Ruthenium-Me-BIPAM-catalyzed addition reaction of aryl-boronic acids to benzofuran-2,3-diones for the enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones

Article abstract of DOI:10.1016/j.tetasy.2015.10.010

We have developed an enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones via the ruthenium-catalyzed 1,2-addition of arylboronic acids to benzofuran-2,3-diones. The use of RuCl₂(PPh₃)₃ with a chiral bidentate p

Full text of DOI:10.1016/j.tetasy.2015.10.010

Tetrahedron: Asymmetry 26 (2015) 1430–1435
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Ruthenium–Me-BIPAM-catalyzed addition reaction of aryl-boronic
acids to benzofuran-2,3-diones for the enantioselective synthesis of
3-aryl-3-hydroxybenzofuran-2-ones
a
b,
⇑
Masaaki Yohda , Yasunori Yamamoto
a
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Japan
Division of Chemical Process Engineering and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-Ku, Sapporo 060-8628, Japan
b
a r t i c l e i n f o
a b s t r a c t
Article history:
We have developed an enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones via the
ruthenium-catalyzed 1,2-addition of arylboronic acids to benzofuran-2,3-diones. The use of
Received 25 September 2015
Accepted 12 October 2015
Available online 29 October 2015
RuCl
amount of acetonitrile (20 mol %) gave optically active 3-aryl-3-hydroxybenzofuran-2-ones with up to
6% ee. This reaction is the first example of a catalytic asymmetric 1,2-addition reaction of arylboronic
2 3 3
(PPh ) with a chiral bidentate phosphoramidite ligand [(R,R)-Me-BIPAM] in the presence of a small
9
acids to benzofuran-2,3-diones for the highly efficient and enantioselective synthesis of quaternary
carbon containing benzofuran-2-ones.
Ó 2015 Elsevier Ltd. All rights reserved.
1
. Introduction
O
HO
Ar
R
RuCl2 complex
R
(
R,R)-Me-BIPAM
O
+
ArB(OH)2
O
Optically active 3-substituted-1-benzofuran-2-ones are impor-
O
O
tant structures contained in biologically active compounds and
are also used as fundamental building blocks in synthetic chem-
istry. Recently, various methods for the synthesis of these com-
pounds have been developed. Transition metal-catalyzed or
organocatalyzed reactions have also been successfully employed.
1
2
3
1
,2
3
4
5
O
Similarly, 3-substituted-3-hydroxy-1-benzofuran-2-ones are also
synthetically important compounds,6 but approaches to these
,7
O
P
O
P
derivatives are limited compared with other derivatives.8
O
O
Over the past decade, much interest has been shown in the use
of stable, commercially available arylboronic acids in transition
metal-catalyzed carbon–carbon bond-forming reactions such as
NMe2
Me2N
(
R,R)-Me-BIPAM
9
10
rhodium-catalyzed asymmetric addition reactions to ketoesters,
Scheme 1. Enantioselective arylation of 1-benzofuran-2,3-diones.
1
1
11a,12
diketones, and isatins.
Although transition metal-catalyzed
asymmetric addition reactions of organoboronic acids to
benzofuran-2,3-diones are particularly powerful and straight
forward approaches, benzofuran-2,3-diones have not been used
in asymmetric addition reactions.
our studies on bisphosphoramidites as chiral auxiliaries for
enantioselective bond-forming reactions, we herein report on
asymmetric addition reactions of arylboronic acids to benzofuran-
2
,3-diones catalyzed by
a
ruthenium/Me-BIPAM complex
In this field, we previously developed chiral bidentate
phosphoramidites (Me-BIPAM and N-Me-BIPAM), derived from
(Scheme 1).
0
0
linked-BINOL (BINOL = 1,1 -binaphthalene-2,2 -diol), for ruthenium-
1
3a,b,e
catalyzed enantioselective arylation reactions to aldehydes,
2. Results and discussion
As shown in Table 1, when [RuCl
1
3b
13c
13d
ketoesters,
glyoxylates, and isatins.
As part of the course of
2 2 2 3 3
(p-cymene)] or RuCl (PPh )
with Me-BIPAM were used for this reaction, the addition products
were obtained in 29%, 34% ee and 27%, 54% ee, respectively (entries
⇑
Corresponding author. Fax: +81 11 706 8117.
E-mail address: yasuyama@eng.hokudai.ac.jp (Y. Yamamoto).
http://dx.doi.org/10.1016/j.tetasy.2015.10.010
957-4166/Ó 2015 Elsevier Ltd. All rights reserved.
0

M. Yohda, Y. Yamamoto / Tetrahedron: Asymmetry 26 (2015) 1430–1435
1431
Table 1
Table 2
Reaction conditionsa
Arylation of 4,6-dimethyl-1-benzofuran-2,3-dione
a
O
O
Ru catalyst
R,R)-Me-BIPAM
additive
HO
O
RuCl2(PPh3)3 (2 mol%)
(R,R)-Me-BIPAM
(2.2 mol%)
HO
Ph
Ar
(
O
+
PhB(OH)2
O
O
+
ArB(OH)2
O
base, toluene/H2O
0 °C, 24 h
O
MeCN (20 mol%)
KF (0.5 mmol),
toluene/H2O (10/1)
80 °C, 18 h
O
O
8
1a
2a
3aa
1a
0.5 mmol)
2b-n
(0.75 mmol)
3ab-an
(
Entry
Ru catalyst
[RuCl (p-cymene)]
(PPh
(nbd)(MeCN)
(PPh (MeCN)
(nbd)(MeCN)
Additive
Base Yieldb (%)
eec (%)
Entry
ArB(OH)
2
(Ar=)
Product
Yieldb (%)
eec (%)
1
2
3
4
2
2
—
—
—
—
KF
KF
KF
KF
KF
KF
KF
KF
KF
KF
KF
29
27
39
60
65
76
74
82
87
48
77
34
48
46
57
51
34
54
81
82
80
91
90
92
93
86
93
82
79
91
36
61
1
2
3
4
5
6
4-PhOC
4-MeSC
6
H
H
4
4
2b
2c
3ab
3ac
3ad
3ae
3af
3ag
3ah
3ai
3aj
3ak
3al
3am
3an
82
75
85
81
83
96
52
86
86
71
96
65
78
91
90
91
95
95
94
94
94
96
88
92
94
87
RuCl
RuCl
RuCl
RuCl
RuCl
RuCl
RuCl
2
3 3
)
6
2
2
2
2
2
2
2
4-MeC
4-PhC
4-ClC
6
H
H
6 4
4
2d
2e
2f
2g
2h
@CHC
2-Naphthyl 2j
3,4-(CH )C
3,5-Me
3-ClC
2-FC
3
)
2
2
d
5
2
PPh
3
e
H
4
6
(PPh
(PPh
(PPh
3
3
3
)
3
)
3
)
3
MeCN
MeCN
MeCN
MeCN
MeCN
PhCN
MeCN
MeCN
MeCN
MeCN
MeCN
6
e,f
4-FC
4-CF
H
7
6
4
d,e
e,g
7
3 6 4
C H
8
e,g,h
8
9
4-CH
H
4
2i
9
RuCl
2
(PPh
)
3 3
2
6
g,i
10
11
12
13
14
15
16
RuCl
RuCl
RuCl
RuCl
RuCl
RuCl
RuCl
2
(PPh
(PPh
(PPh
(PPh
(PPh
(PPh
(PPh
3
3
3
3
3
3
3
)
)
)
)
)
)
)
3
g,j
10
11
12
O
6
H
2k
2
2
3
2
2
2
2
2
2
3
3
3
3
3
3
e,g,h
e,g,h
k
2 6 3
C H 2l
K
K
2
CO
PO
3
6
H
4
2m
2n
3
4
d
13
6 4
H
KF
KF
KF
l
a
Conditions: a mixture of 1a (0.5 mmol), 2b–n (0.75 mmol), KF (0.5 mmol),
MeCN (20 mol %), RuCl (PPh (2 mol %) and (R,R)-Me-BIPAM (2.2 mol %) in
toluene/H O (3 mL/0.3 mL) was stirred at 80 °C for 18 h.
m
2
3 3
)
a
Conditions: a mixture of 1a (0.5 mmol), 2a (1 mmol), base (1 mmol), Ru catalyst
2 mol %) and (R,R)-Me-BIPAM (2.2 mol %) in toluene/H O (3 mL/0.3 mL) was stirred
at 80 °C for 24 h.
2
b
Isolated yield.
Determined by HPLC analysis.
ArB(OH)
In toluene/H
(
2
c
d
e
b
(1.5 mmol) was used.
O (3 mL/0.15 mL).
Isolated yield.
Determined by HPLC analysis.
2
c
2
d
PPh
3
(6 mol %) was added.
e
f
MeCN (20 mol %) was added.
diones with 4-methyl substituent proceeded efficiently to give
the corresponding products in high yield and with high enantiose-
lectivity. However, 1e and 1f gave the corresponding products 3ea
and 3fa with low enantioselectivity. From the above results, we
thought that steric effects of 4-methyl substituent could make
the lactone ring stable against hydrolysis and give high
2
2
a (0.75 mmol) and base (0.75 mmol) were used.
a (0.75 mmol) and base (0.5 mmol) were used.
g
h
i
The mixture was stirred for 18 h.
a (0.75 mmol) and base (0.25 mmol) were used.
PhCN (20 mol %) was added instead acetonitrile.
2
j
k
l
(R,R)-N-Me-BIPAM was used instead (R,R)-Me-BIPAM.
(R)-Monophos was used instead (R,R)-Me-BIPAM.
(R)-BINAP was used instead (R,R)-Me-BIPAM.
16
enantioselectivities.
m
The structure of 3ca was confirmed unequivocally by its X-ray
1
7
crystallography. The absolute configuration of the product was
assigned as the (S)-enantiomer from X-ray crystallographic analy-
sis of compound 3ca (Fig. 1).
The catalytic cycle involves: (1) the transmetallation of an aryl-
boronic acid to a Ru/Me-BIPAM complex giving an Ar–[Ru] species;
1
(
(
and 2). Furthermore, RuCl
MeCN) gave moderate yields and high enantioselectivities
entries 3 and 4). We thought that both triphenylphosphine and
2 2 2 3 2
(nbd)(MeCN) and RuCl (PPh )
2
acetonitrile inhibited the coordination to the ruthenium catalyst
1
4,15
of benzofurandione.
triphenylphosphine or acetonitrile to the ruthenium precursor.
RuCl (PPh with 20 mol % of acetonitrile afforded the desired
We therefore confirmed the addition of
(
2) the insertion of the C@O bond of benzofuran-2,3-dione into the
Ar–Ru bond; and finally (3) the formation of 3-aryl-3-hydroxy-ben-
zofuran-2-one through hydrolysis of the Ru–O intermediate with
water (Fig. 2). The absolute configuration and enantioselectivity
are determined at the insertion step of the C@O bond into an aryl
ruthenium intermediate. KF play two roles: (1) The reaction of F
with ArB(OH) may form three species ArBF (OH)3ꢀn (n = 1–3) and
these species accelerate the transmetallation step. (2) F sup-
presses the hydrolysis of 4,6-dimethyl-benzofuran-2,3-dione more
than OH (Table 1, entries 12 and 13).
2
3 3
)
product in 76% yield and with 91% ee (entry 6). By further investi-
gation of the amount of base, the desired addition product was
finally obtained in 87% yield and with 93% ee in the presence of
ꢀ
1
2 3 3 4
.0 equiv of KF (entries 7–10). The use of K CO or K PO resulted
in lower yields (entries 12 and 13). Among the chiral ligands
screened, the use of bidentate phosphoramidite derived from N-
linked BINOL, (R,R)-N-Me-BIPAM, monodentate phosphoramidite,
2
n
18
ꢀ
ꢀ
(
R)-Monophos, and (R)-BINAP resulted in lower yields and low
enantioselectivities (entries 14–16).
Based on the optimized reaction conditions, we examined the
substrate scope of the asymmetric addition reactions of various
3. Conclusion
arylboronic
acids
to
4,6-dimethyl-1-benzofuran-2,3-dione
In conclusion, we have developed the asymmetric arylation of
(
Table 2). The para- and meta-substituted arylboronic acids with
benzofuran-2,3-diones with arylboronic acids using [RuCl
(PPh ]/(R,R)-Me-BIPAM with an acetonitrile catalyst system. The
2
an electron-donating group or electron-withdrawing group
afforded 3-aryl-3-hydroxy-benzofuran-2-ones in good yields and
with enantioselectivities in the range of 87–96% ee. However,
para-trifluoromethylphenylboronic acid gave a moderate yield
with the use of 3 equiv of boronic acid and changing the solvent
ratio of toluene/H
can also be employed in the addition reaction with the use of
3
3 3
)
high performance of Me-BIPAM for enantioselective 1,2-addition
to benzofuran-2,3-diones was demonstrated. A variety of chiral
3-aryl-3-hydroxybenzofuran-2-ones were obtained with good
enantioselectivities for various substituted arylboronic acids (87–
96% ee). To the best of our knowledge, this is the first example of
a catalytic asymmetric addition of arylboronic acids to benzofu-
ran-2,3-diones. To elucidate upon the enantioselection in the
mechanism, the characterization of Ru/(R,R)-Me-BIPAM catalyst,
2
O (entry 7). The ortho-fluorophenylboronic acid
equiv of arylboronic acid (entry 13).
Next, we investigated the substrate scope of several substituted
benzofuran-2,3-diones (Table 3). Arylation of benzofuran-2,3-
3
PPh and MeCN are currently in progress.

1
432
M. Yohda, Y. Yamamoto / Tetrahedron: Asymmetry 26 (2015) 1430–1435
Table 3
a
Ru-catalyzed asymmetric addition of phenylboronic acid to 1-benzofuran-2,3-diones
RuCl2(PPh3)3
(
2 mol%)
O
HO
(
R,R)-Me-BIPAM
Ph
R
R
(
2.2 mol%)
O
+
PhB(OH)2
O
MeCN (20 mol%)
KF (0.5 mmol),
toluene/H2O (10/1)
80 °C, 18 h
O
O
1
2a
3ba-fa
(
0.5 mmol)
(0.75 mmol)
b
c
Product, Yield [%] , ee [%]
HO
HO
HO
HO
Ph
Ph
Ph
Ph
Ph
OH
Br
O
O
O
O
O
O
O
O
O
O
3
ba
3ca
80%, 94% ee (S)
3da
68%, 92% ee
tBu 3ea
46%, 2% ee
3fa
64%, 5% ee
>
99%, 93% ee
b
Isolated yield. c Determined by HPLC analysis.
a
Conditions:
(PPh (2 mol %) and (R,R)-Me-BIPAM (2.2 mol %) in toluene/H
0 °C for 18 h.
a
mixture of
1
(0.5 mmol), 2a (0.75 mmol), KF (0.5 mmol), MeCN (20 mol %),
RuCl
8
2
3
)
3
2
O (3 mL/0.3 mL) was stirred at
6
d = 53.84) or acetone-d (relative to residual acetone d = 206.26).
Chemical shifts are reported in part per million (ppm). HPLC anal-
ysis was directly performed with chiral stationary phase column,
Chiralpak AD-H or Chiralcel OD-H purchased from DAICEL Co.,
Ltd. High resolution mass spectra (HRMS) were performed on an
electron Ionization (EI) and electrospray ionization (ESI). Optical
rotations were measured on a HORIBA SEPA-300 digital polarime-
ter. Kanto Chemical silica gel 60N (particle size 0.063–0.210 mm)
was used for flash column chromatography. RuCl
3
ꢁxH
2
O was
1
9
obtained from commercial source. [RuCl (p-cymene)]
2
2
,
RuCl
and were
prepared by the literature procedure. BIPAM ligand (Me-BIPAM)
2
2
0
21
22
(
3
PPh )
3
,
RuCl
2
(nbd)(MeCN)
2
,
2 3 2 2
RuCl (PPh ) (MeCN)
Figure 1. ORTEP diagram of 3ca (ORTEP drawing at 50% ellipsoid probability).
2
3
was prepared according to our previous procedure.
O
R
4
.2. Preparation of benzofuran-2,3-diones 1a24
O
O
Ar
O
RuII
A
solution of the 3,5-xylenol (20 mmol), oxalyl chloride
R
(
36 mmol) and 4-(N,N-dimethylamino)-pyridine (0.1 g, 0.82 mmol)
O
ArB(OH)2
KF
in chloroform (30 mL) was refluxed for 10 h. During the reaction
the color changed from yellow to light yellow. After 10 h, the solu-
tion was concentrated. The oily residue was dissolved in 1,2-
dichloroethane (20 mL) and at room temperature dropped into a
suspension of aluminum chloride (50 mmol) in 1,2-dichloroethane
O
ArBFn(OH)3-n
RuII
RuII Ar
H2O
(
20 mL). After 10 h, the dark colored reaction mixture was hydro-
lyzed cold water (50 mL). The yellow organic material was
collected by extraction with chloroform, and washed with brine.
The extracted solution was dried over magnesium sulfoxide for
2 h and then concentrated. The yellow-red residue was purified
by silica column chromatography. After evaporation of the chloro-
form, the residue was recrystallized from chloroform and hexane.
Ar
O
R
H
O
ArBFn(OH)3-n
RuII OH
O
Figure 2. Proposed catalytic cycle.
4
.3. Typical procedure for ruthenium-catalyzed asymmetric
4
4
. Experimental
.1. General
additions of arylboronic acids to benzofuran-2,3-dione
2 3 2
A flask was charged with RuCl (PPh ) (0.01 mmol, 2 mol %) and
(
R,R)-Me-BIPAM (0.011 mmol, 2.2 mol %) under a nitrogen atmo-
1H NMR spectra were recorded on a JEOL ECX-400 (400 MHz) or
JEOL ECS-400 (400 MHz) in CDCl with tetramethylsilane (d = 0.00)
as internal standard or CD Cl (relative to residual CH Cl d = 5.32).
sphere. Next, toluene (3.0 mL) and MeCN (0.1 mmol, 20 mol %) were
added to the flask and the mixture was stirred at room temperature
for 30 min to prepare the catalyst. Benzofuran-2,3-dine (0.5 mmol),
3
2
2
2
2
Chemical shifts are reported in part per million (ppm), and signal
are expressed as singlet (s), doublet (d), triplet (t), quartet (q), mul-
tiplet (m), and broad (br). 13C NMR spectra were recorded on a JEOL
2
arylboronic acid (0.75 mmol), KF (0.5 mmol), and H O (0.3 mL) were
then added to the catalyst solution. The reaction mixture was stirred
at 80 °C for 18 h, at which time the crude reaction mixture was
ECX-400 (100 MHz) in CDCl
3
(d = 77.00) with tetramethylsilane as
Cl (relative to residual CH Cl
2
extracted using ethyl acetate, washed with saturated NH
4
Cl and
an internal standard (d = 0.0) or CD
2
2
2
brine, dried over MgSO , filtered, and concentrated in vacuo. The
4

M. Yohda, Y. Yamamoto / Tetrahedron: Asymmetry 26 (2015) 1430–1435
1433
residue was purified by flash column chromatography on silica gel
Hexane/EtOAc) to give 3-aryl-3-hydroxybenzofuran-2-one.
(t, J = 7.3 Hz, 1H), 6.87 (s, 1H), 6.82 (s, 1H), 3.23 (br s, 1H), 2.39
1
3
(
(s, 3H), 2.11 (s, 3H);
54.0, 142.3, 141.9, 140.6, 137.3, 129.2, 128.0, 127.75, 127.44,
126.2, 124.6, 109.6, 77.7, 21.9, 17.4; MS (ESI) m/z: 313.12 (54),
2 2
C NMR (100 MHz, CD Cl ): d = 177.0,
1
4
.3.1. (3S)-3-Hydroxy-4,6-dimethyl-3-phenyl-2,3-dihydro-1-ben-
+
zofuran-2-one 3aa
18 3
353.11 (100); HRMS (ESI) m/z calcd for C22H O Na (M+Na) :
Colorless oil: 87% yield (111 mg) and 93% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
353.11482, found: 353.11435.
wavelength = 230 nm, t
R
= 25.9 min (major) and 32.6 min (minor)];
4.3.6. (3S)-3-(4-Chlorophenyl)-3-hydroxy-4,6-dimethyl-2,3-di-
hydro-1-benzofuran-2-one 3af
2
2
1
[a]
D
3 2 2
= +49.0 (c 0.5, CHCl ), H NMR (400 MHz, CD Cl ): d = 7.40–
7
2
1
1
.30 (br s, 5H), 6.87 (s, 1H), 6.83 (s, 1H), 3.48 (br s, 1H), 2.39 (s, 3H),
.05 (s, 3H); C NMR (100 MHz, CD Cl ): d = 176.9, 154.0, 142.2,
2 2
38.3, 137.2, 129.08, 129.05, 127.9, 125.6, 124.6, 109.5, 77.7, 21.9,
Colorless oil: 83% yield (119 mg) and 95% ee [HPLC condition:
Chiralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/
1
3
R
min, wavelength = 230 nm, t = 24.5 min (major) and 39.0 min
2
2
1
7.3; MS (ESI) m/z: 237.09 (33), 272.13 (39), 277.08 (100); HRMS
D 3 3
(minor)]; [a] = +86.0 (c 0.5, CHCl ), H NMR (400 MHz, CDCl ):
+
(
ESI) m/z calcd for
C
16
H
14
O
3
Na (M+Na) : 277.08352, found:
d = 7.34 (d, J = 8.7 Hz, 2H), 7.29 (d, J = 8.7 Hz, 2H), 6.86 (s, 1H),
2
77.08343.
6.82 (s, 1H), 3.05 (br s, 1H), 2.39 (s, 3H), 2.06 (s, 3H); 13C NMR
(
6
100 MHz, acetone-d ): d = 176.3, 154.4, 142.2, 138.7, 137.4,
4
.3.2. (3S)-3-Hydroxy-4,6-dimethyl-3-(4-phenoxyphenyl)-2,3-di-
134.5, 129.3, 128.11, 128.06, 125.7, 109.6, 77.1, 21.6, 17.1; MS
hydro-1-benzofuran-2-one 3ab
Colorless oil: 82% yield (142 mg) and 91% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95/5, flow = 0.5 mL/min,
(ESI) m/z 271.05 (36), 311.05 (100); HRMS (ESI) m/z calcd for
+
C
16
H13ClO
3
Na (M+Na) : 311.04454, found: 311.04458.
wavelength = 230 nm, t
R
= 50.7 min (major) and 58.5 min (minor)];
), H NMR (400 MHz, CDCl ): d = 7.33–7.23
3 3
4.3.7. (3S)-3-(4-Fluorophenyl)-3-hydroxy-4,6-dimethyl-2,3-di-
hydro-1-benzofuran-2-one 3ag
Colorless oil: 96% yield (131 mg) and 94% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
2
3
1
[
(
a
]
D
= +68.0 (c 0.5, CHCl
m, 4H), 7.10 (t, J = 7.3 Hz, 1H), 6.99 (d, J = 8.2 Hz, 2H), 6.93 (d,
J = 9.1 Hz, 2H), 6.80 (s, 1H), 6.78 (s, 1H), 3.56 (br s, 1H), 2.35 (s, 3H),
1
3
2
1
1
1
3
3
.08 (s, 3H); C NMR (100 MHz, CD
2 2
Cl ): d = 177.0, 158.2, 156.9,
R
wavelength = 230 nm, t = 23.7 min (major) and 35.2 min (minor)];
2
3
1
53.9, 142.2, 137.3, 132.7, 130.2, 128.0, 127.4, 124.4, 124.2, 119.7,
18.8, 109.5, 77.3, 21.9, 17.4; MS (EI) m/z: 77.05 (53), 115.06 (21),
48.07 (57), 209.12 (24), 225.11 (100), 300.14(29), 317.14 (93),
[a]
D
= +69.0 (c 0.5, CHCl
3 3
), H NMR (400 MHz, CDCl ): d = 7.34–7.31
(m, 2H), 7.03 (m, 2H), 6.84 (s, 1H), 6.80 (s, 1H), 3.30 (br s, 1H), 2.38
1
3
2 2
(s, 3H), 2.06 (s, 3H); C NMR (100 MHz, CD Cl ): d = 176.9, 163.3
46.15(38);HRMS(EI) m/z calcd forC22
H O
18 4
(M):346.12051, found:
(d, J = 247.0 Hz), 153.9, 142.4, 137.3, 134.2 (d, J = 2.9 Hz), 128.1,
127.9 (d, J = 8.6 Hz), 124.4, 116.0 (d, J = 21.9 Hz), 109.6, 77.2, 21.9,
46.12001.
1
7.3; MS (ESI) m/z 255.08 (27), 295.07 (100); HRMS (ESI) m/z calcd
+
4
2
.3.3. (3S)-3-Hydroxy-4,6-dimethyl-3-(4-methylsulfanylphenyl)-
,3-dihydro-1-benzofuran-2-one 3ac
3
for C16H13FO Na (M+Na) : 295.07409, found: 295.07422.
Colorless oil: 75% yield (112 mg) and 90% ee [HPLC condition:
4.3.8. (3S)-3-Hydroxy-4,6-dimethyl-3-(4-(trifluoromethyl)phenyl)-
2,3-dihydro-1-benzofuran-2-one 3ah
Yellow oil: 52% yield (84 mg) and 94% ee [HPLC condition: Chiral-
pak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
Chiralpak AD-H column, hexane/2-propanol = 95/5, flow = 0.5 mL/
min, wavelength = 230 nm, t = 43.1 min (major) and 82.5 min
R
2
3
1
(
minor)]; [
D 3 3
a] = +114.0 (c 0.5, CHCl ), H NMR (400 MHz, CDCl ):
d = 7.23 (d, J = 8.7 Hz, 2H), 7.18 (d, J = 9.1 Hz, 2H), 6.81 (s, 1H),
wavelength = 230 nm, t
R
= 17.7 min (major) and 29.7 min (minor)];
2
3
1
6
.78 (s, 1H), 3.49 (s, 1H), 2.44 (s, 3H), 2.36 (s, 3H), 2.05 (s, 3H);
[a]
D
3 2 2
= +57.0 (c 0.5, CHCl ), H NMR (400 MHz, CD Cl ): d = 7.64 (d,
1
3
C NMR (100 MHz, CD
2
Cl
2
): d = 176.8, 153.9, 142.2, 140.1, 137.2,
J = 8.7 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 6.89 (s, 1H), 6.84 (s, 1H), 3.65
(s, 1H), 2.39 (s, 3H), 2.02 (s, 3H); C NMR (100 MHz, CD Cl ):
2 2
1
3
1
34.7, 127.9, 126.5, 126.2, 124.3, 109.5, 77.3, 21.9, 17.3, 15.5; MS
(
2
3
EI) m/z: 77.05 (14), 149.07 (20), 252.11 (100), 271.10 (37),
73.11 (32), 300.11 (58); HRMS (EI) m/z calcd for C17H O S (M):
16 3
00.08201, found: 300.08175.
d = 176.3, 154.0, 142.8, 142.4, 137.3, 131.0 (q, J = 32.6 Hz), 128.2,
126.4, 126.1 (q, J = 2.9 Hz), 124.4 (q, J = 272.2 Hz), 124.1, 109.7, 77.4,
21.9, 17.3; MS (EI) m/z: 77.05 (15), 91.07 (14), 145.06 (29), 149.09
(39), 209.14 (26), 225.14 (100), 293.14 (75), 322.15 (14); HRMS (EI)
4
.3.4. (3S)-3-Hydroxy-4,6-dimethyl-3-(4-methylphenyl)-2,3-di-
m/z calcd for C17 : 322.08168, found: 322.08254.
13 3 3
H F O
hydro-1-benzofuran-2-one 3ad
Colorless oil: 85% yield (114 mg) and 91% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95/5, flow = 0.5 mL/min,
4.3.9. (3S)-3-(4-Ethenylphenyl)-3-hydroxy-4,6-dimethyl-2,3-di-
hydro-1-benzofuran-2-one 3ai
wavelength = 230 nm, t
R
= 27.7 min (major) and 44.9 min (minor)];
Colorless oil: 86% yield (121 mg) and 94% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
2
3
1
[a]
D
3 3
= +83.3 (c 0.54, CHCl ), H NMR (400 MHz, CDCl ): d = 7.22 (d,
J = 8.3 Hz, 2H), 7.16 (d, J = 8.3 Hz, 2H), 6.84 (s, 1H), 6.79 (s, 1H), 3.12
(
R
wavelength = 230 nm, t = 36.3 min (major) and 58.4 min (minor)];
[a] = +63.0 (c 0.5, CHCl ), H NMR (400 MHz, CDCl ): d = 7.39 (d,
D 3 3
J = 8.7 Hz, 2H), 7.29 (d, J = 8.7 Hz, 2H), 6.85 (s, 1H), 6.79 (s, 1H), 6.69
(dd, J = 11.0 Hz 17.4 Hz, 1H), 5.75 (d, J = 17.4 Hz, 1H), 5.27 (d,
J = 11.0 Hz, 1H), 3.21 (br s, 1H), 2.38 (s, 3H), 2.07 (s, 3H); 13C NMR
s, 1H), 2.37 (s, 3H), 2.33 (s, 3H), 2.08 (s, 3H); 1 C NMR (100 MHz, ace-
tone-d ): d = 176.9, 154.5, 141.9, 138.8, 137.5, 137.0, 129.9, 128.0,
26.4, 126.3, 109.5, 77.6, 21.7, 21.1, 17.3; MS (ESI) m/z: 251.11 (36),
86.14 (39), 291.10 (100); HRMS (ESI) m/z calcd for C17 Na (M
3
23
1
6
1
2
16 3
H O
+
+Na) : 291.09917, found: 291.09913.
(100 MHz, acetone-d
37.1, 127.9, 127.0, 126.5, 126.2, 114.8, 109.5, 77.5, 21.6, 17.2; MS
(ESI) m/z: 298.14 (28), 303.10 (100); HRMS (ESI) m/z calcd for C18
6
): d = 176.6, 154.4, 141.9, 139.3, 138.4 137.4,
1
4
.3.5. (3S)-3-Hydroxy-4,6-dimethyl-3-(4-phenylphenyl)-2,3-di-
16
H -
+
hydro-1-benzofuran-2-one 3ae
3
O Na (M+Na) : 303.09917, found: 303.09900.
Colorless solid: 61–63 °C; 81% yield (134 mg) and 95% ee [HPLC
condition: Chiralpak AD-H column, hexane/2-propanol = 95:5,
4.3.10. (3S)-3-Hydroxy-3-(naphthalen-2-yl)-4,6-dimethyl-2,3-di-
hydro-1-benzofuran-2-one 3aj
Colorless solid: 56–58 °C; 86% yield (130 mg) and 96% ee [HPLC
condition: Chiralpak AD-H column, hexane/2-propanol = 95:5,
flow = 0.5 mL/min, wavelength = 230 nm,
R
t = 65.6 min (major)
23
1
and 88.0 min (minor)]; [
a]
D
= +69.0 (c 0.5, CHCl
3
), H NMR
(
400 MHz, CDCl ): d = 7.56–7.53 (m, 4H), 7.44–7.40 (m, 4H), 7.35
3

1
434
M. Yohda, Y. Yamamoto / Tetrahedron: Asymmetry 26 (2015) 1430–1435
flow = 0.5 mL/min, wavelength = 230 nm, t
R
= 60.2 min (major) and
4.3.15. (3S)-3-Hydroxy-3-phenyl-4,7-dimethyl–2,3-dihydro-1-
benzofuran-2-one 3ba
2
3
1
6
8.6 min (minor)]; [
a
]
D
3
= +37.0 (c 0.5, CHCl ), H NMR (400 MHz,
CDCl
3
): d = 7.93 (s, 1H), 7.82 (m, 3H), 7.51 (d, J = 3.2 Hz, 1H), 7.49
Colorless oil: >99% yield (129 mg) and 93% ee [HPLC condition:
Chiralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/
(
d, J = 3.2 Hz, 1H), 7.31 (d, J = 8.7 Hz, 1H), 6.90 (s, 1H), 6.81 (s,
1
H), 3.22 (s, 1H), 2.40 (s, 3H), 2.07 (s, 3H); 13C NMR (100 MHz,
Cl ): d = 176.9, 154.1, 142.3, 137.4, 135.7, 133.6, 133.4, 129.1,
R
min, wavelength = 230 nm, t = 21.2 min (major) and 23.2 min
2
3
1
CD
2
2
(minor)]; [
D 3 3
a] = +57.0 (c 0.5, CHCl ), H NMR (400 MHz, CDCl ):
1
7
28.7, 128.03, 128.00, 127.08, 126.96, 125.1, 124.7, 123.1, 109.6,
d = 7.35–7.30 (br s, 5H), 7.11 (d, J = 7.8 Hz, 1H), 6.86 (d, J = 8.2 Hz,
1
3
7.9, 22.0, 17.3; MS (ESI) m/z: 287.11 (54), 327.10 (100); HRMS
1H), 3.58 (s, 1H), 2.31 (s, 3H), 2.04 (s, 3H); C NMR (100 MHz,
CDCl ): d = 176.50, 151.74, 137.57, 134.14, 132.14, 128.65,
128.62, 126.59, 126.53, 125.21, 118.45, 77.77, 16.88, 14.59; MS
EI) m/z: 77.05 (20), 149.07 (14), 208.10 (33), 225.11 (100),
54.12 (9); HRMS (EI) m/z calcd for C16 (M): 254.09429,
found: 254.09363.
+
(
ESI) m/z calcd for
C
20
H
16
O
3
Na (M+Na) : 327.09917, found:
3
3
27.09869.
(
2
14 3
H O
4
2
.3.11. (3S)-3-(2H-1,3-Benzodioxol-5-yl)-3-hydroxy-4,6-dimethyl-
,3-dihydro-1-benzofuran-2-one 3ak
Colorless oil: 71% yield (106 mg) and 88% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
wavelength = 230 nm, t = 59.0 min (major) and 78.6 min (minor)];
4.3.16. (3S)-5-Bromo-3-hydroxy-4,6-dimethyl-3-phenyl-2,3-di-
hydro-1-benzofuran-2-one 3ca
White solid: mp 146–147 °C; 80% yield (133 mg) and 94% ee
[HPLC condition: Chiralpak AD-H column, hexane/2-propa-
R
2
3
1
[
a]
D
= +100.0 (c 0.5, CHCl
3
), H NMR (400 MHz, CDCl
3
): d = 6.87–
6
2
1
1
(
3
.74 (m, 5H), 5.96 (dd, J = 3.6, 1.4 Hz, 2H), 3.07 (s, 1H), 2.38 (s, 3H),
1
3
.11 (s, 3H); C NMR (100 MHz, acetone-d
6
): d = 176.7, 154.5,
R
nol = 95:5, flow = 0.5 mL/min, wavelength = 230 nm, t = 20.9 min
2
3
1
49.0, 148.7, 142.0, 137.5, 133.7, 128.0, 126.1, 119.9, 109.6, 108.7,
(minor) and 25.8 min (major)]; [
NMR (400 MHz, CDCl ): d = 7.38–7.31 (m, 5H), 7.00 (s, 1H), 3.20
(s, 1H), 2.49 (s, 3H), 2.17 (s, 3H); C NMR (100 MHz, CD
d = 176.3, 152.5, 142.3, 138.0, 137.8, 129.3, 129.3, 126.5, 125.6,
24.1, 111.4, 78.0, 25.0, 19.1; MS (ESI) m/z: 315.00 (5), 354.99
28), 356.99 (28); HRMS (ESI) m/z calcd for C16 13BrO Na (M
a
]
D
= +86.0 (c 0.5, CHCl
3
),
H
07.0, 102.4, 77.3, 21.7, 17.3; MS (ESI) m/z: 281.08 (34), 316.12
3
+
13
18), 321.07 (100); HRMS (ESI) m/z calcd for C17
H
14
O
5
Na (M+Na) :
2
Cl
2
):
21.07334, found: 321.07293.
1
(
+
H
3
4
3
.3.12. (3S)-3-Hydroxy-3-(3,5-dimethylphenyl)-4,6-dimethyl-2,
-dihydro-1-benzofuran-2-one 3al
+
Na) : 354.99403, found: 354.99384.
White solid: mp 162–164 °C; 96% yield (135 mg) and 92% ee
HPLC condition: Chiralpak AD-H column, hexane/2-propa-
4
.3.17. (3S)-3-Hydroxy-4-methyl-3-phenyl-2,3-dihydro-1-benzo-
[
furan-2-one 3da
Colorless oil: 68% yield (84 mg) and 92% ee [HPLC condition:
Chiralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/
nol = 95:5, flow = 0.5 mL/min, wavelength = 230 nm, t = 23.8 min
R
23
1
(
major) and 25.6 min (minor)]; [
NMR (400 MHz, CDCl ): d = 6.94–6.92 (m, 3H), 6.85 (s, 1H), 6.79
s, 1H), 3.07 (br s, 1H), 2.38 (s, 3H), 2.28 (s, 6H), 2.08 (s, 3H);
NMR (100 MHz, acetone-d ): d = 176.9, 154.5, 141.8, 139.8, 138.8,
37.4, 130.6, 128.0, 126.6, 124.0, 109.5, 77.6, 21.7, 21.4, 17.3; MS
ESI) m/z: 265.12 (40), 300.16 (50), 305.11 (100); HRMS (ESI) m/z
D 3
a] = +63.0 (c 0.5, CHCl ), H
3
R
min, wavelength = 230 nm, t = 27.2 min (minor) and 30.0 min
1
3
(
C
23
1
(
major)]; [
a]
D
= +29.0 (c 0.5, CHCl
3
), H NMR (400 MHz, CD
2
Cl
2
):
6
d = 7.30–7.23 (m, 6H), 6.96 (d, J = 8.2 Hz, 1H), 6.92 (d, J = 7.8 Hz,
1
(
13
1
H), 3.21 (br s, 1H), 2.00 (s, 3H); C NMR (100 MHz, CD
d = 176.5, 153.9, 138.1, 137.8, 131.3, 129.2, 127.5, 127.3, 125.6,
09.0, 77.7, 17.4; MS (EI) m/z: 77.05 (22), 105.04 (13), 135.05
16), 194.09 (24), 211.10 (100), 240.10 (10); HRMS (EI) m/z calcd
2
Cl
2
):
+
calcd for C18
18 3
H O Na (M+Na) : 305.11482, found: 305.11486.
1
(
4
.3.13. (3S)-3-Hydroxy-3-(3-chlorophenyl)-4,6-dimethyl-2,3-di-
for C15H12O (M): 240.07864, found: 240.07830.
3
hydro-1-benzofuran-2-one 3am
Colorless oil: 65% yield (94 mg) and 94% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
4.3.18. 7-tert-Butyl-3-hydroxy-5-methyl-3-phenyl-2,3-dihydro-
1-benzofuran-2-one 3ea
wavelength = 230 nm, t
R
= 23.9 min (major) and 28.0 min (minor)];
), H NMR (400 MHz, CDCl ): d = 7.39–7.18
3 3
White solid: 46% yield (68 mg) and 2% ee [HPLC condition: Chi-
ralpak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/
2
3
1
[a
]
D
= +64.0 (c 0.5, CHCl
(
m, 4H), 6.87 (s, 1H), 6.82 (s, 1H), 3.11 (br s, 1H), 2.39 (s, 3H), 2.07 (s,
min, wavelength = 230 nm, t = 19.5 min (minor) and 25.0 min
R
1
3
1
3
1
2
H); C NMR (100 MHz, acetone-d
6
): d = 176.2, 154.5, 142.5, 142.3,
(major)]; H NMR (400 MHz, CDCl ): d = 7.41–7.33 (m, 5H), 7.13
3
13
37.4, 135.0, 131.1, 129.2, 128.2, 126.5, 125.7, 124.8, 109.7, 77.2,
(s, 1H), 6.95 (s, 1H), 3.37 (br s, 1H), 2.31 (s, 3H), 1.42 (s. 9H);
C
1.7, 17.2; MS (ESI) m/z: 271.05 (29), 306.09 (25), 311.05 (100);
NMR (100 MHz, CD Cl ): d = 176.8, 149.5, 139.7, 135.1, 134.8,
2
2
+
HRMS (ESI) m/z calcd for C16
H13ClO
3
Na (M+Na) : 311.04454, found:
130.1, 129.2, 129.1, 125.7, 123.2, 77.0, 34.5, 29.7, 21.4.
3
11.04471.
4
3
.3.19. 1-Hydroxy-1-phenyl-1H,2H-naphtho[2,1-b]furan-2-one
fa
Yellow oil: 64% yield (89 mg) and 5% ee [HPLC condition: Chiral-
4
.3.14. (3R)-3-(2-Fluorophenyl)-3-hydroxy-4,6-dimethyl-2,3-di-
hydro-1-benzofuran-2-one 3an
pak AD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
wavelength = 230 nm, t = 50.6 min (major) and 63.7 min (minor)];
Cl ): d = 8.02 (d, J = 8.7 Hz, 1H), 7.95–7.92
(m, 1H), 7.68–7.65 (m, 1H), 7.46–7.32 (m, 9H), 3.74 (br s, 1H);
Colorless oil: 78% yield (106 mg) and 87% ee [HPLC condition: Chi-
ralcel OD-H column, hexane/2-propanol = 95:5, flow = 0.5 mL/min,
R
1
H NMR (400 MHz, CD
2
2
R
wavelength = 230 nm, t = 17.9 min (major) and 22.9 min (minor)];
2
4
1
[
(
a
]
D
= ꢀ135.0 (c 0.5, CHCl
3 3
), H NMR (400 MHz, CDCl ): d = 7.83
1
3
C NMR (100 MHz, CD
2 2
Cl ): d = 177.0, 151.9, 138.4, 133.0, 131.8,
dt, J = 8.0, 1.7 Hz, 1H), 7.34–7.28 (m, 1H), 7.22–7.19 (m, 1H), 6.97–
1
29.6, 129.3, 129.2, 128.4, 125.7, 123.3, 121.5, 112.0, 78.3.
6
1
.92 (m, 1H), 6.82 (s, 1H), 6.70 (s, 1H), 3.59 (br s, 1H), 2.33 (s, 3H),
.99 (s, 3H); C NMR (100 MHz, CDCl ): d = 176.3, 158.9 (d,
3
1
3
J = 246 Hz), 153.9, 141.6, 136.3, 130.4 (d, J = 8.6 Hz), 127.7 (d,
J = 2.9 Hz), 127.4, 125.8 (d, J = 11.5 Hz), 124.0 (d, J = 2.9 Hz), 122.9,
Acknowledgments
1
(
15.7 (d, J = 21.1 Hz), 109.1, 74.5, 21.7, 16.8; MS (EI) m/z: 77.05
27), 149.07 (22), 224.10 (36), 243.11 (100), 272.11 (23); HRMS (EI)
m/z calcd for C16 (M): 272.08487, found: 272.08473.
This research was supported by the MEXT (Japan) program
‘‘Strategic Molecular and Materials Chemistry through Innovative
Coupling Reactions” of Hokkaido University, Japan.
H13FO
3

M. Yohda, Y. Yamamoto / Tetrahedron: Asymmetry 26 (2015) 1430–1435
1435
1
2
5, 2958–2961; (j) Wang, Z.-D.; Wang, F.; Li, X.; Cheng, J.-P. Org. Biomol. Chem.
013, 11, 5634–5641; (k) Lakshimi, K. C. S.; Paul, R. R.; Suresh, E.; Nair, V.
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