Vol. 64, No. 7 (2016)
Chem. Pharm. Bull.
713
Methyl (S)-3-(N-(Benzyloxy)benzamido)hexanoate (2d- 128.1 (4C), 77.2, 57.1, 51.8, 37.4, 32.7, 31.7, 29.3, 29.1, 26.3,
[NBz, OMe])
22.6, 14.1; IR (ATR): 1740, 1657cm−1; HR-MS (ESI): Calcd
1
Colorless oil (10.8mg, 61, 90% ee with cat. 6i); H-NMR for C25H34NO4 [M+H]+ 412.2482. Found 412.2483; HPLC
(400MHz, CDCl3) δ: 7.65 (d, J=7.0Hz, 2H), 7.51–7.37 (m, [Chiralcel IC, n-hexane–2-propanol=90:10, 1.0mL/min,
3H), 7.35–7.27 (m, 3H), 7.27–7.00 (m, 2H), 5.04–4.40 (m, λ=254nm, retention times: (major) 23.3min (minor) 16.3min];
3H), 3.68 (s, 3H), 2.85 (dd, J1=15.4Hz, J2=8.4Hz, 1H), 2.56 [α]D25+1.3 (c 1.00, CHCl3) for 86% ee.
(dd, J1=15.4Hz, J2=4.3Hz, 1H), 1.94–1.77 (m, 1H), 1.76–1.20
(m, 3H), 0.88 (t, J=6.4Hz, 3H); 13C-NMR (100MHz, CDCl3) [OMe])
δ: 171.6, 171.5, 135.0, 134.5, 130.5, 129.4 (2C), 128.7, 128.4 Colorless oil (14.3mg, 57, 76% ee, with cat. 6i); H-NMR
Methyl (R)-3-((Benzyloxy)amino)-4-methylpentanoate (2g-
1
(2C), 128.1 (4C), 78.1, 57.1, 51.8, 37.4, 34.9, 19.5, 13.8; IR (400MHz, CDCl3) δ: 7.39–7.27 (m, 5H), 5.81 (brs, 1H), 4.67
(ATR): 1739, 1655cm−1; HR-MS (ESI): Calcd for C21H26NO4 (s, 2H), 3.64 (s, 3H), 3.16 (ddd, J1=9.7Hz, J2=J3=3.9Hz, 1H),
[M+H]+ 356.1856. Found 356.1850; HPLC [Chiralcel IC, n- 2.47 (dd, J1=15.7Hz, J2=4.6Hz, 1H), 2.42 (dd, J1=15.7Hz,
hexane–2-propanol=80:20, 1.0mL/min, λ=254nm, retention J2=7.8Hz, 1H), 1.97–1.84 (m, 1H), 0.94 (t, J=7.0Hz, 3H), 0.90
times: (major) 17.4min (minor) 12.2min]; [α]D23+17.4 (c 1.00, (t, J=7.0Hz, 3H); 13C-NMR (100MHz, CDCl3) δ: 173.4, 137.8,
CHCl3) for 90% ee.
128.4 (2C), 128.3 (2C), 127.7, 76.2, 62.7, 51.6, 33.9, 29.0, 19.2,
Methyl (S)-3-((Benzyloxy)amino)octanoate (2e-[OMe])
18.2; IR (ATR): 1737, 1202cm−1; HR-MS (ESI): Calcd for
Colorless oil (21.3mg, 76, 88% ee with cat. 6i); H-NMR C14H22NO3 [M+H]+ 252.1594. Found 252.1594; [α]D23+8.6 (c
1
(400MHz, CDCl3) δ: 7.38–7.26 (m, 5H), 5.79 (brs, 1H), 4.67 1.02, CHCl3) for 76% ee.
(s, 2H), 3.64 (s, 3H), 3.35–3.25 (m, 1H), 2.57 (dd, J1=15.7Hz,
Methyl (R)-3-(N-(Benzyloxy)benzamido)-4-methylpentano-
J2=7.5Hz, 1H), 2.44 (dd, J1=15.7Hz, J2=4.9Hz, 1H), ate (2g-[NBz, OMe])
1
1.57–1.47 (m, 1H), 1.42–1.19 (m, 7H), 0.88 (t, J=6.8Hz, 3H);
Colorless oil (16.0mg, 90, 76% ee with cat. 6i); H-NMR
13C-NMR (100MHz, CDCl3) δ: 173.0, 137.8, 128.37 (2C), (400MHz, CDCl3) δ: 7.66 (d, J=7.0Hz, 2H), 7.50–7.37 (m,
128.30 (2C), 127.7, 76.5, 57.6, 51.5, 37.0, 31.8, 31.8, 25.7, 22.5, 3H), 7.36–6.94 (m, 5H), 5.00–4.20 (m, 3H), 3.70 (s, 3H), 2.89
14.0; IR (ATR): 1735, 1204cm−1; HR-MS (ESI): Calcd for (dd, J1=15.4Hz, J2=9.9Hz, 1H), 2.76–2.67 (m, 1H), 2.20–2.08
C16H26NO3 [M+H]+ 280.1907. Found 280.1909; [α]D31+2.2 (c (m, 1H), 1.12–0.93 (m, 6H); 13C-NMR (100MHz, CDCl3)
1.00, CHCl3) for 88% ee.
δ: 172.1, 171.4, 135.1, 134.5, 130.4, 129.2 (2C), 128.6, 128.3
Methyl (S)-3-(N-(Benzyloxy)-4-methylbenzamido)octanoate (2C), 128.1 (4C), 77.8, 63.1, 51.8, 35.4, 31.4, 20.2, 19.8; IR
(2e-[N-4-toluoyl, OMe])
(ATR): 1738, 1650cm−1; HR-MS (ESI): Calcd for C21H26NO4
1
Colorless oil (15.1mg, 76, 88% ee with cat. 6i); H-NMR [M+H]+ 356.1856. Found 356.1854; HPLC [Chiralcel IC, n-
(400MHz, CDCl3) δ: 7.56 (d, J=8.1Hz, 2H), 7.38–7.15 (m, hexane–2-propanol=90:10, 1.0mL/min, λ=254nm, retention
7H), 4.98–4.46 (m, 3H), 3.67 (s, 3H), 2.82 (dd, J1=15.7Hz, times: (major) 28.3min (minor) 18.9min]; [α]D22+24.6 (c 1.01,
J2=8.4Hz, 1H), 2.54 (dd, J1=15.7Hz, J2=5.7Hz, 1H), 2.40 (s, CHCl3) for 76% ee.
3H), 1.90–1.85 (m, 1H), 1.73–1.15 (m, 7H), 0.85 (t, J=7.1Hz,
3H); 13C-NMR (100MHz, CDCl3) δ: 171.6, 171.4, 140.9, 134.8, (2h-[OMe])
132.0, 129.4 (2C), 128.8 (2C), 128.6, 128.4 (2C), 128.2 (2C), Colorless oil (58.9mg, 89, 85% ee with cat. 6i); H-NMR
Methyl (R)-4-(Benzyloxy)-3-((benzyloxy)amino)butanoate
1
77.8, 57.7, 51.8, 37.4, 32.7, 31.4, 26.0, 22.4, 21.5, 13.9; IR (400MHz, CDCl3) δ: 7.37–7.26 (m, 10H), 6.08 (brs, 1H), 4.67
(ATR): 1740, 1652cm−1; HR-MS (ESI): Calcd for C24H32NO4 (s, 2H), 4.52 (d, J=12.2Hz, 1H), 4.48(d, J=12.2Hz, 1H), 3.64
[M+H]+ 398.2326. Found 398.2326; HPLC [Chiralcel IC, n- (s, 3H), 3.62–3.52 (m, 3H), 2.61 (dd, J1=15.9Hz, J2=7.0Hz,
hexane–2-propanol=80:20, 1.0mL/min, λ=254nm, retention 1H), 2.48 (dd, J1=15.9Hz, J2=5.5Hz, 1H); 13C-NMR
times: (major) 19.2min (minor) 12.2min]; [α]D22+11.0 (c 1.00, (100MHz, CDCl3) δ: 172.4, 138.0, 137.6, 128.36 (2C), 128.35
CHCl3) for 88% ee.
Methyl (S)-3-((Benzyloxy)amino)decanoate (2f-[OMe])
(2C), 128.29 (2C), 127.8, 127.65, 127.61 (2C), 76.4, 73.2, 69.3,
57.2, 51.6, 34.2; IR (ATR): 1734, 1099cm−1; HR-MS (ESI):
Colorless oil (23.1mg, 75, 86% ee with cat. 6i); H-NMR Calcd for C19H24NO4 [M+H]+ 330.1700. Found 330.1703;
(400MHz, CDCl3) δ: 7.37–7.26 (m, 5H), 5.79 (brs, 1H), 4.67 HPLC [Chiralcel IC, n-hexane–2-propanol=98:2, 1.0mL/min,
(s, 2H), 3.64 (s, 3H), 3.34–3.25 (m, 1H), 2.57 (dd, J1=15.5Hz, λ=254nm, retention times: (major) 20.1min (minor) 17.9min];
J2=7.7Hz, 1H), 2.44 (dd, J1=15.5Hz, J2=4.9Hz, 1H), [α]D26+3.2 (c 1.02, CHCl3) for 85% ee.
1
1.57–1.47 (m, 1H), 1.42–1.19 (m, 11H), 0.88 (t, J=6.8Hz, 3H);
Methyl (S)-4-(Benzyloxy)-3-((benzyloxy)amino)butanoate
13C-NMR (100MHz, CDCl3) δ: 172.9, 137.8, 128.36 (2C), (ent-2h-[OMe])
128.28 (2C), 127.7, 76.5, 57.6, 51.5, 37.0, 31.9, 31.8, 29.5, 29.1,
Colorless oil (24.9mg, 76, 83% ee with cat. 6i); HPLC [Chi-
26.0, 22.6, 14.1; IR (ATR): 1737, 1199cm−1; HR-MS (ESI): ralcel IC, n-hexane–2-propanol=98:2, 1.0mL/min, λ=254nm,
Calcd for C18H30NO3 [M+H]+ 308.2220. Found 308.2222; retention times: (major) 17.9min (minor) 20.1min]; [α]D25−3.0 (c
[α]D24+2.6 (c 0.96, CHCl3) for 86% ee.
Methyl (S)-3-(N-(Benzyloxy)benzamido)decanoate (2f-
[NBz, OMe])
1.03, CHCl3) for 83% ee.
(S)-4-((Benzyloxy)amino)-6-methoxy-6-oxohexyl Benzoate
(2i-[OMe])
1
1
Colorless oil (17.5mg, 85, 86% ee, with cat. 6i); H-NMR
Colorless oil (31.9mg, 86, 91% ee with cat. 6i); H-NMR
(400MHz, CDCl3) δ: 7.65 (d, J=7.0Hz, 2H), 7.51–7.38 (m, (400MHz, CDCl3) δ: 8.10–8.01 (m, 2H), 7.62–7.53 (m, 1H),
3H), 7.35–7.27 (m, 3H), 7.26–7.03 (m, 2H), 5.00–4.35 (m, 3H), 7.49–7.42 (m, 2H), 7.37–7.27 (m, 5H), 5.87 (brs, 1H), 4.68 (s,
3.68 (s, 3H), 2.84 (dd, J1=15.4Hz, J2=8.4Hz, 1H), 2.58 (dd, 2H), 4.30 (t, J=6.5Hz, 2H), 3.65 (s, 3H), 3.39–3.30 (m, 1H),
J1=15.4Hz, J2=4.3Hz, 1H), 1.91–1.77 (m, 1H), 1.70–1.15 (m, 2.63 (dd, J1=15.9Hz, J2=7.8Hz, 1H), 2.46 (dd, J1=15.9Hz,
11H), 0.86 (t, J=6.8Hz, 3H); 13C-NMR (100MHz, CDCl3) δ: J2=4.9Hz, 1H) 1.95–1.49 (m, 4H); 13C-NMR (100MHz,
171.6, 171.5, 135.0, 134.7, 130.5, 129.4 (2C), 128.7, 128.4 (2C), CDCl3) δ: 172.7, 166.6, 137.7, 132.9, 130.2, 129.5 (2C), 128.39