8
Tetrahedron
ACCEPTED MANUSCRIPT
Hz, 1H), 2.32 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 21.56,
66:34 dr; HPLC [Chiralpak ODH, hexane/i-PrOH, 80:20, 1
29.70, 34.65, 57.92, 114.8, 117.7, 118.6, 126.7, 126.8, 128.5,
128.7, 128.9, 129.1, 129.9, 145.3, 193.4, 194.1; HRMS calcd. for
C32H25ClN2NaO6S [M+Na]+ 623.1020; found 623.1022.
mL/min, 254 nm, tR = 26.8 min (major), tR = 53.5 min (major),
tR = 41.1 min (minor) and tR = 64.7 min (minor)]; 1H NMR (500
MHz,CDCl3) δ 7.38-8.04 (m, 16H), 7.09-7.36 (m, 10H), 5.38-
5.46 (m, 2H), 4.66-4.96 (m, 6H), 2.34 (s, 3H), 2.31 (s, 3H), 2.26
(s, 3H), 1.94 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 21.54,
28.32, 29.69, 30.39, 30.65, 31.33, 34.13, 34.26, 62.72, 64.03,
113.7, 114.1, 117.6, 118.7, 118.9, 123.9, 124.7, 125.4, 125.6,
126.6, 126.7, 128.6, 129.1, 129.2, 129.8, 129.9, 134.4, 134.5,
135.9, 145.1, 169.2, 173.4, 200.7, 201.6; HRMS calcd. for
C22H22N2NaO6S [M+Na]+ 527.1523; found 527.1529.
(S)-2-(1-(5-Bromo-1-tosyl-1H-indol-3-yl)-2-nitroethyl)-1,3-
diphenylpropane-1,3-dione (3k): Brown semi-solid; 88% yield;
Rf (25% EtOAc/hexane) 0.49; [α]D20 = -66.94 (c 0.10, CHCl3);
84% ee; HPLC [Chiralpak IA, hexane/i-PrOH, 85:15, 1 mL/min,
254 nm, tR
=
19.4 min (major) and tR = 24.3 min (minor)];1H
NMR (500 MHz, CDCl3) δ 7.50-8.02 (m, 10H), 6.89-7.45 (m,
7H), 6.00 (d, J= 7.5 Hz, 1H), 4.98 (t, J= 5.0 Hz, 2H), 4.77 (d, J=
5.0 Hz, 1H), 2.32 (s, 3H);13C NMR
(S)-Ethyl 2-acetyl-4-nitro-3-(1-tosyl-1H-indol-3-yl)butanoate
(3p): Brown semi-solid; 89% yield; Rf (20% EtOAc/hexane)
0.44; [α]D20 = -28.97 (c 0.10, CHCl3); 90% ee; 62:38 dr; HPLC
[Chiralpak ADH, hexane/i-PrOH, 85:15, 1 mL/min, 254 nm, tR =
22.8 min (major), tR = 25.5 min (major)], tR = 35.9 min (minor),
tR = 39.8 min (minor); 1H NMR (500 MHz, CDCl3) δ 7.95-7.96
(m, 2H), 7.67-7.71 (m, 4H), 7.49-7.56 (m, 4H), 7.23-7.36 (m,
8H), 4.85-4.97 (m, 3H), 4.73-4.77 (m, 1H), 4.44-4.50 (m, 2H),
4.32 (d, J= 9.5 Hz, 1H), 4.18-4.25 (m, 3H), 3.95 (q, J= 7.0 Hz,
2H), 2.34 (s, 6H), 2.33 (s, 3H), 2.14 (s, 3H), 1.26 (t, J= 7.0 Hz,
3H), 0.95 (t, J= 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ
13.61, 13.88, 13.96, 19.47, 21.56, 30.15, 30.32, 33.31, 33.50,
33.65, 60.55, 60.76, 62.16, 62.33, 113.8, 113.9, 118.1, 118.2,
118.9, 119.0, 123.6, 123.7, 124.6, 124.7, 125.4, 125.5, 126.7,
126.8, 129.0, 129.2, 129.9, 130.0, 134.6, 134.7, 134.8, 135.0,
145.1, 145.2, 166.7, 167.4, 200.1, 201.1; HRMS calcd. for
C23H24N2NaO7S [M+Na]+ 495.1202; found 495.1205.
(125 MHz, CDCl3) δ 21.57, 29.70, 34.62, 57.92, 93.17, 115.2,
121.7, 126.6, 126.7, 127.2, 128.3, 128.5, 128.7, 128.8, 128.9,
129.1, 129.9, 132.5, 134.1, 134.3, 135.5, 145.4, 193.4, 194.1;
HRMS calcd. for C32H25BrN2NaO6S [M+Na]+ 667.0514; found
667.0517.
(S)-2-(1-(5-Iodo-1-tosyl-1H-indol-3-yl)-2-nitroethyl)-1,3-
diphenylpropane-1,3-dione (3l): Brown semi-solid; 87% yield;
Rf (25% EtOAc/hexane) 0.48; [α]D20 = -70.83 (c 0.10, CHCl3);
67% ee; HPLC [Chiralpak IA, hexane/i-PrOH, 85:15, 1 mL/min,
254 nm, tR
=
16.3 min (major) and tR = 33.4 min (minor)];1H
NMR (500 MHz, CDCl3) δ 7.50-8.03 (m, 7H), 7.13-7.45 (m,
11H), 5.98 (d, J= 8.0 Hz, 1H), 4.98 (t, J= 5.0 Hz, 2H), 4.73-4.77
(m, 1H), 2.32 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 21.56,
34.57, 57.96, 87.88, 93.17, 115.5, 117.3, 126.7, 127.2, 128.6,
128.7, 128.9, 129.1, 129.9, 145.3, 193.4, 194.1; HRMS calcd. for
C32H25IN2NaO6S [M+Na]+ 715.0376; found 715.0381.
(S)-Allyl 2-acetyl-4-nitro-3-(1-tosyl-1H-indol-3-yl)butanoate
(3q): Light brown semi-solid; 91% yield; Rf (20%
EtOAc/hexane) 0.46; [α]D20 = -22.98 (c 0.10, CHCl3); 92% ee;
56:44 dr; HPLC [Chiralpak ADH, hexane/i-PrOH, 85:15, 1
mL/min, 254 nm, tR = 23.8 min (major), tR = 26.2 min (major),
tR = 32.4 min (minor) and tR = 43.1 min (minor)]; 1H NMR (500
MHz, CDCl3) δ 7.91-7.96(m, 2H), 7.67-7.75 (m, 4H), 7.49-7.55
(m, 4H), 7.22-7.36 (m, 8H), 5.82-5.90 (m, 1H), 5.53-5.61 (m,
1H), 5.29-5.35 (m, 2H), 5.09-5.14 (m, 2H), 4.86-4.95 (m, 3H),
4.74-4.78 (m, 1H), 4.64-4.66 (m, 2H), 4.46-4.51 (m, 2H), 4.34-
4.38 (m, 3H), 4.22 (d, J=8.0 Hz, 1H), 2.34 (s, 3H), 2.33 (s, 3H),
2.14 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 21.56, 29.70, 30.26,
30.42, 33.35, 33.55, 60.45, 60.69, 66.62, 66.75, 113.8, 113.9,
118.0, 118.9, 119.0, 119.8, 120.0, 123.7, 123.8, 124.6, 124.7,
125.4, 125.5, 126.7, 126.8, 129.9, 130.4, 130.7, 145.1, 145.2,
166.5, 167.1, 190.9, 200.9; HRMS calcd. for C24H24N2NaO7S
[M+Na]+ 507.1202; found 507.1202.
(S)-2-(1-(5-Methoxy-1-tosyl-1H-indol-3-yl)-2-nitroethyl)-1,3-
diphenylpropane-1,3-dione (3m): Light brown semi-solid; 82%
20
yield; Rf (30% EtOAc/hexane) 0.51; [α]D
= -80.93 (c 0.10,
CHCl3); 69% ee; HPLC [Chiralpak IA, hexane/i-PrOH, 80:20, 1
mL/min, 254 nm, tR 22.7 min (major) and tR = 26.0 min
=
(minor)]; 1H NMR (500 MHz, CDCl3) δ 7.38-8.03 (m, 16H), 7.28
(s, 1H), 7.10 (d, J= 8.5 Hz, 1H), 6.04 (d, J= 5.0 Hz, 1H), 4.79-
5.03 (m, 3H), 3.83 (s, 3H), 2.30 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 21.54, 29.31, 34.73,55.71, 57.70, 101.1, 114.6, 114.7,
118.3, 126.6, 128.5, 128.7, 128.9, 129.0, 129.8, 134.6, 144.9,
156.7, 193.5, 194.3; HRMS calcd. for C33H28N2NaO7S [M+Na]+
619.1515; found 619.1513.
(S)-2-(1-(4-Bromo-1-tosyl-1H-indol-3-yl)-2-nitroethyl)-1,3-
diphenylpropane-1,3-dione (3n): Brown semi-solid; 88% yield;
Rf (25% EtOAc/hexane) 0.48; [α]D20 = -81.93 (c 0.10, CHCl3);
95% ee; HPLC [Chiralpak IA, hexane/i-PrOH, 85:15, 1 mL/min,
1
254 nm, tR = 19.9 min (minor) and tR = 24.6 min (major)]; H
(S)-3-(1-(3,5-Dimethyl-1H-pyrazol-4-yl)-2-nitroethyl)-1-tosyl-
NMR (500 MHz, CDCl3) δ 7.37-7.92 (m, 13H), 7.35 (s, 1H),
7.14-7.19 (m, 4H), 6.23 (d, J= 5.0 Hz, 1H), 5.73-5.77 (m, 1H),
5.30-5.34 (m, 1H), 4.82-4.87 (m, 1H), 2.33 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 21.59, 30.01, 33.98, 57.92, 113.1, 118.1,
118.4, 126.1, 126.8, 127.0, 128.4, 128.6, 128.8, 128.9, 129.0,
130.0, 132.6, 133.8, 134.0, 134.3, 135.8, 136.2, 139.8, 145.5,
193.7, 195.1; HRMS calcd. for C32H25BrN2NaO6S [M+Na]+
667.0514; found 667.0511.
1H-indole
(3r)
Brown semi-solid; 89% yield; Rf (35% EtOAc/hexane) 0.50;
20
[α]D = -44.67 (c 0.10, CHCl3); 92% ee; HPLC [Chiralpak IA,
hexane/i-PrOH, 70:30, 1 mL/min, 254 nm, tR = 8.51 min (minor)
and tR = 9.71 min (major)]; 1H NMR (500 MHz, CDCl3) δ 8.02 (d,
J= 10.0 Hz, 1H), 7.74 (d, J= 10.0 Hz, 2H), 7.16-7.39 (m, 6H),
5.00-5.11 (m, 1H), 4.97-4.99 (m, 1H), 4.80-4.96 (m, 1H), 2.36 (s,
3H), 2.12 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 11.36, 21.56,
29.33, 31.55, 36.93, 113.9, 119.6, 120.3, 122.4, 123.5, 125.4,
126.8, 129.4, 129.9, 134.8, 135.5, 145.2; HRMS calcd. for
C22H22N4NaO4S [M+Na]+ 461.1259; found 461.1262.
(S)-2-(2-Nitro-1-(1-tosyl-1H-indol-3-yl)ethyl)-1-phenylbutane-
1,3-dione (3o): Brown semi-solid; 90% yield; Rf (30%
EtOAc/hexane) 0.47; [α]D20 = -84.93 (c 0.10, CHCl3); 98% ee;