Asymmetric ring-opening reaction of azabenzonorbornadienes with phenols promoted by palladium/(R,R)-DIOP complex

Article abstract of DOI:10.1016/j.tet.2018.03.029

An efficient asymmetric ring opening reaction of azabenzonorbornadienes with various phenols using Palladium/(R,R)-DIOP complex has been demonstrated, the reaction afforded the corresponding products in excellent yields (80–95%) with moderate enantioselec

Full text of DOI:10.1016/j.tet.2018.03.029

Accepted Manuscript
Asymmetric ring-opening reaction of azabenzonorbornadienes with phenols promoted
by palladium/(R,R)-DIOP complex
Zhen Xiu He, Yong Yun Zhou, Baiqiu Han, Xin Xu, Yun Li, Hongyu Qin, Ruifeng Fan,
Laishram Ronibala Devi, Baomin Fan
PII:
S0040-4020(18)30272-2
10.1016/j.tet.2018.03.029
TET 29369
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 10 January 2018
Revised Date: 9 March 2018
Accepted Date: 12 March 2018
Please cite this article as: He ZX, Zhou YY, Han B, Xu X, Li Y, Qin H, Fan R, Devi LR, Fan B,
Asymmetric ring-opening reaction of azabenzonorbornadienes with phenols promoted by palladium/
(R,R)-DIOP complex, Tetrahedron (2018), doi: 10.1016/j.tet.2018.03.029.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Asymmetric Ring-Opening Reaction of
Azabenzonorbornadienes with Phenols
Promoted by Palladium/(R,R)-DIOP
Complex
Zhenxiu He,a Yongyun Zhou,a* Baiqiu Han,a Xin Xu,a Yun Li,a Hongyu Qin,a Ruifeng Fan,a Laishram
Ronibala Devi,a and Baomin Fana,b*
aYMU-HKBU Joint Laboratory of Traditional Natural Medicine, Yunnan Minzu University, Kunming 650500,
China,Fax: (+86)-871-65913103, E-mail: zhouyy@ynni.edu.cn (Yongyun Zhou); FanBM @ynni.edu.cn
(Baomin Fan)
bKey Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu University, Kunming, Yunnan
650500, People's Republic of China.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Asymmetric Ring-Opening Reaction of Azabenzonorbornadienes with Phenols
Promoted by Palladium/(R,R)-DIOP Complex
Zhen Xiu He,a Yong Yun Zhou,a* Baiqiu Han,a Xin Xu,a Yun Li,a Hongyu Qin,aRuifeng Fana Laishram
Ronibala Devi,a Baomin Fan*a,b
aYMU-HKBU Joint Laboratory of Traditional Natural Medicine, Yunnan Minzu University, Kunming 650500, China
Fax: (+86)-871-65913103, E-mail: adams.bmf@hotmail.com
bKey Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu University, Kunming, Yunnan 650500, People's Republic of China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient asymmetric ring opening reaction of azabenzonorbornadienes with various phenols
using Palladium/(R,R)-DIOP complex has been demonstrated, the reaction afforded the
corresponding products in excellent yields (80-95%) with moderate enantioselectivities (50-
64% ees). The syn-configuration of the product was confirmed by the single X-ray
crystallography.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Asymmetric ring-opening reaction,
azabenzonorbornadienes, phenols, palladium
1. Introduction
stereoselectivities. In addition, we also demonstrated the kinetic
resolution of ring opening product.
Asymmetric ring-opening (ARO) reactions of oxo-
/azabenzonorbornadienes with various nucleophiles have
attracted much attention over the past few years due to its direct
access to the chiral hydronapthalenes which are the structural
motifs of bioactive natural products.1 ARO of heterobicyclic
alkenes with various nucleophiles catalyzed by transition metal
such as rhodium,2 palladium,3 iridium,4 copper,5 nickel,6 etc. have
been extensively investigated. Generally, before our group
reported syn-stereoselectivities were achieved in Pd-catalyzed
ring opening reaction of azabenzonorbornadienes with carbon-
based nucleophiles such as organic halides,7 aryl boronic acids,8
organo zinc,9 terminal acetylenes10 and anti-stereoselectivities
were achieved in Rh-or Ir-catalyzed ring opening reaction with
hetero nucleophiles.11 Recently, Yang’s group reported anti-
2. Result and Discussion
The transition metal catalyzed asymmetric ring opening
(ARO) reaction of oxo-/azabenzonorbornadienes is of long-
standing interest in our research group. We commenced our
investigation by exploring suitable ligand for ARO of
azabenzonorbornadiene 1a with phenol 2a by using Pd(OAc)2
and Zn(OTf)2 catalytic system.
As a preliminary investigation, chiral biaryl (R)-Binap ligand
was used under the catalytic condition and gave excellent yield,
96 % with poor ee 10 % in 2.5 h (Table 1, entry 1). Other chiral
biaryl ligands like (R)-P-Phos, (R)-Segphos, (R)-Diflurophos
were also tested but could not achieve higher ees. (Table 1,
entries 3,4,6). However, to our delight when we used point
chirality bidentate ligand (R,R)-DIOP it gave excellent yield 95
% with moderate ee 46 % in shortest duration of 0.5 h (Table 1,
entry 5). This encourages us to the use of point chirality bidentate
ligands such as (R,R)-BDPP, (R)-Phanephos, but could not lead
to higher yields and ees. Interestingly, with (R)-SDP, the ring
opening product was formed in 87% yield and 3% ee in 4h. As
the reaction progressed, yield decreased to 47% while ee
increased drastically to 82% and when the reaction reached 19 h,
it fully converted into tert-butylnaphthalen-1-yl-carbamate (Table
1, entry 8). The P,N-bidentate ligand such as (Sa,S)-DTB-Bn-
SIPHOX was also used, but it only showed chirality control with
no improvement in yield. When ligands like (R)-SINHOS-Me
stereoselective
ring-opening
reactions
of
azabenzonorbornadienes with phenols by applying chiral biaryl
ligand (S)-BINAP in Ir-catalyst.12 They offered excellent yield
with moderate to good ees. To the best of our knowledge, no syn-
stereoselective ring-opening reaction of azabenzonorbornadienes
with phenols has been reported.
In our previous work, we explored ARO reaction of
azabenzonorbornadienes using Pd-catalyst with various
nucleophiles like alcohols, carboxylic acids, amines and terminal
alkynes which offered the desired products in good yields and
ees.13This prompted us to study the ARO reaction of
azabenzonorbornadienes with phenols catalyzed by palladium.
Compared to that of Yang’s group catalyzed by Ir which offered
anti-stereoselectivities, our methodology offered syn-

2
Tetrahedron
ACCEPTED MANUSCRIPT
Table1. Screening of chiral ligands for the ARO reaction of azabenzonorbornadiene 1a with phenol 2aa
Entry
L*
Time (h)
Yield(%)
trans
ee (%)b
syn
Tert-
Butylnaphthalen-
1-yl-carbamate
1
2
3
4
5
6
7
(R)-Binap
(R,R)-BDPP
(R)-P-Phos
2.5
3.0
1.5
6.0
0.5
3.0
7.0
96
83
94
83
95
91
56
-
-
-
-
-
-
-
10
26
33
40
46
15
30
(R)-Segphos
(R,R)-DIOP
(R)-DiFluorphos
(R)-
PHANEPHOS
8
4.0
7.0
19
87
47
-
-
-
-
-
-
3
(R)-SDP
82
-
80
9
(R)-SIPHOS
1.5
21
79
5
17
80
10
(Sa,S)-DTB-Bn-
SIPHOX
11
12
(R)-SINHOS-Me
(S)-iPr-PHOX
22
21
11
26
12
6
73
62
50/ 84c
40/ 68c
aReaction conditions: Pd(OAc)2 (2.3 mg, 0.01 mmol), ligand (0.012 mmol), Zn(OTf)2 (7.3 mg, 0.02 mmol), 1a (48.6 mg, 0.2 mmol), 2a (0.6 mmol), toluene 2.0
mL at 70 ºC (oil bath) under argon atmosphere.bDetermined by HPLC with a Chiralcel OD-H column. cTrans ee%
and (S)-iPr-PHOX were used, it leads to the formation of trans
and naphthylamine in addition to the syn products. But, the yield
and ees of the corresponding trans products are higher than there
syn counterpart these may be due to the transformation of syn
products to tert-butylnaphthalen-1-yl-carbamate which ultimately
leads to the higher yield of the tert-butylnaphthalen-1-yl-
carbamate (Table 1, entries 11,12). But, no trans products were
observed with the other ligands. Thus, (R,R)-DIOP ligand was
found to be an optimal ligand for the ring opening reaction.
Zn(OTf)2, other additives were also evaluated. AgOTf gave
similar yield with lower enantioselectivity (Table 2, entry 5).
Interestingly, when Cu(OTf)2 was used it leads to the
transformation of napthylamine, while the used of ZnI2 failed the
reaction. Besides Lewis acid, organic halide like n-Bu4NCl was
also tested but it could not improve the reaction. It is apparent
that additive was necessary for the reaction since without it the
reaction gave poor ee with moderate yield (Table 2, entry 8).
Generally, Lewis acids help in activating the reactions by
coordinating heteroatom of azabenzonorbornadiene with the
heteroatom of the nucleophile and the complex generated from
metal salt and the ligand. The role of Lewis acids in such reaction
was discussed in our earlier work also.14 Thus, Zn(OTf)2 was
found to be the best additive.
Next, we studied the influence of the additives and palladium
salts using optimized ligand (R,R)-DIOP in the asymmetric ring
opening reaction of azabenzonorbornadiene (Table 2). Among
the palladium salts evaluated, Pd(OAc)2 was found to be the most
effective giving the highest yield with moderate ee (Table 2,
entry 3) but, it failed with PdBr2 (Table 2, entry 1). Besides

3
Table 2ꢀScreening of [Pd] and Additivea
ACCEPTED MANUSCRIPT
Table 4. ARO of azabenzonorbornadienes with various phenolsa
Entry
[Pd]
Additive
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Cu(OTf)2
Fe(OTf)2
Fe(OTf)3
AgOTf
Time (h)
3.0
Yield (%)
trace
58
ee (%)b
Entry
1
2a-m
Time (h)
35
Yield (%)
95
ee (%)b
64
1
2
3
2
3
4
5
6
7
8
PdBr2
-
Pd2(DBA)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
2.5
50
46
2a
2
3
48
24
95
80
56
55
0.5
95
0.5
tert-butylnaphthalen-1-
yl-carbamate
2b
5.0
68
10
96
NR
78
60
36
39
40
-
1.5
2c
4
5
45
33
90
84
50
65
0.75
48
ZnI2
2d
n-Bu4NCl
-
6.0
5
22
5
2e
aReaction conditions: [Pd] (0.01 mmol), (R,R)-DIOP (6.0 mg, 0.012 mmol),
Additives (0.02 mmol), 1a (48.6 mg, 0.2 mmol) 2a (0.6 mmol), toluene
2.0 mL at 70 ºC under argon atmosphere. bDetermined by HPLC with a
Chiralcel OD-H column.
6
7
47
72
85
60
-
2f
Trace
Table 3. Optimization of reaction temperature and solventa
2g
8
41
87
69
Entry
Solvent
Toluene
Toluene
Toluene
Toluene
THF
T(ºC)
70
50
30
0
Time (h)
0.5
2.0
21
Yield (%)
95
ee (%)b
2h
1
2
46
49
56
53
4
9
60
25
93
87
60
63
88
2i
3
78
10
4
89
42
5
30
30
30
30
30
30
30
34
93
2j
11
48
83
61
6
DCM
6.5
17
93
6
7
DCE
74
6
8
DME
39
59
43
64
-
2k
12
13
72
26
72
96
45
55
9
1,4-Dioxane
CH3CN
MTBE
35
95
10
72
trace
78
2l
11
106
63
aReaction conditions: [Pd](0.01 mmol), (R,R)-DIOP (6.0 mg, 0.012 mmol),
Zn(OTf)2 (7.3 mg, 0.02 mmol), 1a (48.6 mg, 0.2 mmol), 2a (0.6mmol),
toluene (1.0mL) at 70 ºC (oil bath) under argon atmosphere. bDetermined by
HPLC with a Chiralcel OD-H column.
2m
aReaction conditions: Pd(OAc)2 (2.3 mg, 0.01 mmol), (R,R)-DIOP (6.0 mg,
0.012 mmol), Zn(OTf)2 (7.3 mg, 0.02 mmol), 1a (48.6 mg, 0.2 mmol), 2a-m
(0.6 mmol) 1,4-Dioxane (1.0mL) at 30 ºC under argon atmosphere.
bDetermined by HPLC with a Chiralcel OD-H column
.
Other reaction parameters like temperature and solvents were
also investigated to improve the reaction result. Temperature has
played a significant role on the reactivity of the reaction.
Lowering the temperature to 50 ºC could not improve the yield
and ee of the reaction. However, on further lowering the
temperature to room temperature there was an appreciable
improvement in the ee 56 % with good yield 78 % (Table 3, entry
3). Even at 0 ºC it gave moderate yield and ee but it required
longer duration 89 h. Among the solvents studied THF, DCE,
DCM gave good yield with poor ee. The use of MTBE could not
improve the yield and ee of the reaction even after 106 h. When
switched to 1,4-dioxane it gave the highest ee value 64% with
excellent yield (Table 3, entry 9). Thus among the various
examined solvents, 1,4-dioxane was found to be an optimal
solvent for the ARO reaction.
With the optimized reaction conditions, the scope of the
reaction was studied by various phenols (Table 4). No
appreciable effect was observed on the reactivities and
enantioselectivities by the electronic property of the substituents

4
Tetrahedron
ACCEPTED MANUSCRIPT
on the phenols. Except for para-cyanophenol, which gave no
of azabenzonorbornadienes gave the expected products in high
desired product even after 72 h, other monosubstituted or
disubstituted phenols with activating, deactivating, or neutral
substituents, gave the desire products in good yields (83-96%)
and moderate enantioselectivities (45-69% ees) (Table 4).
However, significant impact on the reactivity was observed by
the positional property of the substituent. Generally, para-
deactivating substituted phenol gave better results than ortho-
and meta-substituted counterpart (Table 4, entries 2-4). Sterically
hindered 1-naphthol gave lower yield and enantioselectivity
(72% and 45% respectively) than 2-naphthol (96%, 55% ee)
(Table 4, entry 12 and 13). Additionally, multi-substituted phenol
gave excellent yield and moderate enantioselectivity (Table 4,
entry 9). However, excellent performance of this catalytic system
was shown by the para-methoxy phenol giving the desired
product in highest enantioselectivity with good yield (Table 4,
entry 8).
yields with moderate to excellent ees. There was not much effect
on the reactivities and ees with the nature of the substituent on
the N-atom of azabenzonorbornadiene. However, dimethoxy
substituted on the phenyl ring of the azabenzonorbornadiene gave
high yield and ee (Table 5, entry 3).
The absolute configuration of the ring opening product was
determined to be (1R, 2S) by X-ray crystallography (Fig. A).
Suitable crystal was obtained by reacting phenol with dibromo
substituted at the phenyl ring of the azabenzonorbornadiene.
To extend the scope of this reaction, we turned our attention
toward the substrate generality of the process using para-
methoxy phenol with other azabenzonorbornadienes and the
results were summarized in Table 5. It shows that all reactions
Table 5. Scope of Azabenzonorbornadiene derivativesa
Boc
Boc
HN
OH
N
Fig. A: ORTEP diagram of tert-butyl(1R,2S)-6,7-dibromo-2-
phenoxy-1,2-dihydro naphthalen-1-yl)carbamate, 3fa
O
Pd(OAc)2 /(R,R)-DIOP
R
R
Zn(OTf)2,Dioxane, 30 0
C
O
O
3aa-hh
1a-h
2h
Kinetic Resolution Studies
Entry
1
1a-h
Time (h)
41
Yield (%)
ee (%)b
Based on the results of ring opening reaction of
azabenzonorbornadiene using ligand (R)-SDP (Table 1, entry 8)
we inferred that there should be kinetic resolution process for
3aa. This prompted us to study kinetic resolution of
dihydronapthalene which is an effective tool for getting
enantioenriched from the racemic mixture using chiral catalyst.
Thus, we studied the kinetic resolution by subjecting racemic
3aa′′ which lead to the formation of enantiomer 3aa with
naphthylamine 4a and recovery of phenol 2a.
87
69
1a
1b
2
3
52
55
91
88
69
90
1c
Table 6: Screening of ligands for kinetic resolution of racemic
product 3aa˝a
4
5
55
48
78
75
68
59
1d
1e
6
52
50
83
73
64
68
Entry
L*
Time (h)
Yield (%)
ee (%)b
product, 3aa
1f
1
2
(R)-PHANEPHOS
(Sa,S)-DTB-Bn-
SIPHOX
1.5
17
71
54
8
4
7
1g
3
4
5
(R)-SDP
0.5
1.5
1.5
55
49
49
80
-
(R)-Xyl-SDP
(R,R)-DIOP
8
52
75
85
trace
aReaction conditions: Pd(OAc)2 (2.3 mg, 0.01 mmol), Ligand (0.012
mmol), Zn(OTf)2 (7.3 mg, 0.02 mmol), Racemic 3aa˝ (0.2 mmol), 1,4-
Dioxane (1.0mL) at 70 ºC (oil bath) under argon atmosphere. bDetermined by
HPLC with a Chiralcel OD-H column.
1h
aReaction conditions: Pd(OAc)2 (2.3 mg, 0.01 mmol), (R,R)-DIOP (6.0
mg, 0.012 mmol), Zn(OTf)2 (7.3 mg, 0.02 mmol), 1a-h (0.2 mmol) phenols
2h (0.6mmol), 1,4-Dioxane (1.0mL) at 30 ºC under argon atmosphere.
bDetermined by HPLC with a Chiralcel OD-H column.

5
4. Experimental section
We first investigated the reaction by screening ligands under
the standard condition at 70 ºC (Table 6). When (R)-Xyl-SDP
ACCEPTED MANUSCRIPT
4.1. General method
was used in the kinetic resolution reaction it gave enantiomer 3aa
with moderate yield 49% and highest ee value 80% (Table 6,
entry 4). Interestingly, (R,R)-DIOP which was good in ring
opening gave no appreciable enantioenriched 3aa in the kinetic
resolution (Table 6, entry 5). (Sa,S)-DTB-Bn-SIPHOX which showed
chirality control in the ring opening reaction does not show
chirality control in the kinetic resolution reaction even after 17 h
(Table 6, entry 2). With (R)-PHANEPHOS it gave the enantiomer
3aa in good yield and poor ee. Thus, (R)-Xyl-SDP was found to
be an excellent ligand for the kinetic resolution. We further
investigated the reaction of azabenzonorbornadiene with phenol
by adding ligands viz (R)-Xyl-SDP and (R,R)-DIOP
simultaneously under the same reaction condition, no appreciable
effect on the enantioselectivity was observed indicating no
obvious kinetic resolution. In another experiment, these two
ligands were added separately in two steps. (R,R)-DIOP ligand
was first added under the standard reaction condition and
continued till all the azabenzonorbornadiene was consumed,
followed by adding R-Xyl-SDP with Pd(OAc)2 at 60 ºC (Table
7). Surprisingly, there was an improvement in the
enantioselectivity after the addition of R-Xyl-SDP with
Pd(OAc)2. This ascribed the in situ kinetic resolution of ring
opening product formed by the R-Xyl-SDP/Pd complex leading
to the enantioenriched 3aa with the formation of tert-
butylnaphthalen-1-yl-carbamate and phenol. Highest ee value
was found when R-Xyl-SDP and Pd(OAc)2 was used in the molar
ratio of 3% and 2.5% (Table 7, entry 2). Thus, from the above
experiments, it was revealed that (R,R)-DIOP was effective only
for the ring opening reaction but not for the kinetic resolution
whereas R-Xyl-SDP was a good ligand for kinetic resolution but
not for the ring opening reaction.
The reactions and manipulations were performed under an
atmosphere of argon by using standard Schlenk techniques and
Drybox (Mikrouna, Supper 1220/750). Anhydrous toluene, DME
(Dimethoxyethane), THF (Tetrahydrofuran), MTBE (Methyl
tert-butyl ether), ether and dioxane were distilled from sodium
benzophenone ketyl prior to use. Anhydrous DCE (sym-
Dichloroethane), CH3CN (acetonitrile) and DCM were distilled
1
from calcium hydride and stored under argon. H NMR and 13C
NMR spectra were recorded on Bruker-Avance 400 MHz
spectrometer. CDCl3 was used as solvent. Chemical shifts (δ)
were reported in ppm with tetramethylsilane as internal standard,
and J values were given in Hz. The enantioselective excesses
were determined by Agilent 1260 Series HPLC using Daicel AD-
H,AS-H,OD-H,OJ-H chiral columns eluted with a mixture of
isopropyl alcohol and hexane. Melting points were measured on
X-4 melting point apparatus and uncorrected. High resolution
mass spectra (HRMS) were performed on a VG Autospec-3000
spectrometer. Column chromatography was performed with silica
gel (200-300 mesh).
4.2. General procedure for the asymmetric ring opening
reactions
Pd(OAc)2 (2.3 mg, 0.01 mmol), (R,R)-DIOP (6.0 mg, 0.012
mmol) and 1,4-Doxane (1.0 mL) 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 another 10 min, then a solution
of azabenzonorbornadiene (0.2 mmol) in 1,4-Dioxane ( 1.0 mL)
was added, and the mixture was stirred for additional 10 min,
followed by the addition of phenol (0.6 mmol) solution in 1,4-
Dioxane (1.0 mL). The mixture was then stirred at 30 ℃ unde
argon atmosphere. The progress of the reaction was monitored
3. Conclusion
We have successfully developed an efficient catalytic system
of Pd(OAc)2/ (R,R)-DIOP/ Zn(OTf)2 for the syn-steroselective
ARO of azabenzonorbordienes with phenols in good to excellent
yield with moderate enantioselectivities. A wide range of phenols
and various substituents on the phenyl ring of the
with
TLC
until
the
complete
consumption
of
azabenzonorbornadiene. The reaction mixture was then
concentrated and the residue was purified by column
chromatography loaded with silica gel to afford the desired
product. The enantioselective excess value of all the products
was determined by HPLC on a chiral stationary phase.
Table 7: Tanden Reactions Promoted by Separately Added Catalystsa
Entry
Pd(OAc)2
2.5%
R-xyl-SDP
2.5%
3%
Time (h)
1.25
Yield (%)
ee (%)b
81
1
2
3
65
53
72
2.5%
1.25
96
5.0%
6%
1.25
77
aReaction conditions: (R,R)-DIOP (0.012 mmol), Pd(OAc)2 (0.01mmol), Zn(OTf)2 (0.02 mmol), 1a (0.2 mmol), 2a (0.6 mmol), 1,4-Dioxane (1.0mL) at 30 ºC;
Kinetic resolution: R-xyl-SDP and Pd(OAc)2 were added against the table at 70 ºC under argon atmosphere. bDetermined by HPLC with a Chiralcel OD-H colum
20.7
1
4.4.1. tert-butyl ((1R,2S)-2-phenoxy-1,2-dihydronaphthalen-1-
yl)carbamate 3aa. White solid, 95% yield, 64% ee. mp 79-81˚C.
[α]D
= = -266.25 (c =0.32, CH2Cl2). H NMR (400 MHz,
Chloroform-d): δ 7.40 (d, J = 7.3 Hz, 1H), 7.32-7.23 (m, 4H),

6
Tetrahedron
ACCEPTED MANUSCRIPT
7.14 (d, J = 7.1 Hz, 1H), 6.95 (t, J = 7.4 Hz, 1H), 6.89 (d, J =
117.72, 117.64, 116.04, 115.81, 79.95, 72.34, 51.70, 28.42.
HRMS calcd for C21H22FNO3 (M+Na): 378.1476; Found:
378.1476. The ee of 3ae 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; t minor
= 5.09 min;tmajor = 14.62 min.
7.9 Hz, 2H), 6.66 (d, J = 9.7 Hz, 1H), 6.23 (dd, J = 9.7, 4.9 Hz,
1H), 5.35-5.18 (m, 2H), 4.87 (t, J = 4.8 Hz, 1H), 1.52 (s, 9H).13C
NMR (101 MHz, CDCl3): δ 157.75, 155.96, 134.64, 132.13,
131.90, 129.58, 128.63, 127.72, 127.34, 125.50, 124.22, 121.46,
116.08, 79.89, 71.16, 51.75, 28.42. HRMS calcd for C21H23NO3
(M+Na): 360.1570; Found:360.1571.The ee of 3aa was
determined by HPLC analysis using Daicel ChiralcelOD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
90/10, 1.0 mL/min, 254 nm; t major = 5.47min, tminor= 7.13 min.
4.4.6. tert-butyl ((1R,2S)-2-(4-chlorophenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3af. White solid, 85% yield, 60%
ee. mp 132-134℃. [α]D16.2= -263.2 (c = 0.72, CH2Cl2) H NMR
1
(400 MHz, Chloroform-d): δ 7.39 (d, J = 7.2 Hz, 1H), 7.33-
7.27(m, 2H), 7.22-7.18 (m, 2H), 7.15-7.13 (m, 1H), 6.83-6.80
(m, 2H), 6.67 (d, J = 9.7 Hz, 1H), 6.17 (dd, J = 9.7, 4.9 Hz, 1H),
5.46 -5.05 (m, 2H), 4.82 (t, J = 4.8 Hz, 1H), 1.48 (s, 9H). 13C
NMR (101 MHz, CDCl3) δ 156.39, 155.87, 134.43, 132.04,
129.42, 128.71, 127.38, 126.39, 125.54, 123.82, 117.56, 79.99,
71.88, 51.69, 28.40. HRMS calcd for C21H22ClNO3 (M+ Na):
394.1180; Found: 394.1183. The ee of 3af 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; t minor = 5.28min;t major= 10.98 min.
4.4.2. tert-butyl ((1R,2S)-2-(4-bromophenoxy)-1,2-dihydro
naphthalen-1-yl) carbamate 3ab. White solid, 95% yield, 58%
1
ee. mp 141-143˚C. [α]D16 = -282.5 (c = 0.32, CH2Cl2). H NMR
(400 MHz, Chloroform-d): δ 7.40 (d, J= 7.2 Hz, 1H), 7.35-7.25
(m, 4H), 7.14 (d, J = 6.8 Hz, 1H), 6.77 (d, J = 8.4 Hz, 2H), 6,67
(d, J = 9.6 Hz, 1H), 6.17 (dd, J = 9.6, 4.8 Hz, 1H), 5.29-5.19 (m,
2H), 4.82(t, J= 4.8 Hz 1H), 1.48 (s, 9H).13C NMR (101 MHz,
CDCl3): δ 156.91, 155.86, 134.42, 132.37, 132.10, 132.01
128.72, 127.83, 127.39, 125.52, 123.75, 118.02, 113.68, 79.99,
71.77, 51.68, 28.40. HRMS calcd for C21H22BrNO3 (M+Na):
438.0675; Found: 438.0683.The ee of 3ab 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; t major = 15.17 min, t minor = 17.65 min.
4.4.7. tert-butyl ((1R,2S)-2-(4-methoxyphenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3ah. White solid, 87% yield, 69%
15.9
1
ee. mp 89-91ºC. [α]D = -284.7 (c = 0.60, CH2Cl2) H NMR
(400 MHz, Chloroform-d): δ 7.39 (d, J = 7.2 Hz, 1H), 7.32-7.24
(m, 2H), 7.15-7.13 (m, 1H), 6.85- 6.78 (m, 4H), 6.65 (d, J = 9.7
Hz, 1H), 6.17 (dd, J = 9.7, 4.9 Hz, 1H), 5.39- 5.13 (m, 2H), 4.74
(t, J = 4.9 Hz, 1H), 3.75 (s, 3H), 1.49 (s, 9H). 13C NMR (101
MHz, CDCl3): δ 156.00, 154.50, 151.78, 134.68, 132.18, 131.59,
128.57, 127.70, 127.28, 125.58, 124.63, 117.87, 114.63, 79.85,
72.54, 55.70, 51.77, 28.44. HRMS calcd for C22H25NO3
(M+Na):390.1676; Found: 390.1673 The ee of 3ah was
determined by HPLC analysis using Daicel Chiralcel OD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
98/2,0.8 mL/min, 254 nm; t major = 18.60 min; t minor = 23.25 min.
4.4.3. tert-butyl ((1R,2S)-2-(3-bromophenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3ac. Colorless oil, 80% yield, 55%
20
1
ee. [α]D = -221.9 (c = 1.29, CH2Cl2) H NMR (400 MHz,
Chloroform-d): δ 7.40 (d, J = 7.2 Hz, 1H), 7.33-7.25 (m, 2H),
7.16-7.05 (m, 4H), 6.81 (d, J = 7.4 Hz, 1H), 6.68 (d, J = 9.7 Hz,
1H), 6.20 (dd, J = 9.6, 4.8 Hz, 1H), 5.29- 5.18(m, 2H), 4.84 (t, J
= 4.7 Hz, 1H), 1.48 (s, 9H). 13C NMR (101 MHz, CDCl3) δ
158.55, 155.87, 134.38, 132.26, 131.99, 130.63, 128.75, 127.83,
127.42, 125.45, 124.57, 123.55, 122.84, 119.63, 114.73, 80.04,
71.66, 51.68, 28.40. HRMS calcd for C21H22BrNO3 (M+Na):
438.0675; Found: 438.0672 The ee of 3ac was determined by
HPLC analysis using Daicel Chiralcel OD-H column (25 cm ×
0.46 cm ID), conditions: n-hexane/i-PrOH =98/2, 1.0 mL/min,
254 nm; t major = 9.86 min, t minor = 13.31 min.
4.4.8. tert-butyl ((1R,2S)-2-(2,5-dimethylphenoxy)-1,2-dihydro
naphthalen-1-yl) carbamate 3ai. Colorless oil, 93% yield, 60%
16.4
1
ee. [α]D = -209.6 (c = 1.28, CH2Cl2). H NMR (400 MHz,
Chloroform-d): δ 7.41 (d, J = 7.2 Hz, 1H), 7.31-7.26 (m, 2H),
7.14-7.12 (m, 1H), 6.96 (d, J = 7.5 Hz, 1H), 6.73- 6.62 (m, 3H),
6.19 (dd, J = 9.7, 4.7 Hz, 1H), 5.35- 5.16 (m, 2H), 4.87 (t, J = 4.7
Hz, 1H), 2.30 (s, 3H), 1.97 (s, 3H), 1.48 (s, 9H). 13C NMR (101
MHz, CDCl3) δ 155.92, 155.43, 136.59 , 134.86, 132.20, 131.50,
130.70, 128.52, 127.70, 127.14,126.05,125.89, 125.71, 125.02,
124.96, 121.98, 114.80, 79.80, 71.67, 51.87, 28.44, 21.40,15.81.
HRMS calcd for C23H27NO3 (M+Na): 388.1883; Found:
388.1884. The ee of 3ai was determined by HPLC analysis using
Daicel ChiralcelOD-H column (25 cm × 0.46 cm ID), conditions:
4.4.4. tert-butyl ((1R,2S)-2-(2-bromophenoxy)-1,2-dihydro
naphthalen-1-yl) carbamate 3ad. Colorless oil,90%yield,50% ee.
19.7
[α]D
= -177.8(c =1.25, CH2Cl2). 1H NMR (400 MHz,
Chloroform-d): δ 7.46 (dd, J = 16.1, 7.6 Hz, 2H), 7.28 (dq, J =
24.0, 7.6 Hz, 3H), 7.15 (d, J = 7.2 Hz, 1H), 6.97 (d, J = 8.1 Hz,
1H), 6.85 (t, J = 7.6 Hz, 1H), 6.71 (d, J = 9.6 Hz, 1H), 6.20 (dd, J
= 9.1, 4.4 Hz, 1H), 5.57-5.17 (m, 2H), 4.83 (t, J = 4.1 Hz, 1H),
1.46 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 156.03, 154.39,
134.58, 133.44, 132.47, 131.99, 128.78, 128.48, 127.72, 127.36,
125.48, 123.66, 123.09, 116.98, 113.96, 79.82, 73.74, 67.10,
51.91, 28.39. HRMS calcd for C21H22BrNO3 (M+Na):
438.0675; Found: 438.0674. 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 = 99/1, 1.0 mL/min,
254 nm;t major = 14.24 min, t minor = 16.13 min.
n-hexane/i-PrOH = 99/1, 0.5 mL/min, 254 nm; t
= 18.55
major
min, t minor = 23.16 min.
4.4.9. tert-butyl ((1R,2S)-2-(3-methylphenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3aj. Colorless oil, 87% yield, 63%
20.2
1
ee. [α]D
= -231.9 (c = 0.77, CH2Cl2) H NMR (400 MHz,
Chloroform-d): δ 7.39 (d, J = 7.3 Hz, 1H), 7.28 (dd, J = 16.6, 8.6
Hz, 2H), 7.13 (t, J = 7.1 Hz, 2H), 6.76 (d, J = 7.5 Hz, 1H), 6.70-
6.63 (m, 3H), 6.22 (dd, J = 9.5, 4.8 Hz, 1H), 5.36- 5.16 (m, 2H),
4.84 (t, J = 4.8 Hz, 1H), 2.28 (s, 3H), 1.48 (s, 9H). 13C NMR (101
MHz, CDCl3): δ 157.78, 155.98, 139.65, 134.70, 132.16, 131.78,
129.30, 128.59, 127.69, 127.32, 125.50, 124.36, 122.31, 117.05,
112.85, 79.85, 71.12, 51.78, 28.43, 21.51. HRMS calcd for
C22H25NO3 (M+Na): 374.1727; Found: 374.1728. 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-
4.4.5. tert-butyl ((1R,2S)-2-(4-fluorophenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3ae. White solid, 84% yield, 64%
ee. mp 111-113℃. [α]D15.8 = -245.6 (c = 0.16, CH2Cl2) .1H NMR
(400 MHz, Chloroform-d): δ 7.43 (d, J = 7.2 Hz, 1H), 7.36-7.31
(m, 2H), 7.19 (d, J = 7.0 Hz, 1H), 6.98 (t, J = 8.6 Hz, 2H), 6.89-
6.85 (m, 2H), 6.71 (d, J = 9.7 Hz, 1H), 6.20 (dd, J = 9.7, 4.9 Hz,
1H), 5.38- 5.19 (m, 2H), 4.81 (t, J = 4.8 Hz, 1H), 1.52 (s, 9H).
13C NMR (101 MHz, CDCl3): δ 158.87, 156.49, 155.92, 153.81,
134.50, 132.07, 131.92, 128.69, 127.80, 127.36, 125.55, 124.09,

7
PrOH = 98/2,0.8mL/min, 254 nm; t
17.16 min.
= 11.10 min, t
=
PrOH = 98/2,1.0 mL/min, 254 nm; t major = 11.91 min, t
14.50 min.
=
minor
major
ACCEPT
m
E
inorD MANUSCRIPT
4.4.10. tert-butyl ((1R,2S)-2-(4-methylphenoxy)-1,2-dihydro
naphthalen-1 -yl) carbamate 3ak. Colorless oil, 83% yield, 61%
4.4.14.
tert-butyl
((1R,2S)-6,7-dimethoxy-2-(4-
methoxyphenoxy)-1,2-dihydro naphthalen-1-yl) carbamate 3ch.
White solid, 88% yield, 90% ee. mp113-115 ºC. [α]D15.7 = -199.7
(c = 0.38, CH2Cl2) 1H NMR (400 MHz, Chloroform-d); δ 7.51 (d,
J = 8.1 Hz, 1H), 7.30 (d, J = 7.9 Hz, 1H), 7.10 (s, 2H), 6.75-6.66
(m, 5H), 3.97 (d, J = 4.1 Hz, 6H), 3.73 (s, 3H), 1.54 (s, 9H). 13C
NMR (101 MHz, CDCl3): δ 153.41, 149.91, 149.71, 149.42,
131.62, 130.11, 124.09, 116.03, 114.74, 106.98, 100.49, 80.88,
55.90, 55.85, 55.78, 28.40. HRMS calcd for C24H29NO6
(M+Na): 450.1887; Found: 450.1888. The ee of 3ch 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, t major = 20.94min, t minor = 28.01 min.
21.4
1
ee. [α]D
= -38.5 (c = 0.87, CH2Cl2) H NMR (400 MHz,
Chloroform-d): δ 7.39 (d, J = 7.3 Hz, 1H), 7.32-7.25 (m, 2H),
7.13 (d, J = 7.1 Hz, 1H), 7.05 (d, J = 8.3 Hz, 2H), 6.80- 6.77 (m,
2H), 6.65 (d, J = 9.7 Hz, 1H), 6.21 (dd, J = 9.7, 4.9 Hz, 1H),
5.37- 5.16 (m, 2H), 4.80 (t, J = 4.9 Hz, 1H), 2.27 (s, 3H), 1.48 (s,
7H). 13C NMR (101 MHz, CDCl3): δ 155.99, 155.61, 134.69,
132.16, 131.72, 130.86, 130.00, 128.58, 127.69, 127.30, 125.51,
124.43, 116.15, 79.86, 71.48, 51.74, 28.43, 26.95, 20.56. HRMS
calcd for C22H25NO3 (M+Na): 374.1727; Found: 374.1703.
The ee of 3ak was determined by HPLC analysis using Daicel
Chiralcel OD-H column (25 cm × 0.46 cm ID), conditions: n-
hexane/i-PrOH = 98/2,0.8mL/min, 254 nm; t
= 6.03 min, t
major
minor = 6.82 min.
4.4.15. tert-butyl((5R,6S)-6-(4-methoxyphenoxy)-5,6-dihydro
naphtho[2,3-d][1,3]dioxol-5-yl)carbamate 3dh. White solid,
78% yield, 68% ee. mp 110-112 ºC. [α]D16 = -211.2 (c = 0.60,
CH2Cl2) 1H NMR (400 MHz, Chloroform-d): δ 7.54 (s, 1H), 7.48
(d, J=8.1 Hz, 1H), 7.28 (t, J = 7.9 Hz, 1H), 7.18 (s, 1H), 7.10 (s,
1H), 6.76- 6.70 (m, 4H), 6.56 (s, 1H), 6.03 (s, 2H), 3.74 (s, 3H),
1.54 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 154.18, 153.56,
149.70, 148.22, 147.60, 132.21, 131.38, 124.72, 124.28, 119.87,
116.03, 114.78, 104.52, 101.24, 98.10, 80.81, 55.80, 28.41.
HRMS calcd for C23H25NO6 (M+Na): 434.1574; Found:
434.1570. The ee of 3dh 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, t minor
= 13.18 min, t major = 16.74 min.
4.4.11. tert-butyl ((1R,2S)-2-( naphthalen-1-yloxy)-1,2-
dihydro naphthalen-1-yl) carbamate 3al. White solid, 72% yield,
1
45% ee. mp 116-118 ºC. [α]D20.4= -270.8 (c = 0.13, CH2Cl2) H
NMR (400 MHz, Chloroform-d): δ 7.96 (d, J = 8.2 Hz, 1H), 7.80
(d, J = 8.2 Hz, 1H), 7.49 (dt, J = 15.0, 7.1 Hz, 3H), 7.38 (tt, J =
14.4, 7.7 Hz, 4H), 7.20 (d, J = 7.3 Hz, 1H), 6.98 (d, J = 7.5 Hz,
1H), 6.71 (d, J = 9.7 Hz, 1H), 6.34 (dd, J = 9.6, 4.7 Hz, 1H),
5.46-5.34 (m, 2H), 5.17 (t, J = 4.5 Hz, 1H), 1.50 (s, 9H).13C
NMR (101 MHz, CDCl3): δ 155.93, 153.19, 134.67, 132.21,
131.90, 128.69, 127.86, 127.49, 127.36, 126.44, 126.30, 125.77,
125.72, 125.25, 124.37, 122.11, 121.00, 106.98, 79.93, 71.82,
51.92, 28.40. HRMS calcd for C25H25NO3 (M+Na): 410.1727;
Found: 410.1728. The ee of 3al was determined by HPLC
analysis using Daicel Chiralcel OD-H column (25 cm × 0.46 cm
ID), conditions: n-hexane/i-PrOH = 98/2, 1.0 mL/min, 254 nm; t
major = 11.98 min, t minor = 16.63 min.
4.4.16. tert-butyl ((6R,7S)-7-(4-methoxyphenoxy)-2,3,6,7-
tetrahydronaphtho[2,3-b][1,4]dioxin-6-yl)carbamate 3eh. White
16.3
solid, 75% yield, 59% ee. mp 115-117 ºC. [α]D
-259.9 (c =
1
1.22, CH2Cl2) H NMR (400 MHz, Chloroform-d): δ 6.90 (s,
1H), 6.85-6.82 (m, 2H), 6.81- 6.77 (m, 2H), 6.67 (s, 1H), 6.52 (d,
J = 9.7 Hz, 1H), 6.06 (dd, J = 9.6, 4.9 Hz, 1H), 5.33 (d, J = 9.9
Hz, 1H), 5.05 (dd, J = 9.7, 4.6 Hz, 1H), 4.67 (t, J = 4.9 Hz, 1H),
4.24-4.22 (m, 4H), 3.75 (s, 3H), 1.48 (s, 9H). 13C NMR (101
MHz, CDCl3): δ 155.91, 154.45, 151.85, 143.62, 142.62, 130.97,
128.40, 125.91, 122.96, 117.89, 116.32, 115.18, 114.60, 79.79,
72.60, 64.53, 64.38, 55.69, 51.41, 28.43. HRMS calcd for
C24H27NO6 (M+Na): 448.1731; Found: 448.1728. The ee of 3eh
was determined by HPLC analysis using Daicel Chiralcel OD-H
column (25 cm × 0.46 cm ID), conditions: n-hexane/i-PrOH =
98/2, 1mL/min, 230 nm; t minor = 23.84 min, t major = 27.82 min.
4.4.12. tert-butyl ((1R,2S)-2-( naphthalen-2-yloxy)-1,2-
dihydro naphthalen-1-yl) carbamate 3am. White solid, 96%
yield, 55% ee. mp 119-121ºC. [α]D15.8 = -275.4 (c = 0.70, CH2Cl2)
1H NMR (400 MHz, Chloroform-d): δ 7.73 (dd, J = 14.6, 8.6 Hz,
3H), 7.45-7.41 (m, 2H), 7.35- 7.22 (m, 4H), 7.16 (d, J = 7.1 Hz,
1H), 7.06 (dd, J = 8.9, 2.4 Hz, 1H), 6.69 (d, J = 9.7 Hz, 1H), 6.33
(dd, J = 9.7, 4.9 Hz, 1H), 5.39- 5.24 (m, 2H), 5.04 (t, J = 4.9 Hz,
1H), 1.47 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 155.97,
155.58, 134.63, 134.40, 132.15, 132.00, 129.57, 129.25, 128.68,
127.79, 127.66, 127.39, 126.81, 126.50, 125.55, 124.16, 123.97,
119.40, 109.02, 79.94, 71.29, 51.79, 28.42. HRMS calcd for
C25H25NO3 (M+Na): 410.1727; Found: 410.1725 The ee of
3am was determined by HPLC analysis using Daicel Chiralcel
OD-H column (25 cm×0.46 cm ID), conditions: n-hexane/i-
4.4.17.
tert-butyl
((1R,2S)-6,7-dibromo-2-(4-
3fh.
methoxyphenoxy)-1,2-dihydronaphthalen-1-yl)carbamate
PrOH= 98/2, 1.0 mL/min, 254 nm; t
13.93 min.
= 10.22min, t
=
major
minor
White solid, 83% yield, 60% ee. mp 159-161℃. [α]D16 = -188.3 (c
= 0.42, CH2Cl2) 1H NMR (400 MHz, Chloroform-d): δ 7.61 (s,
1H), 7.39 (s, 1H), 6.80 (s, 4H), 6.56 (d, J = 9.7 Hz, 1H), 6.26 (dd,
J = 9.7, 5.1 Hz, 1H), 5.35 (d, J = 9.7 Hz, 1H), 5.09 (dd, J = 9.5,
4.4 Hz, 1H), 4.66 (t, J = 4.9 Hz, 1H), 3.76 (s, 3H), 1.50 (s, 9H).
13C NMR (101 MHz, CDCl3): δ 155.86, 154.72, 151.39, 135.59,
132.95, 131.78, 130.89, 129.84, 126.50, 124.38, 123.63, 117.81,
114.68, 80.40, 71.50, 55.70, 51.40, 28.38. HRMS calcd for
C22H23Br2NO4 (M+Na): 545.9892; Found: 545.9888. The ee
of 3fh was determined by HPLC analysis using Daicel Chiralcel
OD-H column (25 cm × 0.46 cm ID), conditions: n-hexane/i-
4.4.13.
tert-butyl
((1R,2S)-2-(4-methoxyphenoxy)-6,7-
dimethyl-1,2-dihydronaphthalen-1-yl)carbamate 3bh. White
20.6
solid, 91% yield, 69% ee. mp 142-144ºC. [α]D = -240.4 (c =
1
0.24, CH2Cl2) H NMR (400 MHz, Chloroform-d): δ 7.06 (s,
1H), 6.83 (s, 1H), 6.77- 6.69 (m, 4H), 6.51 (d, J = 9.6 Hz, 1H),
6.00 (dd, J = 9.7, 4.8 Hz, 1H), 5.27- 4.99 (m, 2H), 4.63 (t, J = 4.8
Hz, 1H), 3.66 (s, 3H), 2.17 (d, J = 15.9 Hz, 6H), 1.41 (s, 9H). 13
C
NMR (101 MHz, CDCl3) δ 156.04, 154.43, 151.93, 137.00,
135.76, 131.93, 131.38, 129.84, 128.70, 127.10, 123.72, 117.89,
114.60, 79.71, 72.91, 55.67, 51.55, 28.45, 19.95, 19.38. HRMS
calcd for C24H29NO4 (M+Na): 418.1989; Found: 418.1985. The ee
of 3bh was determined by HPLC analysis using Daicel Chiralcel
OD-H column (25 cm × 0.46 cm ID), conditions: n-hexane/i-
PrOH = 98/2, 1.0 mL/min, 254 nm; t
12.51 min.
= 9.71 min, t
=
minor
major

8
Tetrahedron
ACCEPTED MANUSCRIPT
Lett. 2008, 10, 3689-3692. e) Huang, X.-J.; Mo, D.-L.; Ding, C.-
4.4.18.
N-((1R,2S)-2-(4-methoxyphenoxy)-1,2-dihydro
H.; Hou, X.-L. Synlett 2011, 7, 943-946. f) Mo, D.-L.; Chen, B.;
Ding, C.-H.; Dai, L.-X.; Ge, G.-C.; Hou, X.-L. Organometallics
2013, 32, 4465-4468.
naphtha lene-yl)-4-methylbenzenesulfonamide 3gh. White solid,
73% yield, 68% ee. mp 147-149 ºC. [α]D20.4 = -200.5 (c = 0.42,
1
CH2Cl2) H NMR (400 MHz, Chloroform-d): δ 7.75 (d, J = 8.3
4. a) Long, Y.-H.; Yang, D.-Q.; Zhang, Z.-M.; Wu, Y.-J.; Zeng, H.-
P.; Chen, Y. J. Org. Chem. 2010, 75, 7291-7299. b) 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. Organometallics 2010, 29, 5936-5940.
c) Cheng, H.-C.; Yang, D.-Q. J. Org. Chem. 2012, 77, 9756-9765.
d) Li, S.-F.; Chen, H.-L.; Yang, Q.-J.; Yu, L.; Fan, C.-L.; Zhou,
Y.-Y.; Wang, J.; Fan, B.-M. Asian J. Org. Chem. 2013, 2, 494-
497. f) Yang, D.-Q.; Xia, J.-Y.; Long, Y.-H.; Zeng, Z.-Y.; Zuo,
X.-J.; Wang, S.-Y.; Li, C.-R. Org. Biomol. Chem. 2013, 11, 4871-
4881.
Hz, 2H), 7.55 (dd, J = 5.4, 3.0 Hz, 1H), 7.27-7.25 (m, 2H), 7.21
(d, J = 8.0 Hz, 2H), 7.10-7.09 (m, 1H), 6.76-6.71 (m, 2H), 6.62-
6.58 (m, 3H), 6.00 (dd, J = 9.7, 4.9 Hz, 1H), 5.50 (d, J = 9.7 Hz,
1H), 4.77 (dd, J = 9.6, 4.9 Hz, 1H), 4.34 (t, J = 5.0 Hz, 1H), 3.75
(s, 3H), 2.40 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 154.64,
151.09, 143.49, 138.08, 133.31, 131.97, 131.76, 129.78, 128.74,
128.13, 127.28, 126.99, 126.41, 123.86, 117.69, 114.51, 71.45,
55.68, 54.75, 21.57. HRMS calcd for C24H25NO4S (M+Na):
440.1240; Found: 440.1240. The ee of 3gh was determined by
HPLC analysis using Daicel Chiralcel OD-H column (25 cm ×
0.46 cm ID), conditions: n-hexane/i-PrOH = 90/10, 1.0 mL/min,
254 nm, t minor = 18.00 min, t major = 23.16 min.
5.
a) Zhang, W.; Wang, L.-X.; Shi, W.-J.; Zhou, Q.-L. J. Org.
Chem. 2005, 70, 3734-3736. b) Millet, R.; Gremaud, L.;
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Lett. 2009, 50, 3474-3477. d) Bos, P. H.; Rudolph, A.; Pérez, M.;
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11091. b) Lautens, M.; Rovis, T. J. Org. Chem. 1997, 62, 5246-
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4.4.19.
benzyl
((1R,2S)-2-(4-methoxyphenoxy)-1,2-
6.
dihydronaphthalen-1-yl)carbamate 3hh. White solid, 75% yield,
85% ee. mp 125-127 ºC. [α]D20.8 = -354.3 (c = 0.14, CH2Cl2) H
1
NMR (400 MHz, Chloroform-d): δ 7.44-7.37 (m, 6H), 7.33- 7.28
(m, 2H), 7.23-7.15 (m, 1H), 6.87-6.80 (m, 4H), 6.70 (d, J = 9.7
Hz, 1H), 6.21 (dd, J = 9.7, 4.7 Hz, 1H), 5.70 (d, J = 9.7 Hz, 1H),
5.26 (dd, J = 9.7, 4.8 Hz, 1H), 5.22 (s, 2H), 4.80 (t, J = 4.8 Hz,
1H), 3.79 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 156.55,
154.55, 151.55, 136.37, 134.16, 132.10, 131.56, 128.62, 128.26,
127.93, 127.35, 125.77, 124.67, 117.86, 114.63, 72.55, 67.15,
55.68, 52.32. HRMS calcd for C25H23NO4 (M+Na): 425.1519;
Found: 425.1524. The ee of 3hh was determined by HPLC
analysis using Daicel Chiralcel OD-H column (25 cm × 0.46 cm
ID), conditions: n-hexane/i-PrOH = 90/10, 1.0 mL/min, 254 nm;
t minor = 21.50 min, t major = 25.77 min.
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Acknowledgments
We gratefully thank the National Natural Science Foundation of
China (21572198, 21362043, 21302162) and the Government of
Yunnan Province (2017ZDX046, 2017FA004) for financial
support.
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Supplementary Material
Supplementary data associated with this article can be found
online.