370
M. J. García-Muñoz et al. / Tetrahedron: Asymmetry 25 (2014) 362–372
4.3.9. (R,RS)-N-(tert-Butylsulfinyl)-2-methyl-1-nitrobutan-2-
4H), 1.63 (d, J = 6.9 Hz, 3H), 1.47 (d, J = 6.9 Hz, 3H), 1.31 (s, 9H),
1.28 (s, 9H); dC 140.3 (C), 128.6, 128.6, 128.4, 128.3, 126.4, 126.3,
86.3 85.7, 59.4, 58.6 (CH), 56.7, 56.6 (C), 34.9, 31.9, 31.4 (CH2),
22.8, 22.7, 16.3, 15.3 (CH3); LRMS (EI) m/z 208 (M+ꢁC4H8SO,
0,6%), 206 (11), 145 (19), 144 (11), 133 (15), 132 (26), 117 (14),
115 (10), 105 (26), 104 (57), 103 (15), 91 (100), 77 (18), 65 (17),
57 (13), 56 (14); HRMS (ESI): Calculated for C15H25N2O3S (M++H)
313.1586, found 313.1584.
amine 3f
Yellow oil; ½a 2D3
¼ ꢁ89:0 (c 1.24, CH2Cl2); Rf 0.23 (hexane/
ꢀ
EtOAc: 1/1); IR
m
(KBr) 3208, 2977, 2873, 1547, 1458, 1374, 1248,
dH 4.69 (d, J = 12.1 Hz, 1H), 4.50 (d,
1051, 939, 735 cmꢁ1
;
J = 12.1 Hz, 1H), 4.23 (s, 1H), 1.76–1.62 (m, 1H), 1.44 (s, 3H), 1.25
(s, 9H), 0.96 (t, J = 7.4 Hz, 3H); dC 83.7 (CH2), 57.3, 56.1 (C), 31.9
(CH2), 22.62, 22.54, 7.67 (CH3); LRMS (EI) m/z 180 (M+ꢁC4H8,
6%), 119 (27), 118 (9), 69 (27), 57 (100), 55 (8); HRMS (ESI): Calcu-
lated for C9H21N2O3S (M++H) 237.1273, found 237.1262.
4.3.14. (2R⁄,3R,RS)-N-(tert-Butylsulfinyl)-5-methyl-2-nitrohexan-
3-amine 7h
4.3.10. (R,RS)-N-(tert-Butylsulfinyl)-2-methyl-1-nitroheptan-2-
Diastereomeric mixture (1:1), white solid, mp 74–76 °C (hex-
amine 3g
ane/CH2Cl2); Rf 0.27 and 0.29 (hexane/EtOAc: 1/1); IR
m (KBr)
Yellow oil; ½a 2D3
ꢀ
¼ ꢁ52:3 (c 1.28, CH2Cl2); Rf 0.33 (hexane/
3229, 2958, 2927, 2870, 1545, 1456, 1388, 1364, 1036, 899 cmꢁ1
;
EtOAc: 1/1); IR
m
(KBr) 3218, 2956, 2931, 2869, 1548, 1457,
dH 5.05 (qd, J = 6.8, 2.6 Hz, 1H), 4.84 (qd, J = 6.8, 4.5 Hz, 1H), 4.29
(d, J = 10.1 Hz, 1H), 3.91 (d, J = 9.6 Hz, 1H), 3.74–3.60 (m, 1H),
3.58–3.42 (m, 1H), 1.90–1.70 (m, 2H), 1.64 (d, J = 6.9 Hz, 3H),
1.55 (d, J = 6.9 Hz, 3H), 1.51–1.41 (m, 2H), 1.26 (s, 9H), 1.25 (s,
9H), 0.94 (d, J = 1.2 Hz, 3H), 1.02–0.95 (m, 2H), 0.92 (d, J = 1.2 Hz,
3H), 0.90 (d, J = 2.2 Hz, 3H), 0.88 (d, J = 2.2 Hz, 3H); dC 86.6, 85.9,
58.6, 57.5 (CH), 56.7, 56.5 (C), 41.6, 38.5 (CH2), 24.3, 24.2 (CH),
23.4, 23.2, 22.7, 22.7, 21.2, 21.0, 15.8, 15.3 (CH3); LRMS (EI) m/z
208 (M+ꢁC4H8, 5%), 160 (7), 133 (44), 97 (15), 57 (100), 56 (11),
1374, 1048, 940 cmꢁ1
; dH 4.67 (d, J = 12.1 Hz, 1H), 4.49 (d,
J = 12.0 Hz, 1H), 4.22 (s, 1H), 1.74–1.55 (m, 2H), 1.44 (s, 3H),
1.41–1.26 (m, 6H), 1.24 (s, 9H), 0.89 (t, J = 6.6 Hz, 3H); dC 83.9
(CH2), 57.2, 56.1 (C), 39.1, 31.8 (CH2), 23.2 (CH3), 22.9 (CH2), 22.6
(CH3), 22.4 (CH2), 13.9 (CH3); LRMS (EI) m/z 222 (M+ꢁC4H8, 1%),
178 (8), 151 (10), 135 (28), 114 (34), 70 (25), 57 (100), 56 (12),
55 (13); HRMS (ESI): Calculated for
279.1742, found 279.1732.
C
12H27N2O3S (M++H)
55 (15); HRMS (ESI): Calculated for
265.1586, found 265.1584.
C
11H25N2O3S (M++H)
4.3.11. (2R⁄,3R,RS)-N-(tert-Butylsulfinyl)-2-nitroundecan-3-amine
7a
Diastereomeric mixture (1:1); colorless wax; Rf 0.36 (hexane/
4.3.15. (2R,3R⁄,RS)-N-(tert-Butylsulfinyl)-3-nitro-1-phenylbutan-
2-amine 7i
EtOAc: 1/1); IR
m (KBr) 3215, 2947, 2924, 2855, 1546, 1457, 1390,
1363, 1048 cmꢁ1; dH 5.01 (qd, J = 6.9, 2.9 Hz, 1H), 4.85 (qd, J = 6.8,
4.6 Hz, 1H), 4.23 (d, J = 9.7 Hz, 1H), 3.96 (d, J = 8.7 Hz, 1H), 3.61–
3.49 (m, 1H), 3.49–3.40 (m, 1H), 1.64 (d, J = 6.9 Hz, 3H), 1.56 (d,
J = 6.9 Hz, 3H), 1.54–1.42 (m, 4H), 1.39–1.17 (m, 42H), 0.88 (t,
J = 6.7 Hz, 6H); dC 86.4, 85.6, 60.2, 59.4 (CH), 56.6, 56.5 (C), 32.8,
31.7, 29.7, 29.3, 29.1, 29.0, 28.9 (CH2), 22.7, 22.7 (CH3), 22.6
(CH2), 16.0, 15.2, 14.1 (CH3); LRMS (EI) m/z 216 (M+ꢁC4H8SO,
9%), 187 (25), 170 (17), 168 (10), 143 (32), 142 (81), 140 (17),
111 (10), 110 (11), 104 (19), 103 (44), 97 (28), 96 (17), 95 (19),
84 (18), 83 (32), 82 (16), 81 (23), 71 (49), 70 (21), 69 (59), 68
(13), 67 (23), 64 (15), 58 (12), 57 (95), 56 (97), 55 (100), 54 (16),
Diastereomeric mixture (1:1), yellow oil; Rf 0.23 (hexane/
EtOAc: 1/1); IR
m
(KBr) 3227, 3055, 3026, 2981, 2951, 2868,
dH 7.45–7.08
1545, 1455, 1390, 1241, 1045 746, 700 cmꢁ1
;
(m, 10H), 4.92 (qd, J = 6.9, 3.7 Hz, 1H), 4.83 (qd, J = 6.9, 3.9 Hz,
1H), 4.11 (d, J = 8.8 Hz, 2H), 3.94–3.84 (m, 1H), 3.84–3.74 (m,
1H), 2.95–2.80 (m, 3H), 2.78–2.65 (m, 3H), 1.69 (d, J = 3.5 Hz,
3H), 1.67 (d, J = 3.5 Hz, 3H), 1.10 (s, 9H), 1.08 (s, 9H); dC
136.5, 136.5 (C), 129.4, 129.3, 128.7, 128.6, 127.0, 126.9, 85.8,
84.1, 61.1, 61.0 (CH), 56.5 (C), 39.6, 36.7 (CH2), 22.4, 22.4,
16.5, 15.2 (CH3); LRMS (EI) m/z 194 (M+ꢁC4H8SO, 0.8%), 119
(15), 118 (15), 117 (12), 103 (11), 92 (12), 91 (100), 65 (10);
HRMS (EI): Calculated for C14H23N2O3S (M++H) 299.1429, found
299.1428.
53 (12); HRMS (ESI): Calculated for
321.2212, found 321.2198.
C
15H33N2O3S (M++H)
4.3.12. (3R,4R⁄,RS)-N-(tert-Butylsulfinyl)-2-methyl-4-nitropen-
tan-3-amine 7b
4.4. General procedure for the synthesis of
atives 4
a-amino acid deriv-
Diastereomeric mixture (1:1); white solid, mp 88–91 °C (hex-
ane/CH2Cl2); Rf 0.28 (hexane/EtOAc: 1/1); IR
m
(KBr) 3120, 2967,
Solid NaNO2 (207 mg, 3.0 mmol) was added to a stirred solution
of compound 3 or 7 (0.50 mmol) and AcOH (150 mg, 0.143 mL,
2.50 mmol) in a 7:1 mixture of DMF and water (1.25 mL) at
23 °C. The reaction was heated at 45 °C for 12 h, after which it
was quenched with a 2 M NaOH water solution (10 mL) and ex-
tracted with CH2Cl2 (2 ꢂ 15 mL). The aqueous layer was acidified
with 2 M hydrochloric acid (12 mL) and extracted with EtOAc
(3 ꢂ 15 mL), dried over anhydrous MgSO4, and evaporated
(15 Torr) to give pure compounds 4. Yields are given in Table 3.
Physical and spectroscopic data follow.
2902, 2873, 1545, 1454, 1390, 1359, 1008, 864 cmꢁ1; dH 4.95
(qd, J = 6.9, 4.1 Hz, 1H), 4.76 (p, J = 6.8 Hz, 1H), 4.43 (d,
J = 8.1 Hz, 1H), 3.67 (d, J = 9.8 Hz, 1H), 3.56–3.46 (m, 1H), 3.12
(td, J = 7.9, 4.0 Hz, 1H), 1.93–1.82 (m. 1H), 1.81–1.72 (m, 1H),
1.69 (d, J = 6.8 Hz, 6H), 1.29 (s, 9H), 1.28 (s, 9H), 1.02 (d,
J = 6.7 Hz, 3H), 1.00-0.95 (m, 6H), 0.88 (d, J = 6.7 Hz, 3H); dC
85.2, 83.7 64.9, 64.8 (CH), 57.1, 56.9 (C), 32.3, 29.5 (CH), 23.0,
22.9, 21.2, 20.2, 18.9, 18.1, 16.5, 16.3 (CH3); LRMS (EI) m/z 194
(M+ꢁC4H8, 4%), 146 (11), 119 (39), 83 (26), 76 (10), 57 (100),
56 (21), 55 (10); HRMS (ESI): Calculated for
(M++H) 251.1429, found 251.1423.
C10H23N2O3S
4.4.1. (R,RS)-N-(tert-Butylsulfinyl)-2-aminodecanoic acid 4a
Colorless oil; ½a D23
¼ ꢁ20:2 (c 2.26, CHCl3); Rf 0.75 (MeOH/CH2-
ꢀ
4.3.13. (3R,4R⁄,RS)-N-(tert-Butylsulfinyl)-4-nitro-1-phenylpentan-
3-amine 7c
Cl2: 2/1); IR m (KBr) 3143, 2947, 2920, 2852, 1721, 1467, 1213,
1034, 900, 694 cmꢁ1; dH 9.89 (br s, 1H), 4.48 (d, J = 7.6 Hz, 1H),
3.87 (dd, J = 12.3, 6.8 Hz, 1H), 1.85–1.72 (m, 1H), 1.71–1.58 (m,
1H), 1.24–1.29 (m, 12H), 1.26 (s, 9H), 0.88 (t, J = 6.5 Hz, 3H); dC
174.9 (C), 58.7 (CH), 56.6 (C), 34.0, 31.8, 29.3, 29.1, 29.0, 25.1
(CH2), 22.7 (CH3), 22.6 (CH2), 14.0 (CH3); LRMS (EI) m/z 187 (M+-
ꢁC4H8SO, 0.4%), 131 (10), 75 (43), 57 (100); HRMS (ESI): Calculated
for C14H30NO3S (M++H) 292.1946, found 292.1935.
Diastereomeric mixture (1:1), white wax; Rf 0.28 (hexane/
EtOAc: 1/1); IR
m (KBr) 3222, 3026, 2976, 2957, 1544, 1455, 1390,
1363, 1048, 699 cmꢁ1; dH 7.37–7.06 (m, 10H), 5.04 (qd, J = 6.9,
2.8 Hz, 1H), 4.85 (qd, J = 6.8, 4.9 Hz, 1H), 4.40 (d, J = 10.1 Hz, 1H),
4.10 (d, J = 10.0 Hz, 1H), 3.63–3.51 (m, 1H), 3.42 (tt, J = 10.4,
2.8 Hz, 1H), 2.94–2.81 (m, 2H), 2.74–2.53 (m, 2H), 1.95–1.81 (m,