T. Mino et al. / Tetrahedron: Asymmetry 26 (2015) 1065–1068
1067
Shimadzu GCMS-QP5050A using EI, and presented as m/z (% rel
intensity). HRMS were recorded on a Thermo Fisher Scientific Exac-
tive using ESI. Analytical high-performance liquid chromatography
7.06–7.14 (m, 3H), 7.21–7.32 (m, 2H); 13C NMR (CDCl
d 21.4, 37.0, 40.6, 117.1, 124.6, 125.9, 128.2, 128.3, 128.4x2,
3
, 75 MHz)
128.7, 129.0, 138.8, 140.2, 151.7, 167.7; EI-MS m/z (rel intensity)
+
(
HPLC) was done with a JASCO GULLIVER 900 or 2000 system cou-
238 (M , 100); HRMS (ESI-orbitrap) m/z calcd for C16
14
H O
2
+H
pled with the UV detector using a chiral column. Optical rotations
were measured on JASCO P-2100.
239.1067 found 239.1066; HPLC (Daicel CHIRALCELÒ OD-H, 0.46
/ Â 25 cm, UV 254 nm, hexane/2-propanol = 95:5, 1.0 mL/min)
t
R
= 20.6 min (major) and 24.6 min (minor).
4
.2. General procedure for the BICMAP-rhodium(I)-catalyzed
4
.2.5. (S)-4-(3,5-Dimethylphenyl)chroman-2-one 3e (Table 1,
asymmetric 1,4-addition of arylboronic acids to coumarins
entry 16)
2
0
8
5% yield (83.3 mg, 0.331 mmol), 99% ee; [
a]
D
= +40.1 (c 0.40,
Under an atmosphere of argon, [Rh(OH)(cod)]
2
(2.7 mg,
1
CHCl
3
); white solid; mp 87–88 °C; H NMR (CDCl , 300 MHz) d
3
6
.0
l
mol) and (S)-BICMAP (8.2 mg, 13.2 mol) were added to aryl-
l
2
2
.28 (s, 6H), 2.95–3.10 (m, 2H), 4.26 (t, J = 7.0 Hz, 1H), 6.76 (s,
boronic acid (4.0 or 2.0 mmol) in 1,4-dioxane (1.0 or 0.5 mL) and
water (0.1 or 0.05 mL). After stirring the mixture for 1 h at room
temperature, the coumarin derivative (0.40 or 0.20 mmol) was
added. The reaction mixture was stirred at 60 °C for 16 h. After
being cooled to room temperature, the mixture was quenched with
H), 6.92–6.99 (m, 2H), 7.05–7.14 (m, 2H), 7.26–7.32 (m, 1H);
1
3
3
C NMR (CDCl , 75 MHz) d 21.3, 37.0, 40.5, 117.0, 124.6, 125.3,
1
26.0, 128.4, 128.6, 129.3, 138.7, 140.2, 151.6, 167.8; EI-MS m/z
+
(
rel intensity) 252 (M , 100); HRMS (ESI-orbitrap) m/z calcd for
Ò
17 16 2
C H O +H 253.1223 found 253.1224; HPLC (Daicel CHIRALCEL
sat. NaHCO
3
aq and diluted with EtOAc. The organic layer was
SO . The filtrate
OD-H, 0.46 / Â 25 cm, UV 254 nm, hexane/2-propanol = 95:5,
washed with water and brine, and dried over Na
2
4
1
.0 mL/min) t
R
= 14.3 min (major) and 15.7 min (minor).
was concentrated with a rotary evaporator and the residue was
purified by column chromatography (elution with n-hexane/
EtOAc = 10-8/1).
4
.2.6. (S)-4-(2-Naphthalenyl)chroman-2-one 3f (Table 1, entry 17)
2
0
1
2% yield (13.5 mg, 0.049 mmol), 80% ee; [
a]
D
= +42.6 (c 0.45,
1
CHCl
3
); white solid; mp 147–148 °C; H NMR (CDCl , 300 MHz) d
3
8
4
.2.1. (S)-4-Phenylchroman-2-one 3a (Table 1, entry 2)
3
1
2
.14 (d, J = 7.1 Hz, 2H), 4.52 (t, J = 7.1 Hz, 1H), 6.99 (d, J = 7.3 Hz
H), 7.09 (t, J = 7.5 Hz, 1H), 7.17 (d, J = 8.2 Hz, 1H), 7.25–7.35 (m,
H), 7.47–7.50 (m, 2H), 7.59 (s, 1H), 7.76–7.86 (m, 3H); C NMR
2
0
7
4% yield (66.1 mg, 0.295 mmol), 99% ee; [
a]
D
= +41.2 (c 0.62,
) for 98% ee (S)}; white solid;
, 300 MHz) d 2.98–3.13 (m, 2H),
.35 (t, J = 7.0 Hz, 1H), 6.98 (d, J = 7.3 Hz, 1H), 7.06–7.18 (m, 4H),
.26–7.38 (m, 4H); C NMR (CDCl
24.6, 125.8, 127.55, 127.66, 128.3, 128.8, 129.1, 140.3, 151.7,
3
3
CHCl
3
) {lit. [
a
]
D
= +37.4 (c 0.74, CHCl
3
13
1
mp 114–115 °C; H NMR (CDCl
3
(
3
CDCl , 75 MHz) d 36.9, 40.8, 117.1, 124.7, 125.2, 125.7, 126.2,
4
7
1
1
1
1
26.5, 126.6, 127.7, 127.8, 128.4, 128.9, 129.1, 132.7, 133.4,
37.5, 151.7, 167.6; EI-MS m/z (rel intensity) 274 (M , 92); HRMS
1
3
3
, 75 MHz) d 37.0, 40.7, 117.1,
+
(
2
2
ESI-orbitrap) m/z calcd for
C
19
H
14
O
2
+H 275.1067 found
75.1065; HPLC (Daicel CHIRALCEL OD-H, 0.46 / Â 25 cm, UV
54 nm, hexane/2-propanol = 95:5, 1.0 mL/min) = 22.2 min
+
67.6; EI-MS m/z (rel intensity) 224 (M , 58); HPLC (Daicel CHIRAL-
Ò
Ò
CEL OD-H, 0.46 / Â 25 cm, UV 254 nm, hexane/2-propanol = 95:5,
t
R
0
.5 mL/min) t
R
= 23.9 min (major) and 25.7 min (minor).
(
major) and 27.4 min (minor).
4
.2.2. (S)-4-(4-Methylphenyl)chroman-2-one3b(Table1, entry11)
4
1
.2.7. (S)-4-(2-Methylphenyl)chroman-2-one 3g (Table 1, entry
20
7
D
5% yield (71.5 mg, 0.300 mmol), 98% ee; [a] = +45.5 (c 0.45,
8)
6
2
0
7
2
0
CHCl
3
) {lit. [
a]
D
= À41.4 (c 0.99, CHCl
3
) for 99% ee (R)}; white
, 300 MHz) d 2.34 (s, 3H),
.01–3.05 (m, 2H), 4.31 (t, J = 7.1 Hz, 1H), 6.96–7.17 (m, 7H),
D
8% yield (64.8 mg, 0.272 mmol), 99% ee; [a] = +75.5 (c 0.35,
1
2
0
4
solid; mp 70–71 °C; H NMR (CDCl
3
CHCl
3
) {lit. [
a]
D
= À62.9 (c 0.97, CHCl
3
) (for 97% ee (R)}; white
, 300 MHz) d 2.41 (s, 3H),
.92–3.07 (m, 2H), 4.59 (t, J = 7.5 Hz, 1H), 6.83–6.93 (m, 2H),
.04–7.33 (m, 6H); C NMR (CDCl , 75 MHz) d 19.5, 35.9, 36.5,
3
17.0, 124.7, 125.8, 126.8, 126.9, 127.5, 128.0, 128.7, 131.0,
1
3
7
1
1
solid; mp 112–113 °C; H NMR (CDCl
3
.26–7.32 (m, 1H); 1 C NMR (CDCl
3
3
, 75 MHz) d 21.0, 37.1, 40.3,
2
7
1
1
1
1
3
17.1, 124.6, 126.0, 127.4, 128.3, 128.7, 129.8, 137.2, 137.4,
51.7, 167.8; EI-MS m/z (rel intensity) 238 (M , 80); HRMS (ESI-or-
+
+
bitrap) m/z calcd for C16
14
H O
2
+H 239.1067 found 239.1065; HPLC
Daicel CHIRALCEL OD-H, 0.46 / Â 25 cm, UV 254 nm, hex-
ane/2-propanol = 95:5, 1.0 mL/min) = 14.4 min (major) and
35.9, 137.9, 152.0, 167.9; EI-MS m/z (rel intensity) 238 (M ,
00); HRMS (ESI-orbitrap) m/z calcd for C16H O +H 239.1067
14 2
Ò
(
Ò
t
R
found 239.1067; HPLC (Daicel CHIRALCEL OD-H, 0.46 / Â 25 cm,
1
6.4 min (minor).
UV 254 nm, hexane/2-propanol = 95:5, 1.0 mL/min) t = 14.8 min
R
(
major) and 16.9 min (minor).
4
.2.3. (S)-4-(4-Methoxyphenyl)chroman-2-one 3c (Table 1, entry 12)
20
.2.8. (S)-6-Methyl-4-phenylchroman-2-one 3h14 (Table 1, entry 20)
6
D
6% yield (67.1 mg, 0.264 mmol), 95% ee; [a] = +35.7 (c 0.51,
4
2
0
4
2
0
CHCl
solid; mp 161–162 °C; H NMR (CDCl
H), 3.80 (s, 3H), 4.31 (t, J = 7.5 Hz, 1H), 6.87–6.91 (m, 2H), 6.98
3
) {lit. [
a
]
D
= À30.5 (c 0.96, CHCl
3
) (for 93% ee (R)}; white
7
5% yield (35.9 mg, 0.151 mmol), 96% ee; [
a
]
D
= +3.5 (c 0.51,
) for 97% ee (S)}; white solid;
, 300 MHz) d 2.26 (s, 3H), 2.95–
.10 (m, 2H), 4.30 (t, J = 6.8 Hz, 1H), 6.78 (s, 1H), 7.01–7.16 (m,
1
2
0
3
, 300 MHz) d 2.95–3.10 (m,
CHCl
3
D 3
) {lit. [a] = +6 (c 1.00, CHCl
1
2
mp 107–109 °C; H NMR (CDCl
3
1
3
(
d, J = 7.4 Hz, 1H), 7.06–7.14 (m, 4H), 7.26–7.32 (m, 1H);
C
3
4
4
1
1
3
3
NMR (CDCl , 75 MHz) d 37.2, 39.9, 55.3, 114.4, 117.1, 124.6,
3
H), 7.26–7.37 (m, 3H); C NMR (CDCl , 75 MHz) d 20.7, 37.1,
1
26.2, 128.3, 128.6, 128.7, 132.1, 151.6, 159.0, 167.8; EI-MS m/z
0.7, 116.8, 125.3, 127.5, 127.6, 128.6, 129.1, 129.3, 134.3, 140.5,
+
+
(
rel intensity) 254 (M , 100); HRMS (ESI-orbitrap) m/z calcd for
49.6, 167.8; EI-MS m/z (rel intensity) 238 (M , 54); HPLC (Daicel
+H 255.1016 found 255.1019; HPLC (Daicel CHIRALCELÒ
Ò
16 14 3
C H O
CHIRALCEL OD-H, 0.46 / Â 25 cm, UV 254 nm, hexane/2-propa-
OD-H, 0.46 / Â 25 cm, UV 254 nm, hexane/2-propanol = 95:5,
nol = 95:5, 1.0 mL/min)
R
t = 11.2 min (major) and 12.4 min
1
.0 mL/min) t
R
= 16.4 min (major) and 17.9 min (minor).
(
minor).
4
.2.4. (S)-4-(3-Methylphenyl)chroman-2-one3d(Table1, entry 15)
4
.2.9. (R)-6-Methyl-4-phenylchroman-2-one ent-3h9 (Table 1,
20
8
D
5% yield (81.0 mg, 0.340 mmol), 95% ee; [a] = +41.5 (c 0.50,
entry 21)
2
0
7
2
0
CHCl
solid; mp 91–92 °C; H NMR (CDCl
.02–3.06 (m, 2H), 4.30 (t, J = 7.1 Hz, 1H), 6.94–6.99 (m, 3H),
3
) {lit. [
a]
D
= À44.6 (c 0.98, CHCl
3
) (for 99% ee (R)}; white
7
1% yield (33.6 mg, 0.141 mmol), 98% ee; [
a
]
D
= À2.4 (c 0.59,
) for 99% ee (R)}; white
3
, 300 MHz) d 2.26 (s, 3H),
1
2
0
3
, 300 MHz) d 2.33 (s, 3H),
CHCl
3
) {lit. [
a
]
D
= À3.6 (c 1.0, CHCl
3
1
3
solid; mp 108–109 °C; H NMR (CDCl