2286
K. Ditrich
PAPER
1H NMR (500 MHz, CDCl3): d = 1.50 (d, J = 7.4 Hz, 3 H,
CH3CHN), 3.40 (s, 3 H, CH2OCH3), 3.84 and 3.90 (AB-system,
JA,B = 15.0 Hz, 2 H, CH2OCH3), 5.18 (quint, J = 7.4 Hz, 1 H,
CH3CHNH), 6.80 (br s, 1 H, CONH), 7.23–7.50 (m, 5 H).
13C NMR (125 MHz, CDCl3): d = 21.9, 48.0, 59.1, 72.0, 126.1,
127.4, 128.7, 143.0, 168.5.
(AB-system, JA,B = 15.0 Hz, 2 H, CH2OCH3), 5.23 (m, 1 H,
CHNH), 6.83 (br s, 1 H, CONH), 6.99–7.06 (m, 1 H), 7.08–7.15 (m,
2 H), 7.21 (dd, J = 2.0, 8.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 22.8, 28.5, 46.1, 59.1, 71.9,
124.5, 126.8, 128.1, 130.3, 132.4, 133.6, 168.6.
2-Methoxy-N-[(2R)-2-nonyl]acetamide [(R)-3g]
2-Methoxy-N-[(1R)-1-phenylpropyl]acetamide [(R)-3b]
Following TP1, the amide (R)-3b was obtained as colorless crystals;
chiral HPLC: tR = 4.60 min (R), 5.46 min (S); mp 75 °C;
[a]D25 +107.4 (c = 2.0, MeOH).
Following TP1, the amide (R)-3g was obtained as colorless crystals;
chiral GC (column: Chiraldex-GTA, 20 m × 0.25 mm × 0.12 mm,
constant flow: 0.8 mL/min, program: 140/20/10/180/20): tR = 9.59
min (S), 10.11 min (R); mp 58 °C; [a]D25 +5.3 (c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.3 Hz, 3 H, CH3CH2),
1.80–1.92 (m, 2 H, CH3CH2CNH), 3.38 (s, 3 H, CH2OCH3), 3.83
and 3.92 (AB-system, JA,B = 15.0 Hz, 2 H, CH2OCH3), 4.93 (q,
J = 7.3 Hz, 1 H, CH2CHNH), 6.80 (br s, 1 H, CONH), 7.18–7.35
(m, 5 H).
13C NMR (125 MHz, CDCl3): d = 10.7, 29.2, 54.1, 59.1, 72.0,
126.6, 127.3, 128.6, 142.0, 168.7.
1H NMR (500 MHz, CDCl3): d = 0.88 (t, J = 7.2 Hz, 3 H, CH3CH2),
1.18 (d, J = 7.3 Hz, 3 H, CH3CHNH), 1.22–1.38 (m, 12 H), 1.43–
1.50 (m, 2 H), 3.40 (s, 3 H, CH2OCH3), 3.85 (s, 2 H, CH2OCH3),
4.05 (sext, J = 7.2 Hz, 1 H, CHNH), 6.30 (br s, 1 H, CONH).
13C NMR (125 MHz, CDCl3): d = 13.1, 20.0, 21.7, 25.1, 28.3, 28.5,
31.0, 36.0, 43.7, 58.1, 71.2, 167.7.
2-Methoxy-N-[(1R)-1,2,2-Trimethylpropyl]acetamide [(R)-3h]
Following TP1, the amide (R)-3h was obtained as a colorless oil;
chiral HPLC: tR = 2.99 min (R), 3.48 min (S); bp 101 °C/10 Torr;
[a]D25 –2.4 (c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 0.90 [s, 9 H, (CH3)3CH], 1.05 (d,
J = 7.1 Hz, 3 H, CH3CHN), 3.42 (s, 3 H, CH2OCH3), 3.85 (s, 2 H,
CH2OCH3), 3.88 (q, J = 7.2 Hz, 1 H, CH3CHNH), 6.40 (br s, 1 H,
CONH).
N-[(1R)-1-(4-Bromophenyl)ethyl]-2-methoxyacetamide [(R)-3c]
Following TP1, the amide (R)-3c was obtained as colorless crystals;
chiral HPLC: tR = 6.30 min (R), 6.90 min (S); mp 94 °C; [a]D25 +104
(c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 1.49 (d, J = 7.4 Hz, 3 H, CH3CH),
3.38 (s, 3 H, CH2OCH3), 3.85 and 3.91 (AB-system, JA,B = 15.0 Hz,
2 H, CH2OCH3), 5.12 (quint, J = 7.4 Hz, 1 H, CHNH), 6.75 (br s, 1
H, CONH), 7.20 and 7.45 (AA¢BB¢-system, J = 8 Hz, 4 H)
13C NMR (125 MHz, CDCl3): d = 16.1, 26.2, 34.2, 52.2, 59.2, 72.1,
168.7.
13C NMR (125 MHz, CDCl3): d = 21.8, 47.5, 59.1, 71.9, 121.1,
127.9, 131.7, 142.2, 168.6.
2-Methoxy-N-[(1R)-1-(6-methoxypyridin-3-yl)ethyl]acetamide
[(R)-3i]
N-[(1R)-1-(2,4-Dichlorophenyl)ethyl]-2-methoxyacetamide
[(R)-3d]
Following TP1, amide (R)-3d was obtained as colorless crystals;
chiral HPLC: tR = 5.38 min (R), 5.79 min (S); mp 90 °C;
[a]D25 +48.5 (c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 1.50 (d, J = 7.2 Hz, 3 H, CH3CH),
3.40 (s, 3 H, CH2OCH3), 3.86 and 3.92 (AB-system, JA,B = 15.0 Hz,
2 H, CH2OCH3), 5.38 (quint, J = 7.2 Hz, 1 H, CHNH), 6.92 (br s, 1
H, CONH), 7.22 (dd, J = 1.2, 8 Hz, 1 H), 7.20–7.28 (m, 2 H), 7.37
(d, J = 1.2 Hz, 1 H).
Following TP1, the mixture of amine (S)-1i and amide (R)-3i ob-
tained were separated from each other by bulb-to-bulb distillation
(100 °C/0.5 Torr). The amide (R)-3i was obtained as colorless crys-
tals; chiral HPLC: tR = 5.95 min (R), 6.25 min (S); mp 83 °C;
[a]D25 +104.8 (c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.4 Hz, 3 H, CH3CH2),
1.78–1.95 (m, 2 H, CH3CH2), 3.40 (s, 3 H, CH2OCH3), 3.82 and
3.90 (AB-system, JA,B = 15.0 Hz, 2 H), 3.90 (s, 3 H, OCH3), 4.87 (q,
J = 8.0 Hz, 1 H, CHNH), 6.75 (br s, 1 H, CONH), 6.75 (d, J = 8.0
Hz, 1 H), 7.50 (dd, J = 2.0, 8.0 Hz, 1 H), 8.09 (d, J = 2.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 20.9, 46.0, 59.2, 72.0, 127.4,
128.0, 129.8, 133.5, 133.6, 139.2, 168.6.
13C NMR (125 MHz, CDCl3): d = 10.7, 28.8, 51.6, 53.5, 59.2, 72.0,
110.9, 130.2, 137.2, 145.2, 163.6, 168.8.
N-[(1R)-2,3-Dihydro-1H-inden-1-yl]-2-methoxyacetamide [(R)-
3e]
Following TP1, the amide (R)-3e was obtained as colorless crystals;
chiral HPLC: tR = 4.81 min (R), 6.71 min (S); mp 94 °C;
[a]D25 +112.4 (c = 2.0, MeOH).
2-Methoxy-N-[(1R)-(1-naphthyl)ethyl]acetamide [(R)-3j]
Following TP1, the amide (R)-3j was obtained as colorless crystals;
chiral HPLC: tR = 3.79 min (R), 6.83 min (S); mp 80 °C;
[a]D25 +30.8 (c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 1.78–1.88 (m, 1 H), 2.58–2.68 (m,
1 H), 2.82–2.95 (m, 1 H), 2.98–3.08 (m, 1 H), 3.38 (s, 3 H,
CH2OCH3), 3.85 and 3.91 (AB-system, JA,B = 15.0 Hz, 2 H,
CH2OCH3), 5.53 (dd, J = 7, 9 Hz, 1 H, CHNH), 6.85 (br s, 1 H,
CONH), 7.18–7.29 (m, 4 H).
1H NMR (500 MHz, CDCl3): d = 1.68 (d, J = 7.6 Hz, 3 H, CH3CH),
3.38 (s, 3 H, CH2OCH3), 3.84 and 3.92 (AB-system, JA,B = 15.0 Hz,
2 H, CH2OCH3), 5.98 (quint, J = 7.6 Hz, 1 H, CHNH), 6.80 (br s, 1
H, CONH), 7.48 (m, 4 H), 7.78 (d, J = 8.0 Hz, 1 H), 7.85 (d, J = 8.0
Hz, 1 H), 8.11 (d, J = 8 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 30.3, 34.0, 53.9, 59.1, 72.0,
124.0, 124.8, 126.8, 128.0, 143.0, 143.4, 169.3.
13C NMR (125 MHz, CDCl3): d = 21.0, 43.9, 59.0, 71.9, 122.5,
123.4, 125.2, 125.8, 126.5, 128.3, 128.8, 131.1, 133.9, 138.2, 168.3.
N-[(4R)-3,4-Dihydro-2H-1-benzothiopyran-4-yl]-2-methoxy-
acetamide [(R)-3f]
Following TP1, the amide (R)-3f was obtained as colorless crystals;
chiral HPLC: tR = 6.91 min (R), 7.84 min (S); mp 117 °C;
[a]D25 +130.2 (c = 2.0, MeOH).
2-Methoxy-N-[(1R)-1-(4-methylphenyl)ethyl]acetamide
[(R)-3k]
Following TP1, the amide (R)-3k was obtained as colorless crystals;
chiral HPLC: tR = 4.35 min (R), 5.01 min (S); mp 54 °C; [a]D25 +124
(c = 2.0, MeOH).
1H NMR (500 MHz, CDCl3): d = 2.05–2.18 (m, 1 H), 2.30–2.42 (m,
1 H), 2.90–3.15 (m, 2 H), 3.35 (s, 3 H, CH2OCH3), 3.90 and 3.92
1H NMR (500 MHz, CDCl3): d = 1.50 (d, J = 7.4 Hz, 3 H, CH3CH),
2.33 (s, 3 H, ArCH3), 3.37 (s, 3 H, CH2OCH3), 3.84 and 3.90 (AB-
Synthesis 2008, No. 14, 2283–2287 © Thieme Stuttgart · New York