The Journal of Organic Chemistry
Note
aqueous K3PO4 (67 μL, 1.5 M). After being stirred at 40 °C for 3−5 h,
the mixture was concentrated under reduced pressure. The residue was
purified by silica gel column chromatography to afford the
corresponding addition product 2.
= 14.8 min; 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.7 Hz, 1H),
7.56 (td, J = 7.6, 1.2 Hz, 1H), 7.40 (dd, J = 10.8, 4.1 Hz, 1H), 7.36−
7.24 (m, 3H), 7.10−7.00 (m, 2H), 4.55 (dd, J = 8.0, 3.8 Hz, 1H), 3.21
(dd, J = 19.2, 8.0 Hz, 1H), 2.69 (dd, J = 19.2, 3.9 Hz, 1H), 1.30 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 206.2, 158.1, 149.8, 140.5,
136.7, 135.0, 127.7, 127.2, 126.9, 125.7, 123.3, 46.8, 43.9, 34.4, 31.3; IR
(KBr) ν 3042, 2962, 2926, 2854, 1703, 1603, 1514, 1464, 1389, 759
cm−1; HRMS (EI) for C19H20O [M]+ calcd 264.1514, found 264.1514.
(3S)-(4-Phenylphenyl)indan-1-one (2h): white solid (52.3 mg,
92%); mp 160 °C; [α]D = +76.9 (c 0.5, CHCl3); 95% ee, determined
by HPLC analysis: chiral AD-H column (hexane/2-propanol =97/3,
0.7 mL/min, 214 nm), t(minor) = 19.9 min, t(major) = 21.9 min; 1H
NMR (300 MHz, CDCl3) δ 7.83 (d, J = 7.6 Hz, 1H), 7.62−7.49 (m,
5H), 7.47−7.37 (m, 3H), 7.37−7.27 (m, 2H), 7.19 (d, J = 8.0 Hz,
2H), 4.62 (dd, J = 7.9, 3.6 Hz, 1H), 3.26 (dd, J = 19.2, 8.0 Hz, 1H),
2.73 (dd, J = 19.2, 3.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 206.0,
157.9, 143.6, 136.7, 135.0, 128.8, 127.8, 127.6, 126.9, 126.8, 123.3,
46.8, 44.4; IR (KBr) ν 3020, 2991, 2896,1705, 1635, 1608, 1521, 1464,
752 cm−1; HRMS (EI) for C21H16O [M]+ calcd 284.1201, found
284.1193.
(3S)-(2-Naphthyl)indan-1-one (2i): white solid (49.0 mg, 95%);
mp 152−154 °C; [α]D = +143.2 (c 0.5, CHCl3); 94% ee, determined
by HPLC analysis: chiral AD-3 column (hexane/2-propanol =97/3,
0.6 mL/min, 254 nm), t(minor) = 23.1 min, t(major) = 24.4 min; 1H
NMR (400 MHz, CDCl3) δ 7.93−7.74 (m, 4H), 7.67 (d, J = 1.3 Hz,
1H), 7.56 (td, J = 7.7, 1.2 Hz, 1H), 7.51−7.39 (m, 3H), 7.28 (dd, J =
7.7, 0.8 Hz, 1H), 7.13 (dd, J = 8.5, 1.7 Hz, 1H), 4.73 (dd, J = 8.1, 3.9
Hz, 1H), 3.29 (dd, J = 19.3, 8.1 Hz, 1H), 2.78 (dd, J = 19.3, 3.9 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 206.0, 157.8, 140.8, 136.8,
135.1, 133.4, 132.4, 128.9, 127.9, 127.7, 127.6, 126.9, 126.4, 125.8,
125.4, 123.4, 46.7, 44.6; IR (KBr) ν 3053, 2922, 2854, 1703, 1662,
1602, 1508, 750 cm−1; HRMS (EI) for C19H14O [M]+ calcd 258.1045,
found 258.1045.
(3S)-Phenylindan-1-one (2a):3m white solid (34.2 mg, 82%); mp
82−84 °C; [α]D = +49.7 (c 0.5, CHCl3), 82% ee, determined by
HPLC analysis: chiral OD-H column (hexane/2-propanol = 97/3, 0.6
1
mL/min, 214 nm), t(major) = 18.2 min, t(minor) = 22.1 min; H
NMR (300 MHz, CDCl3) δ 7.81 (d, J = 7.7 Hz, 1H), 7.55 (td, J = 4.7,
2.3 Hz, 1H), 7.46−7.37 (m, 1H), 7.36−7.22 (m, 4H), 7.16−7.08 (m,
2H), 4.57 (dd, J = 8.0, 3.9 Hz, 1H), 3.21 (dd, J = 19.2, 8.0 Hz, 1H),
2.69 (dd, J = 19.2, 3.9 Hz, 1H).
(3S)-(4-Fluorophenyl)indan-1-one (2b): white solid (42 mg,
93%); mp 138−140 °C; [α]D = +34.6 (c 0.5, CHCl3); 88% ee,
determined by HPLC analysis: chiral OD-H column (hexane/2-
propanol = 97/3, 0.6 mL/min, 214 nm), t(major) = 18.0 min,
t(minor) = 21.0 min; 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 7.7
Hz, 1H), 7.59 (t, J = 7.5 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.26 (d, J =
7.9 Hz, 1H), 7.12−7.05 (m, 2H), 7.03−6.96 (m, 2H), 4.58 (dd, J =
8.0, 3.8 Hz, 1H), 3.23 (dd, J = 19.2, 8.1 Hz, 1H), 2.64 (dd, J = 19.2, 3.9
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 205.7, 161.7 (d, 1JCF = 246
Hz), 157.6, 139.4 (d, J = 3.2 Hz), 136.7, 129.1, 129.0, 128.0, 126.7,
2
123.4, 115.7 (d, JCF = 21 Hz), 46.9, 43.6; IR (KBr) ν 3062, 2925,
1703, 1601, 1508, 1462, 768 cm−1; HRMS (EI) for C15H11OF [M]+
calcd 226.0794, found 226.0799;
(3S)-(4-Chlorophenyl)indan-1-one (2c):3m white solid (46.1
mg, 95%); mp 58 °C; [α]D = +55.2 (c 0.5, CHCl3); 94% ee,
determined by HPLC analysis: chiral OD-H column (hexane/2-
propanol = 97/3, 0.6 mL/min, 214 nm), t(major) = 19.6 min,
t(minor) = 22.4 min; 1H NMR (300 MHz, CDCl3) δ 7.81 (dd, J = 7.7,
0.6 Hz, 1H), 7.63−7.54 (m, 1H), 7.50−7.39 (m, 1H), 7.33−7.20 (m,
3H), 7.15−7.00 (m, 2H), 4.56 (dd, J = 8.0, 3.8 Hz, 1H), 3.23 (dd, J =
19.2, 8.1 Hz, 1H), 2.63 (dd, J = 19.2, 3.9 Hz, 1H).
(3S)-(3,4-Dichlorophenyl)indan-1-one (2d):9 white solid (48.8
mg, 88%); mp 96−98 °C; [α]D = +58.0 (c 0.5, CHCl3); 91% ee,
determined by HPLC analysis: chiral OD-H column (hexane/2-
propanol = 97/3, 0.7 mL/min, 220 nm), t(major) = 21.1 min,
t(minor) = 24.4 min; 1H NMR (300 MHz, CDCl3) δ 7.82 (d, J = 7.6
Hz, 1H), 7.61 (t, J = 6 Hz, 1H), 7.46 (t, J = 6 Hz, 1H), 7.41−7.33 (m,
1H), 7.30−7.20 (m, 2H), 6.96 (dd, J = 8.3, 2.1 Hz, 1H), 4.55 (dd, J =
8.0, 3.7 Hz, 1H), 3.23 (dd, J = 19.2, 8.0 Hz, 1H), 2.62 (dd, J = 19.2, 3.7
Hz, 1H).
(3S)-(2-Methoxy)indan-1-one (2j): colorless oil (30.1 mg, 80%);
[α]D = +23.0 (c 0.5, CHCl3); 84% ee, determined by HPLC analysis:
chiral OJ-H column (hexane/2-propanol = 97/3, 0.6 mL/min, λ = 220
nm), t(major) = 32.4 min, t(minor) = 40.8 min; 1H NMR (300 MHz,
CDCl3) δ 7.80 (d, J = 7.6 Hz, 1H), 7.54 (t, J = 7.5 Hz, 1H), 7.39 (t, J =
7.5 Hz, 1H), 7.30 (d, J = 7.7 Hz, 1H), 7.26−7.17 (m, 1H), 6.95 (d, J =
7.3 Hz, 1H), 6.91−6.81 (m, 2H), 4.89 (dd, J = 8.1, 3.5 Hz, 1H), 3.74
(s, 3H), 3.17 (dd, J = 19.2, 8.1 Hz, 1H), 2.69 (dd, J = 19.2, 3.5 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 134.6, 128.3, 128.1, 127.4,
126.6, 123.2, 120.7, 110.8, 55.3, 45.1; IR (KBr) ν 3050, 2987, 2923,
2846, 1712, 1601, 1493, 1462, 756 cm−1; HRMS (EI) for C16H14O2
[M]+ calcd 238.0994, found 238.1003.
(3S)-(3-Methoxy)indan-1-one (2k): colorless oil (33.5 mg, 89%):
[α]D = +52.5 (c 0.5, CHCl3); 82% ee, determined by HPLC analysis:
chiral OD-H column (hexane/2-propanol =97/3, 0.6 mL/min, 214
nm), t(major) = 12.5 min, t(minor) = 19.9 min; 1H NMR (400 MHz,
CDCl3) δ 7.81 (d, J = 7.7 Hz, 1H), 7.57 (td, J = 7.6, 1.2 Hz, 1H), 7.42
(t, J = 7.5 Hz, 1H), 7.30 (dd, J = 7.7, 0.8 Hz, 1H), 7.26−7.20 (m, 1H),
6.79 (dd, J = 8.3, 2.5 Hz, 1H), 6.72 (d, J = 7.6 Hz, 1H), 6.67−6.63 (m,
1H), 4.55 (dd, J = 8.0, 3.8 Hz, 1H), 3.76 (s, 3H), 3.22 (dd, J = 19.2,
8.0 Hz, 1H), 2.70 (dd, J = 19.2, 3.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 206.0, 160.0, 157.7, 145.3, 136.7, 135.1, 129.9, 127.9, 126.9,
123.4, 120.0, 113.6, 111.9, 55.2, 46.7, 44.4; IR (KBr) ν 3381, 2954,
2924, 2852, 1714, 1600, 1585, 1464, 762 cm−1; HRMS (EI) for
C16H14O2 [M]+ calcd 238.0994, found 238.0994.
(3S)-(4-Trifluoromethylphenyl)indan-1-one (2e): colorless oil
(44.2 mg, 80%): [α]D = +44.9 (c = 0.5, CHCl3); 95% ee, determined
by HPLC analysis: chiral OD-H column (hexane/2-propanol = 97/3,
0.6 mL/min, 214 nm), t(major) = 18.5 min, t(minor) = 22.3 min; 1H
NMR (300 MHz, CDCl3) δ 7.84 (d, J = 7.6 Hz, 1H), 7.67−7.53 (m,
3H), 7.46 (t, J = 7.3 Hz, 1H), 7.30−7.20 (m, 3H), 4.65 (dd, J = 8.2, 4.5
Hz, 1H), 3.27 (dd, J = 19.2, 8.2 Hz, 1H), 2.67 (dd, J = 19.2 Hz, 4.5 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 205.2, 156.9, 147.7, 136.8,
2
3
135.3, 129.4 (q, JCF = 32.3 Hz), 128.3, 128.0, 126.7, 125.9 (q, JCF
=
4.0 Hz), 124.0 (q, 1JCF =272.7 Hz), 46.5, 44.2; IR (KBr) ν 3300, 2924,
1716, 1620, 1602, 1464, 1327, 762 cm−1; HRMS (EI) for C16H11OF3
[M]+ calcd 276.0762, found 276.0771.
(3S)-(4-Methylphenyl)indan-1-one (2f): colorless oil (40.0 mg,
90%): [α]D = +62.5 (c 0.5, CHCl3); 91% ee, determined by HPLC
analysis: chiral OD-3 column (hexane/2-propanol =99/1, 0.6 mL/min,
1
214 nm), t(major) = 23.6 min, t(minor) = 25.1 min; H NMR (400
(3S)-(4-Methoxy)indan-1-one (2l):3m white solid (34.6 mg,
92%); mp 108 °C; [α]D = +69.0 (c 0.5, CHCl3); 95% ee, determined
by HPLC analysis: chiral OJ-H column (hexane/2-propanol = 95/5,
1.0 mL/min, 220 nm), t(minor) = 22.7 min, t(major) = 33.1 min; 1H
NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.7 Hz, 1H), 7.57 (td, J = 7.6,
1.2 Hz, 1H), 7.46−7.36 (m, 1H), 7.31−7.24 (m, 1H), 7.14−7.00 (m,
2H), 6.92−6.79 (m, 2H), 4.53 (dd, J = 8.0, 3.9 Hz, 1H), 3.79 (s, 3H),
3.22 (dd, J = 19.2, 8.0 Hz, 1H), 2.65 (dd, J = 19.2, 3.9 Hz, 1H).
(3S)-(4-Chlorophenyl)-5-fluoroindan-1-one (2m): white solid
(46.8 mg, 90%); mp 118 °C; [α]D = +61.6 (c 0.5, CHCl3); 94% ee,
determined by HPLC analysis: chiral AD-3 column (hexane/2-
propanol = 97/3, 0.7 mL/min, λ = 220 nm), t(minor) = 15.8 min,
MHz, CDCl3) δ 7.80 (d, J = 7.7 Hz, 1H), 7.55 (td, J = 7.5, 1.2 Hz,
1H), 7.45−7.36 (m, 1H), 7.29−7.23 (m, 1H), 7.12 (d, J = 7.8 Hz,
2H), 7.01 (d, J = 8.1 Hz, 2H), 4.54 (dd, J = 8.0, 3.8 Hz, 1H), 3.21 (dd,
J = 19.2, 8.0 Hz, 1H), 2.67 (dd, J = 19.2, 3.9 Hz, 1H), 2.32 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 206.2, 158.1, 140.6, 136.6, 136.5,
135.0, 129.5, 127.7, 127.4, 126.8, 123.3, 46.7, 44.0, 21.0; IR (KBr) ν
3022, 2967, 2922, 2853, 1712, 1600, 1514, 1462, 760 cm−1; HRMS
(EI) for C16H14O [M]+ calcd 222.1045, found 222.1045.
(3S)-(4-tert-Butylphenyl)indan-1-one (2g): white solid (45.4
mg, 86%); mp 106−108 °C; [α]D = +54.2 (c 0.5, CHCl3); 89% ee,
determined by HPLC analysis: chiral OD-H column (hexane/2-
propanol =97/3, 0.6 mL/min, 214 nm), t(major) = 11.7 min, t(minor)
E
dx.doi.org/10.1021/jo302656s | J. Org. Chem. XXXX, XXX, XXX−XXX