127.5, 127.2, 115.3, 115.0, 79.4, 64.5, 64.4, 51.9, 44.7, 28.4.
HRMS (EI) calcd for C23H25NO4 [M]+: 379.1784. Found:
379.1801. The ee of 3fa was determined by HPLC analysis
using Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH =95/5, 0.5 mL/min, 254 nm;
(5R,6S)-6-phenyl-5,6-dihydronaphtho[2,3-d][1,3]dioxol-5-ol
(3la): Colorless oil, 95% yield, 95% ee. [α]D27 = -102.8 (c =
1
9.2×10-3, CHCl3). H NMR (400 MHz, CDCl3) δ 7.37 - 7.21 (m,
5H), 6.85 (s, 1H), 6.67 (s, 1H), 6.57 (dd, J = 9.6, 1.7 Hz, 1H),
6.02 (dd, J = 9.6, 3.8 Hz, 1H), 5.93 (s, 2H), 4.78 (t, J = 6.4 Hz,
1H), 3.81 (s, 1H), 1.50 (s, 1H). 13C{1H}NMR (CDCl3, 100 MHz): δ
147.3, 147.1, 138.0, 130.4, 129.3, 128.7, 128.0, 127.9, 127.4, 126.9,
108.1, 107.1, 101.1, 71.5, 47.4. HRMS (EI) calcd for C17H14O3 [M]+:
266.0943. Found [M]+: 266.0946. The ee of 3la was deter-
mined by HPLC analysis using Daicel Chiralcel OD-H col-
umn (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
80/20, 1.0 mL/min, 254 nm; tmajor = 10.7 min, tminor = 14.6 min.
(6R,7S)-7-phenyl-2,3,6,7-tetrahydronaphtho[2,3-
t
major = 12.7 min, tminor = 14.1 min.
benzyl ((1R,2S)-2-phenyl-1,2-dihydronaphthalen-1-
yl)carbamate (3ga): Colorless oil, 94% yield, 91% ee. [α]D27 = -
223.2 (c = 1.32×10-2, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.34
- 6.85 (m, 14H), 6.58 (d, J = 9.6 Hz, 1H), 6.03 (dd, J = 9.4, 4.9
Hz, 1H), 5.29 (t, J = 8.3 Hz, 1H), 4.97 (dd, J = 27.7, 12.2 Hz, 2H),
4.72 (d, J = 8.7 Hz, 1H), 3.76 (s, 1H). 13C{1H}NMR (CDCl3, 100
b][1,4]dioxin-6-ol (3ma): Colorless oil, 95% yield, 95% ee.
[α]D27 = -119.2 (c = 5.2×10-3, CHCl3). 1H NMR (400 MHz, CDCl3)
δ 7.35 - 7.21 (m, 5H), 6.86 (s, 1H), 6.69 (s, 1H), 6.57 (dd, J = 9.6,
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1.7 Hz, 1H), 6.00 (dd, J = 9.6, 3.9 Hz, 1H), 4.79 (t, J = 6.3 Hz,
(7) (a) Arrayás, R. G.; Cabrera, S.; Carretero, J. C. Org. Lett.
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1H), 4.23 (s, 4H), 3.80 (t, J = 5.6 Hz, 1H), 1.47 (s, 1H).
13C{1H}NMR (CDCl3, 100 MHz): δ 143.2, 143.1, 138.2, 129.9, 129.3,
128.7, 128.0, 127.6, 127.4, 126.5, 116.3, 115.4, 71.0, 64.5, 64.4, 47.4.
HRMS (EI) calcd for C18H16O3 [M]+: 280.1099. Found [M]+:
280.1123. The ee of 3ma was determined by HPLC analysis
using a Daicel Chiralcel OD-H column (25 cm × 0.46 cm ID),
conditions: n-hexane/i-PrOH = 80/20, 1.0 mL/min, 254 nm;
2005, 7, 219-221. (b) Arrayás, R. G.; Cabrera, S.; Carretero, J. C.
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Organometallics 2015, 34, 4318-4322.
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Org. Biomol. Chem. 2016, 14, 2480-2486.
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Zhou, Y.-Y.; Wang, J.; Fan, B.-M. Asian J. Org. Chem. 2013, 2,
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(15) Selected examples of chiral aryltetralin containing
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K.; Moore, B. S. J. Am. Chem. Soc. 2000, 122, 5415-5416.
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t
major = 13.7 min, tminor = 18.4 min.
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of products, and X-ray crystallographic data (ORTEP) of 3da.
AUTHOR INFORMATION
Corresponding Author
*E-mail of J. C. Chen: chenjingchao84@163.com
*E-mail of B. M. Fan: adams.bmf@hotmail.com
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(21572198, 21362043, 21302162), the Department of Education
of Yunnan Province (ZD2015012), and the Key Laboratory of
Chemistry in Ethnic Medicinal Resources, Yunnan Minzu
University (MZY1506) for financial support.
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