The Journal of Organic Chemistry
Article
7.8 Hz, 1 H), 7.14 (t, J = 7.8 Hz, 1 H), 6.62 (d, J = 1.2 Hz, 1 H), 6.07
(dd, J = 5.6, 2.8 Hz, 1 H), 5.83 (s, 1 H), 4.72 (dd, J = 7.5, 6.0 Hz, 1 H),
3.76 (dd, J = 17.7, 8.0 Hz, 1 H), 3.53 (dd, J = 17.7, 5.6 Hz, 1 H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ45.5, 136.7, 133.8, 133.6, 131.2,
130.3, 130.1, 128.8, 128.2, 126.9, 122.8, 117.6, 108.0, 105.7, 45.1, 39.1
ppm; IR (KBr pellet) 3382, 3098, 3059, 2900, 1682, 1595, 1579, 1473,
1448, 787, 757, 719, 691 cm−1; HRMS (ESI) m/z [M + H]+ calcd for
C19H16BrNO 354.0488, found 354.0491.
Hz, 1 H), 3.60 (dd, J = 17.7, 4.1 Hz, 1 H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ = 203.5, 143.6, 141.4, 138.7, 138.7, 138.0, 136.1,
133.6, 133.3, 132.8, 132.2, 131.1, 130.4, 130.1, 129.9, 128.1, 121.8,
112.5, 110.4, 49.5, 39.5 ppm; IR (KBr pellet) 3431, 3058, 2901, 1679,
1596, 1579, 1509, 1448, 760, 689 cm−1; HRMS (ESI) m/z [M + H]+
calcd for C23H19NO 326.1539, found 326.1543.
(S)-3-(2-Chlorophenyl)-1-(4-chlorophenyl)-3-(1H-pyrrol-2-
yl)propan-1-one (13q). Purified by flash chromatography with
petroleum ether/ethyl acetate (5/1) to afford the desired product as a
(S)-3-(2-Chlorophenyl)-1-phenyl-3-(1H-pyrrol-2-yl)propan-1-
one (13m). Purified by flash chromatography with petroleum ether/
ethyl acetate (5/1) to afford the desired product as colorless oil: 99%
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colorless oil: 99% yield (86 mg); 98% ee; [α]D = +15.2 (c 0.60,
CHCl3); the ee was determined by HPLC analysis using a chiral OD-
H column (i-PrOH/hexane = 10/90, flow rate = 1.0 mL min−1, λ =
254 nm), tR (major) = 12.950 min, tR (minor) = 16.192 min; 1H NMR
(400 MHz, CDCl3) δ = 8.31 (brs, 1 H), 7.82 (d, J = 8.5 Hz, 2 H),
7.41−7.29 (m, 3 H), 7.14 (m, 3 H), 6.58 (d, J = 1.3 Hz, 1 H), 6.02
(dd, J = 5.6, 2.8 Hz, 1 H), 5.80 (s, 1 H), 5.21 (dd, J = 9.0, 4.8 Hz, 1 H),
3.72 (dd, J = 17.5, 9.1 Hz, 1 H), 3.45 (dd, J = 17.5, 4.8 Hz, 1 H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ = 201.8, 145.1, 144.47, 139.6,
138.1, 137.4, 134.5, 134.2, 133.7, 133.6, 132.7, 131.8, 122.0, 112.6,
110.2, 48.4, 40.5 ppm; IR (KBr pellet) 3383, 3097, 3063, 2923, 1682,
1589, 1570, 1487, 1442, 830, 749, 722 cm−1; HRMS (ESI) m/z [M +
H]+ calcd for C19H15Cl2NO 344.0603, found 344.0602.
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yield (78 mg); 98% ee; [α]D = +12.7 (c 0.39, CHCl3); the ee was
determined by HPLC analysis using a chiral AD column (i-PrOH/
hexane = 10/90, flow rate = 1.0 mL min−1, λ = 254 nm), tR (minor) =
12.950 min, tR (major) = 24.842 min; 1H NMR (400 MHz, CDCl3) δ
= 8.49 (brs, 1 H), 8.03 (d, J = 7.5 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H),
7.51 (t, J = 7.7 Hz, 2 H), 7.45 (dd, J = 7.7, 1.0 Hz, 1 H), 7.34 (dd, J =
7.6, 1.5 Hz, 1 H), 7.28 (d, J = 6.6 Hz, 1 H), 7.23 (td, J = 7.5, 1.7 Hz, 1
H), 6.71 (d, J = 1.3 Hz, 1 H), 6.14 (dd, J = 5.6, 2.7 Hz, 1 H), 5.92 (s, 1
H), 5.37 (dd, J = 9.0, 4.7 Hz, 1 H), 3.89 (dd, J = 17.6, 9.0 Hz, 1 H),
3.63 (dd, J = 17.6, 4.7 Hz, 1 H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ = 203.0, 145.3, 141.3, 138.2, 138.0, 137.7, 134.5, 133.7,
133.3, 132.8, 132.6, 131.8, 121.9, 112.6, 110.2, 48.5, 40.4 ppm; IR
(KBr pellet) 3382, 3098, 3062, 2900, 1674, 1595, 1571, 1448, 767,
760, 716, 687 cm−1; HRMS (ESI) m/z [M + H]+ calcd for
C19H16ClNO 310.0993, found 310.0997.
(S)-3-(3-Bromophenyl)-1-(4-fluorophenyl)-3-(1H-pyrrol-2-
yl)propan-1-one (13r). Purified by flash chromatography with
petroleum ether/ethyl acetate (5/1) to afford the desired product as
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a colorless oil: >99% yield (93 mg); 99% ee; [α]D = −3.4 (c 0.92,
CHCl3); the ee was determined by HPLC analysis using a chiral OD-
(S)-1-Phenyl-3-(1H-pyrrol-2-yl)-3-(p-tolyl)propan-1-one
(13n). Purified by flash chromatography with petroleum ether/ethyl
acetate (5/1) to afford the desired product as a white solid: mp 102−
H column (i-PrOH/hexane = 5/95, flow rate = 1.0 mL min−1, λ = 254
1
nm), tR (major) = 26.758 min, tR (minor) = 32.117 min; H NMR
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104 oC; 94% yield (68 mg); 98% ee; [α]D = −6.3 (c 0.60, CHCl3);
(400 MHz, CDCl3) δ = 8.34 (brs, 1 H), 8.00 (dd, J = 8.7, 5.4 Hz, 2
H), 7.47 (s, 1 H), 7.39 (d, J = 7.8 Hz, 1 H), 7.26 (d, J = 8.9 Hz, 1 H),
7.21 (d, J = 7.7 Hz, 1 H), 7.15 (dd, J = 16.1, 7.6 Hz, 2 H), 6.68 (d, J =
1.1 Hz, 1 H), 6.12 (dd, J = 5.5, 2.7 Hz, 1 H), 5.88 (s, 1 H), 4.76 (dd, J
= 7.3, 6.1 Hz, 1 H), 3.78 (dd, J = 17.6, 8.0 Hz, 1 H), 3.55 (dd, J = 17.6,
5.6 Hz, 1 H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ = 197.0,
167.2/164.7 (J = 253.8 Hz), 145.3, 133.6, 133.2/133.2 (J = 2.8 Hz),
131.1, 130.9/130.8 (J = 9.3 Hz), 130.3, 130.1, 126.8, 122.8, 117.6,
116.0/115.8 (J = 21.7 Hz), 115.8, 108.1, 105.8, 45.0, 39.1 ppm; IR
(KBr pellet) 3385, 3066, 2900, 1681, 1595, 1567, 1506, 1473, 839,
787, 719 cm−1; HRMS (ESI) m/z [M + Na]+ calcd for C19H15BrFNO
394.0213, found 394.0219.
(S)-3-(3-Bromophenyl)-1-(4-bromophenyl)-3-(1H-pyrrol-2-
yl)propan-1-one (13s). Purified by flash chromatography with
petroleum ether/ethyl acetate (5/1) to afford the desired product as a
pale yellow oil: >99% yield (109 mg); 99% ee; [α]D20 = −2.0 (c 1.08,
CHCl3); the ee was determined by HPLC analysis using a chiral OD-
H column (i-PrOH/hexane = 10/90, flow rate = 1.0 mL min−1, λ =
254 nm), tR (major) = 19.275 min, tR (minor) = 24.292 min; 1H NMR
(400 MHz, CDCl3) δ = 8.27 (brs, 1 H), 7.82−7.73 (m, 2 H), 7.61−
7.51 (m, 2 H), 7.42 (s, 1 H), 7.34 (d, J = 7.7 Hz, 1 H), 7.23−7.18 (m,
1 H), 7.15 (t, J = 7.6 Hz, 1 H), 6.63 (s, 1 H), 6.07 (d, J = 2.5 Hz, 1 H),
5.84 (s, 1 H), 4.76−4.65 (m, 1 H), 3.72 (dd, J = 17.6, 7.9 Hz, 1 H),
3.48 (dd, J = 17.6, 5.6 Hz, 1 H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ = 202.1, 149.9, 140.0, 138.0, 136.6, 135.7, 134.9, 134.7,
134.2, 133.3, 131.4, 127.4, 122.2, 112.7, 110.3, 49.5, 43.6 ppm; IR
(KBr pellet) 3385, 3095, 3059, 2899, 1681, 1585, 1567, 1473, 1427,
827, 786, 719 cm−1; HRMS (ESI) m/z [M + H]+ calcd for
C19H15Br2NO 431.9593, found 431.9600.
the ee was determined by HPLC analysis using a chiral OD-H column
(i-PrOH/hexane = 5/95, flow rate = 1.0 mL min−1, λ = 254 nm), tR
(major) = 13.789 min, tR (minor) = 15.933 min; 1H NMR (400 MHz,
CDCl3) δ = 8.35 (brs, 1 H), 8.01 (d, J = 7.8 Hz, 2 H), 7.61 (t, J = 7.3
Hz, 1 H), 7.50 (t, J = 7.6 Hz, 2 H), 7.26 (d, J = 7.8 Hz, 2 H), 7.19 (d, J
= 7.8 Hz, 2 H), 6.69 (s, 1 H), 6.16 (d, J = 2.7 Hz, 1 H), 5.94 (s, 1 H),
4.81 (t, J = 6.8 Hz, 1 H), 3.85 (dd, J = 17.5, 7.9 Hz, 1 H), 3.64 (dd, J =
17.5, 5.8 Hz, 1 H), 2.39 (s, 3 H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ = 199.2, 140.1, 137.0, 136.5, 134.9, 133.4, 129.5, 128.7,
128.2, 128.1, 117.2, 107.9, 105.4, 45.4, 39.0, 21.2 ppm; IR (KBr pellet)
3377, 3007, 2969, 2895, 1667, 1595, 1579, 1515, 1451, 819, 749, 713
cm−1.
(S)-1-Phenyl-3-(1H-pyrrol-2-yl)-3-(m-tolyl)propan-1-one
(13o). Purified by flash chromatography with petroleum ether/ethyl
acetate (5/1) to afford the desired product as a colorless oil: 67% yield
(48 mg); 98% ee; the ee was determined by HPLC analysis using a
chiral OD-H column (i-PrOH/hexane = 10/90, flow rate = 1.0 mL
min−1, λ = 254 nm), tR (major) = 9.925 min, tR (minor) = 11.592 min;
1H NMR (400 MHz, CDCl3) δ = 8.37 (brs, 1 H), 8.03 (d, J = 7.5 Hz,
2 H), 7.63 (t, J = 7.4 Hz, 1 H), 7.52 (t, J = 7.7 Hz, 2 H), 7.29 (t, J = 7.4
Hz, 1 H), 7.19 (d, J = 7.6 Hz, 2 H), 7.13 (d, J = 7.3 Hz, 1 H), 6.71 (d, J
= 1.4 Hz, 1 H), 6.17 (d, J = 2.7 Hz, 1 H), 5.94 (s, 1 H), 4.83 (dd, J =
7.5, 6.1 Hz, 1 H), 3.88 (dd, J = 17.5, 8.1 Hz, 1 H), 3.66 (dd, J = 17.5,
5.6 Hz, 1 H), 2.40 (s, 3 H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
= 3.0, 138.3, 137.0, 134.7, 133.3, 128.9, 128.7, 128.6, 128.2, 127.7,
125.1, 117.2, 107.9, 105.4, 45.3, 39.3, 21.6 ppm; IR (KBr pellet) 3385,
3099, 3057, 3025, 2919, 1682, 1597, 1580, 1489, 1448, 787, 762, 717,
691 cm−1; HRMS (ESI) m/z [M + H]+ calcd for C20H19NO 290.1539,
found 290.1543.
(S)-3-(4-Chlorophenyl)-1-(4-fluorophenyl)-3-(1H-pyrrol-2-yl)-
propan-1-one (13t). Purified by flash chromatography with
petroleum ether/ethyl acetate (5/1) to afford the desired product as
(S)-3-(Naphthalen-2-yl)-1-phenyl-3-(1H-pyrrol-2-yl)propan-
1-one (13p). Purified by flash chromatography with petroleum ether/
ethyl acetate (5/1) to afford the desired product as a colorless oil: 94%
20
a colorless oil: >99% yield (82 mg); 99% ee; [α]D = −1.5 (c 0.81,
20
yield (76 mg); >99% ee; [α]D = −5.4 (c 0.73, CHCl3); the ee was
CHCl3); the ee was determined by HPLC analysis using a chiral AS
determined by HPLC analysis using a chiral OD-H column (i-PrOH/
hexane = 10/90, flow rate = 1.0 mL min−1, λ = 254 nm), tR (major) =
18.458 min, tR (minor) = 20.933 min; 1H NMR (400 MHz, CDCl3) δ
= 8.19 (brs, 1 H), 8.16−8.09 (m, 1 H), 7.92 (d, J = 8.0 Hz, 2 H), 7.83
(dd, J = 5.8, 3.5 Hz, 1 H), 7.72 (d, J = 7.7 Hz, 1 H), 7.50 (t, J = 7.3 Hz,
1 H), 7.46−7.31 (m, 6 H), 6.54 (s, 1 H), 6.03 (d, J = 2.5 Hz, 1 H),
5.83 (s, 1 H), 5.61 (dd, J = 9.0, 4.0 Hz, 1 H), 3.95 (dd, J = 17.7, 9.1
column (i-PrOH/hexane = 10/90, flow rate = 1.0 mL min−1, λ = 254
1
nm), tR (minor) = 14.800 min, tR (major) = 19.275 min; H NMR
(400 MHz, CDCl3) δ = 8.27 (brs, 1 H), 8.02−7.84 (m, 2 H), 7.22 (dd,
J = 20.3, 8.3 Hz, 4 H), 7.09 (t, J = 8.4 Hz, 2 H), 6.63 (s, 1 H), 6.07 (d,
J = 2.3 Hz, 1 H), 5.83 (s, 1H), 4.72 (t, J = 6.7 Hz, 1 H), 3.72 (dd, J =
17.5, 7.7 Hz, 1 H), 3.50 (dd, J = 17.4, 5.8 Hz, 1 H) ppm; 13C{1H}
NMR (100 MHz, CDCl3) δ = 197.1, 167.2/164.7 (J = 254.1 Hz),
H
dx.doi.org/10.1021/jo5023712 | J. Org. Chem. XXXX, XXX, XXX−XXX