The Journal of Organic Chemistry
Article
(2S,3R)-2-Benzyl-4-nitro-3-(1-tosyl-1H-indol-3-yl)butanal (11c).
1H), 7.50 (d, J = 6.9 Hz, 2H), 7.46−7.35 (m, 5H), 7.28 (m, 2H), 7.22
(m, 2H), 7.06 (dd, J = 8.5, 6.9 Hz, 2H), 5.46 (s, 2H), 4.94−4.73 (m,
2H), 4.22−4.05 (m, 1H), 3.35−3.19 (m, 1H), 3.01−2.80 (m, 2H);
13C{1H} NMR (151 MHz, CDCl3): δ 202.7, 150.4, 139.2, 137.1,
134.8, 129.1, 129.0, 128.9, 128.9, 128.8, 128.8, 128.8, 128.7, 128.5,
127.1, 125.5, 125.1, 124.0, 123.4, 118.6, 115.8, 76.6, 69.1, 54.4, 34.7,
34.2, 33.5; 13C NMR (151 MHz, CDCl3, minor diastereomer): δ 202.8,
139.2, 137.1, 134.9, 129.1, 129.0, 128.9, 128.8, 128.7, 128.7, 128.6,
128.6, 128.6, 128.6, 128.5, 127.0, 125.5, 125.2, 123.4, 118.8, 115.8,
76.7, 68.9, 53.7, 34.8; IR (ATR) ν: 3482, 3028, 2925, 2743, 1724,
1604, 1549, 1496, 1453, 1396, 1356, 1307, 1245, 1217, 1075, 1028,
944, 744, 696, 629, 578, 494, 424 cm−1; HRMS (HESI) m/z: [M −
H]− calcd for C27H23N2O5, 455.1612; found, 455.1621; HPLC:
CHIRALCEL IC, hexane/iPrOH 80:20, 0.95 mL/min, λ = 220 nm,
tR1(maj) = 59.48, 62.95; tR2(min) = 24.46, 38.96 min.
(2S,3S)-2-Benzyl-3-ferrocenyl-4nitrobutanal (11h). Pale yellow oil
(36 mg, 52%). [α]2D0 +15.7 (c 1, CHCl3); 1H NMR (600 MHz,
CDCl3) δ 9.60 (s, 1H), 9.43 (d, J = 1.8, CHOminor diastereomer),
7.28−7.26 (m, 1H), 7.25−7.16 (m, 2H), 7.13−7.05 (m, 2H), 4.99
(m, 1H), 4.72 (m, 1H), 4.25−4.15 (m, 2H), 4.12 (s, 4H), 4.02 (dt, J
= 2.6, 1.4 Hz, 1H), 3.97 (ddd, J = 8.5, 5.1, 3.0 Hz, 1H), 3.87 (m, 1H),
3.06−2.84 (m, 2H), 2.81−2.53 (m, 2H); 13C{1H} NMR (151 MHz,
CDCl3): δ 202.3, 138.2, 128.9, 128.8, 128.7, 126.7, 85.3, 77.7, 69.0,
68.4, 68.3, 68.1, 66.3, 55.8, 37.8, 31.4; 13C NMR (151 MHz, CDCl3,
minor diastereomer): δ 203.2, 137.8, 84.9, 77.4, 69.0, 68.8, 68.4, 68.1,
66.5, 54.7, 38.7, 32.9; IR (ATR) ν: 3086, 3026, 2921, 2848, 2728,
2371, 2203, 2115, 1719, 1602, 1546, 1496, 1454, 1430, 1376, 1320,
1215, 1184, 1105, 1029, 1000, 911, 817, 737, 698, 598, 479 cm−1;
HRMS (HESI) m/z: [M − H]− calcd for C21H20FeNO3, 390.0798;
found, 390.0797; HPLC: CHIRALCEL IC, hexane/iPrOH 91:9, 0.9
mL/min, λ = 216 nm, tR1(maj) = 29.16, 32.07; tR2(min) = 34.02, 40.20
min.
Pale yellow oil (44 mg, 79%). [α]2D5 −5.26 (c 1, CHCl3) H NMR
1
(600 MHz, CDCl3): δ 9.72 (d, J = 1.6 Hz, 1H), 9.63 (d, J = 1.6 Hz,
CHOminor diastereomer), 7.98 (m, 1H), 7.69 (t, J = 8.4 Hz, 2H),
7.52 (d, J = 22.0 Hz, 1H), 7.39−7.27 (m, 3H), 7.25−7.18 (m, 5H),
7.04−6.97 (m, 2H), 4.90−4.69 (m, 2H), 4.19−4.00 (m, 1H), 3.31−
3.12 (m, 1H), 3.01−2.75 (m, 2H), 2.32 (s,, 3H), 2.30 (s, CH3minor
diastereomer). 13C{1H} NMR (151 MHz, CDCl3): δ 202.5, 145.3,
137.0, 135.3, 134.6, 130.0, 129.1, 128.9, 128.8, 127.1, 126.7, 125.5,
124.9, 123.7, 119.0, 118.4, 114.2, 76.7, 54.3, 34.6, 34.1, 21.5; 13C
NMR (151 MHz, CDCl3, minor diastereomer): δ 202.5, 136.8, 135.1,
134.6, 129.6, 127.1, 126.8, 125.5, 125.1, 123.7, 119.1, 117.9, 114.0,
76.7, 53.8, 34.8, 33.3, 21.6. Spectral data agree with those in the
literature.57 HPLC: CHIRALCEL IC, hexane/iPrOH 70:30, 0.9 mL/
min, λ = 254 nm, tR1(maj) = 54.33, 70.57; tR2(min) = 37.74, 57.94 min.
(2S,3R)-3-(Benzo[d][1,3]dioxol-5-yl)-2-benzyl-4-nitrobutanal
(11d). Pale yellow oil (64 mg, 94%). [α]2D0 −3.96 (c 1, CHCl3); H
1
NMR (600 MHz, CDCl3) δ 9.70 (d, J = 2.1 Hz, 1H), 9.55 (d, J = 2.0
Hz, CHOminor diastereomer), 7.33−7.26 (m, 2H), 7.25−7.02 (m,
3H), 6.78 (dd, J = 17.4, 7.9 Hz, 1H), 6.69−6.60 (m, 2H), 6.00−5.96
(m, 2H), 4.84−4.60 (m, 2H), 3.74 (td, J = 9.5, 5.0 Hz, 1H), 3.07−
2.84 (m, 2H), 2.80−2.77 (m, 1H); 13C{1H} NMR (151 MHz,
CDCl3): δ 203.0, 148.4, 147.6, 137.1, 130.2, 128.9, 128.8, 128.5,
128.4, 127.0, 121.7, 108.8, 108.0, 101.4, 78.2, 55.4, 43.3, 34.3; 13C
NMR (151 MHz, CDCl3, minor diastereomer): δ 203.1, 137.2, 129.3,
128.9, 128.8, 128.6, 128.4, 128.4, 127.1, 122.0, 108.7, 108.6, 78.0,
54.4, 44.3, 33.8; IR (ATR) ν: 2901, 2733, 2121, 1718, 1604, 1549,
1488, 1443, 1377, 1246, 1105, 1037, 933, 905, 863, 813, 750, 700,
653 cm−1; HRMS (HESI) m/z: [M − H]− calcd for C18H16NO5,
326.1034; found, 326.1040; HPLC: CHIRALCEL IC, hexane/iPrOH
85:15, 1 mL/min, λ = 216 nm, tR1(maj) = 25.44, 33.498; tR2(min)
=
30.68, 39.49 min.
(2S,3S)-2-Benzyl-4-nitro-3-(thiophen-2-yl)butanal (11e). Pale
(2S,3R)-2-Benzyl-3-(naphthalen-1-yl)-4-nitrobutanal (11i). Pale
yellow oil (71 mg, 95%). [α]2D0 +1.56 (c 0.25, CHCl3); H NMR
1
1
yellow oil (62 mg, 67%). [α]2D0 −9.87 (c 1, CHCl3); H NMR (600
(600 MHz, CDCl3): δ 9.70 (d, J = 1.7 Hz, 1H), 9.67 (d, J = 1.6 Hz,
CHOminor diastereomer), 7.34−7.25 (m, 3H), 7.23 (m, 1H), 7.13
(dd, J = 34.8, 7.1 Hz, 2H), 6.98 (m, 1H), 6.94−6.88 (m, 1H), 4.88−
4.65 (m, 2H), 4.22 (td, J = 8.3, 5.8 Hz, 1H), 4.22−4.10 (m, 1H),
3.14−3.02 (m, 1H), 2.88 (m, 1H); 13C{1H} NMR (151 MHz,
CDCl3): δ 202.3, 139.3, 137.9, 137.1, 129.0, 128.9, 128.8, 127.6,
127.2, 127.1, 125.6, 78.3, 55.9, 39.0, 33.9; 13C NMR (151 MHz,
CDCl3, minor diastereomer): δ 202.6, 139.3, 137.1, 128.9, 127.2, 127.1,
125.8, 78.4, 54.5, 39.4, 33.5; IR (ATR) ν: 2920, 2837, 2737, 1719,
1548, 1496, 1454, 1430, 1376, 1251, 1201, 1079, 1030, 913, 850, 747,
697, 520, 486 cm−1; HRMS (HESI) m/z: [M − H]− calcd for
C15H14NO3S, 288.0700; found, 288.0705; HPLC: CHIRALCEL IC,
hexane/iPrOH 90:10, 1 mL/min, λ = 216 nm, tR1(maj) = 26.74, 39.24;
tR2(min) = 20.97, 33.12 min.
(2S,3S)-2-Benzyl-3-(5-(3,4-dichlorophenyl)furan-2-yl)-4-nitrobu-
tanal (11f). Pale yellow oil (56 mg, 95%). [α]2D0 −13.7 (c 1, CHCl3);
1H NMR (600 MHz, CDCl3): δ 9.79 (d, J = 1.3 Hz, 1H), 9.77 (d, J =
1.7 Hz, CHOminor diastereomer), 7.65 (dd, J = 8.2, 2.0 Hz, 1H),
7.47−7.38 (m, 2H), 7.31 (m, 3H), 7.18−7.10 (m, 2H), 6.61 (dd, J =
8.8, 3.4 Hz, 1H), 6.32 (dd, J = 7.3, 3.4 Hz, 1H), 4.86−4.61 (m, 2H),
4.17−3.98 (m, 1H), 3.28−3.09 (m, 1H), 3.01−2.77 (m, 2H);
13C{1H} NMR (151 MHz, CDCl3): δ 201.5, 151.9, 150.5, 149.9,
137.0, 133.0, 131.5, 130.8, 130.0, 129.0, 128.8, 128.3, 127.1, 125.4,
122.9, 111.8, 107.2, 75.7, 53.8, 37.7, 33.4; 13C NMR (151 MHz,
CDCl3, minor diastereomer): δ 201.8, 151.9, 150.5, 149.9, 137.0, 133.1,
131.4, 130.8, 130.0, 128.8, 128.4, 127.2, 125.4, 122.9,111.3, 107.3,
75.8, 53.2, 37.3, 33.4; IR (ATR) ν: 2922, 2852, 2731, 1719, 1603,
1550, 1496, 1465, 1437, 1376, 1340, 1278, 1180, 1135, 1066, 1027,
939, 877, 820, 789, 741, 698, 550, 486, 436 cm−1; HRMS (HESI) m/
z: [M − H]− calcd for C21H16Cl2NO4, 416.0462; found, 416.0461;
HPLC: CHIRALCEL IC, hexane/iPrOH 85:15, 1 mL/min, λ = 212
nm, tR1(maj) = 21.47, 23.56; tR2(min) = 18.54, 26.44 min.
Benzyl 3-((2R,3S)-3-Benzyl-1-nitro-4-oxobutan-2-yl)-1H-indole-
1-carboxylate (11g). Pale yellow oil (35 mg, 62%). [α]2D0 −3.11 (c
1, CHCl3); 1H NMR (600 MHz, CDCl3): δ 9.73 (d, J = 1.8 Hz, 1H),
9.67 (d, J = 1.6 Hz, CHOminor diastereomer), 8.19 (s, 1H), 7.54 (m,
MHz, CDCl3): δ 9.78 (d, J = 2.0, 1H), 9.62 (s, CHOminor
diastereomer), (m, 1H), 8.07−7.86 (m, 1H), 7.81 (t, J = 8.8 Hz, 1H),
7.53−7.44 (m, 3H), 7.30 (d, J = 7.8 Hz, 1H), 7.22−7.18 (m, 4H),
7.05−6.99 (m, 1H), 5.22−5.17 (m, 1H), 5.06−4.98 (m, 1H), 4.96−
4.83 (m, 1H), 3.03−2.65 (m, 4H); 13C{1H} NMR (151 MHz,
CDCl3): δ 203.2, 142.2, 140.2, 137.2, 134.3, 129.5, 129.2, 128.9,
128.9, 128.8, 128.6, 128.5, 128.5, 127.1, 126.9, 126.2, 126.1, 125.4,
122.3, 73.3, 54.9, 45.0, 34.2; 13C NMR (151 MHz, CDCl3, minor
diastereomer): δ 201.6, 141.9, 140.3, 137.4, 134.3, 129.4, 129.1, 128.5,
128.4, 127.1, 127.0, 126.3, 126.2, 125.2, 122.2, 74.4, 56.1, 45.3, 34.6;
IR (ATR) ν: 3059, 3025, 2926, 2856, 2737, 1718, 1600, 1550, 1494,
1452, 1376, 1340, 1132, 1046, 966, 950, 910, 867, 798, 778, 734, 698,
616, 530, 495, 430 cm−1; HRMS (HESI) m/z: [M + H]+ calcd for
C21H20NO3, 334.1438; found, 334.1438; HPLC: CHIRALCEL IC,
hexane/iPrOH 90:10, 1 mL/min, λ = 218 nm, tR1(maj) = 42.58, 54.85;
tR2(min) = 39.24, 22.42 min.
(2S,3S)-2-Benzyl-3-(furan-2-yl)-4-nitrobutanal (11j). Pale yellow
oil (68 mg, 98%). 1H NMR (600 MHz, CDCl3): δ 9.71 (d, J = 1.4 Hz,
1H), 9.69 (d, J = 2.0 Hz, CHOminor diastereomer), 7.40 (d, J = 1.8
Hz, 1H), 7.35−7.18 (m, 2H), 7.17−7.12 (m, 1H), 7.12 (d, J = 7.1 Hz,
2H), 6.35 (m, 1H), 6.23 (m, 1H), 4.79−4.66 (m, 2H), 4.08−3.95 (m,
1H), 3.17−2.97 (m, 1H), 3.05−2.88 (m, 1H), 2.84−2.73 (m, 2H).
13C{1H} NMR (151 MHz, CDCl3): δ 202.0, 149.9, 142.8, 137.2,
129.2, 128.9, 128.9, 128.9, 127.0, 110.6, 109.1, 75.8, 53.8, 37.7, 33.4;
13C NMR (151 MHz, CDCl3, minor diastereomer): δ 202.2, 149.3,
142.9, 137.2, 128.5, 128.5, 128.4, 128.4, 127.1, 110.7, 109.5, 75.9,
53,4, 37.2, 33.3; spectral data agree with those in the literature.76
HPLC: CHIRALCEL AS-H, hexane/iPrOH 90:10, 0.7 mL/min, λ =
220 nm, tR1 = 24.41, tR2 = 26.52.
(2S,3R)-3-(Benzo[d][1,3]dioxol-5-yl)-2-methyl-4-nitrobutanal
(12a). Pale yellow oil (46 mg, 88%). [α]2D0 +1.17 (c 1, CHCl3); H
1
NMR (600 MHz, CDCl3): δ 9.70 (d, J = 1.8 Hz, 1H), 9.53 (d, J = 1.8
Hz, CHOminor diastereomer), 6.75 (dd, J = 7.9, 3.9 Hz, 1H), 6.69−
6.60 (m, 2H), 5.96−5.94 (m, 2H), 4.77−4.57 (m, 2H), 3.72 (td, J =
9.3, 5.2 Hz, 1H), 2.79−2.67 (m, 1H), 1.20 (d, J = 7.3 Hz, CH3
minor diastereomer), 1.02 (d, J = 7.3 Hz, 3H); 13C{1H} NMR (151
H
J. Org. Chem. XXXX, XXX, XXX−XXX