ꢁꢀꢀꢀ
Y. Shimotori et al.: Optically active 4-substituted γ-lactonesꢃ ꢃ7
1240 (C-O-C), 818 cm-1 (Ar, C-H); 1H NMR: δ 2.02 (s, 3H, -OC(ꢀ=ꢀO)CH3), (-OCꢀ=ꢀO), 1606, 1496 (Ar, Cꢀ=ꢀC), 1176 (C-O-C), 760, 700 cm-1 (Ar, C-H);
2.13 (m, 2H, -NHC(ꢀ=ꢀO)CH2CH2-), 2.24 (m, 2H, -NHC(ꢀ=ꢀO)CH2-), 2.31 (s, 1H NMR: δ 2.10 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-), 2.63–2.72 (m, 3H, -OC(ꢀ=ꢀO)
3H, -PhCH3), 2.72 (d, 3H, J ꢀ=ꢀ 4.6 Hz, -NHCH3), 5.69 (m, 1H, -CHOC(ꢀ=ꢀO) CH2CH2-), 5.52 (t, 1H, J ꢀ=ꢀ 6.9 Hz, -OCH(CH2-)Ph), 7.31–7.46 (m, 5H, -Ph);
CH3), 6.18 (br, 1H, -NH-), 7.12 (d, 2H, J ꢀ=ꢀ 7.8 Hz, -Ph-), 7.19 (d, 2H, J ꢀ=ꢀ 7.8 13C NMR: δ 28.9 (-C(ꢀ=ꢀO)CH2CH2-), 31.0 (-C(ꢀ=ꢀO)CH2CH2-), 81.2 (-OCHPh),
Hz, -Ph-); 13C NMR: δ 20.9 (-OC(ꢀ=ꢀO)CH3), 21.0 (-PhCH3), 26.1 (-NHCH3), 125.2, 128.4, 128.7, 139.3 (-Ph), 176.9 (-C(ꢀ=ꢀO)O-). HRMS (ESI). Calcd for
+
+
31.7 (-C(ꢀ=ꢀO)CH2-), 32.1 (-CH2-), 75.1 (-CHOC(ꢀ=ꢀO)CH3), 126.2, 129.0, 136.7, C10H11O2 (M) : m/z 162.0681. Found: (M) , 162.0653.
137.6 (-Ph-), 170.3 (-OC(ꢀ=ꢀO)CH3), 172.7 (-NHC(ꢀ=ꢀO)-). HRMS (FD). Calcd
+
for C14H20NO3 (M) : m/z 249.1365. Found: m/z 249.1368.
4-(p-Tolyl)-γ-butyrolactone (3d, 4d)ꢁColorless oil; Rfꢀ=ꢀ0.18 (eluent:
n-hexane-EtOAc, 4:1, v/v); IR: 3025 (Ar, C-H), 2985 (CH3), 2949 (CH2),
N-methyl-4-acetoxy-5-phenylpentanamide (2e)ꢁColorless oil; 1774 (-OCꢀ=ꢀO), 1616, 1518 (Ar, Cꢀ=ꢀC), 1176 (C-O-C), 806 cm-1 (Ar, C-H); 1H
Rfꢀ=ꢀ0.33 (eluent: CHCl3-MeOH, 10:1, v/v). IR: 3308 (N-H), 3086, 3062, NMR: δ 2.18 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-, 2.35 (s, 3H, -PhCH3), 2.56–2.69
3029 (Ar, C-H), 2938 (-CH3), 1735 (-OCꢀ=ꢀO), 1646 (-NHCꢀ=ꢀO), 1496, (m, 3H, -OC(ꢀ=ꢀO)CH2CH2-), 5.47 (t, 1H, J ꢀ=ꢀ 7.3 Hz, -OCH(CH2-)Ph-), 7.11–
1455 (Ar, Cꢀ=ꢀC), 1242 cm-1 (-OCꢀ=ꢀO); H NMR: δ 1.88 (m, 1H, -NHC(ꢀ=ꢀO) 7.25 (m, 4H, -Ph-); 13C NMR: δ 21.1 (-PhCH3), 29.0 (-C(ꢀ=ꢀO)CH2CH2-), 30.9
1
CH2CH2-), 2.13 (m, 1H, -NHC(ꢀ=ꢀO)CH2CH2-), 1.98 (s, 3H, -OC(ꢀ=ꢀO)CH3), (-C(ꢀ=ꢀO)CH2CH2-), 81.3 (-OCHPh-), 125.3, 129.3, 132.2, 138.3 (-Ph-), 177.0
+
2.21 (m, 2H, -NHC(ꢀ=ꢀO)CH2-), 2.77 (d, 3H, J ꢀ=ꢀ 4.6 Hz, -NHCH3), 2.87 (m, (-C(ꢀ=ꢀO)O-). HRMS (FI). Calcd for C11H13O2 (M) : m/z 176.0837. Found:
2H, -CH2Ph), 5.07 (m, 1H, -CHOC(ꢀ=ꢀO)CH3), 5.79 (s, 1H, -NH-), 7.15–7.39 m/z 176.0834.
(m, 5H, -Ph); 13C NMR: δ 21.0 (-OC(ꢀ=ꢀO)CH3), 26.2 (-NHCH3), 29.7 (-CH2-),
32.6 (-C(ꢀ=ꢀO)CH2-), 40.7 (-CH2Ph), 74.4 (-CHOC(ꢀ=ꢀO)CH3), 126.5, 128.3,
129.3, 137.0 (-Ph), 170.9 (-OC(ꢀ=ꢀO)CH3), 172.7 (-NHC(ꢀ=ꢀO)-). HRMS (FD).
5-Phenyl-γ-pentalactone (3e, 4e)ꢁColorless oil; Rfꢀ=ꢀ0.15 (elu-
ent: n-hexane-EtOAc, 4:1, v/v). IR: 3030 (Ar, C-H), 2943 (CH2), 1774
(-OCꢀ=ꢀO), 1603, 1496 (Ar, Cꢀ=ꢀC), 1178 (C-O-C), 750, 702 cm-1 (Ar, C-H); 1H
NMR: δ 1.96 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-), 2.25 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-),
+
Calcd for C14H20NO3 (M+H) : m/z 250.1443. Found: m/z 250.1444.
N-methyl-4-acetoxy-6-phenylhexanamide (2f)ꢁColorless oil; 2.42 (m, 2H, -OC(ꢀ=ꢀO)CH2CH2-), 2.93 (q, 1H, J ꢀ=ꢀ 6.0, 6.4 Hz, -CHCH2Ph),
Rfꢀ=ꢀ0.33 (eluent: CHCl3-MeOH, 10:1, v/v); IR: 3297 (N-H), 3087, 3062, 3.08 (q, 1H, J ꢀ=ꢀ 6.0, 6.4 Hz, -CHCH2Ph), 4.74 (quint, 1H, J ꢀ=ꢀ 6.9, 6.4
3026 (Ar, C-H), 2943, 2864 (-CH3), 1736 (-OCꢀ=ꢀO), 1644 (-NHCꢀ=ꢀO), Hz, -OCH(CH2-)CH2Ph), 7.18–7.38 (m, 5H, -Ph); 13C NMR: δ 27.1 (-C(ꢀ=ꢀO)
1496, 1454 (Ar, Cꢀ=ꢀC), 1242 cm-1 (-OCꢀ=ꢀO); 1H NMR: δ 1.79–2.01 (m, 4H, CH2CH2-), 28.6 (-C(ꢀ=ꢀO)CH2CH2-), 41.3 (-CHCH2Ph), 80.8 (-OCHCH2Ph),
-CH2CH(OC(ꢀ=ꢀO)CH3)CH2-), 2.04 (s, 3H, -OC(ꢀ=ꢀO)CH3), 2.19 (m, 2H, 127.0, 128.6, 129.4, 135.8 (-Ph), 177.0 (-C(ꢀ=ꢀO)O-). HRMS (FI). Calcd for
+
-NHC(ꢀ=ꢀO)CH2-), 2.63 (m, 2H, -CH2Ph), 2.78 (d, 3H, J ꢀ=ꢀ 4.6 Hz, -NHCH3), C11H13O2 (M) : m/z 176.0837. Found: m/z 176.0812.
4.92 (m, 1H, -CHOC(ꢀ=ꢀO)CH3), 5.94 (s, 1H, -NH-), 7.11–7.35 (m, 5H, -Ph);
13CNMR:δ21.1 (-OC(ꢀ=ꢀO)CH3), 26.3 (-NHCH3), 30.2 (-CH2Ph), 31.6(-CH2-),
6-Phenyl-γ-hexalactone (3f, 4f)ꢁColorless oil; Rfꢀ=ꢀ0.18 (eluent:
32.4 (-C(ꢀ=ꢀO)CH2-), 35.9 (-CH2CH2Ph), 73.5 (-CHOC(ꢀ=ꢀO)CH3), 125.9,
128.2, 128.4, 141.8 (-Ph), 171.3 (-OC(ꢀ=ꢀO)CH3), 173.0 (-NHC(ꢀ=ꢀO)-). HRMS
n-hexane-EtOAc, 4:1, v/v); IR: 3028 (Ar, C-H), 2943 (CH2), 1770 (-OCꢀ=ꢀO),
1
1603, 1495 (Ar, Cꢀ=ꢀC), 1180 (C-O-C), 750, 702 cm-1 (Ar, C-H); H NMR:
+
(FD). Calcd for C15H22NO3 (M) : m/z 263.1521. Found: m/z 263.1517.
δ 1.82–1.96 (m, 2H, -C(ꢀ=ꢀO)CH2CH2CH(O-)CH2-), 2.05 (m, 1H, -CHCH2
CH2Ph), 2.31 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-), 2.53 (m, 2H, -OC(ꢀ=ꢀO)CH2CH2-),
N-methyl-4-acetoxy-4-(p-anisyl)butanamide (2g)ꢁColorless oil; 2.73 (m, 1H, -CH2Ph), 2.83 (m, 1H, -CH2Ph), 4.47 (quint, 1H, J ꢀ=ꢀ 6.9, 6.9
Rfꢀ=ꢀ0.33 (eluent: CHCl3-MeOH, 10:1, v/v); IR: 3306 (N-H), 3094 (Ar, Hz, -C(ꢀ=ꢀO)CH2CH2CH(O-)CH2-), 7.16–7.36 (m, 5H, -Ph); 13C NMR: δ 27.9
C-H), 2938 (CH3), 2838 (CH2), 1736 (-OCꢀ=ꢀO), 1648 (-NHCꢀ=ꢀO), 1613, (-C(ꢀ=ꢀO)CH2CH2-), 28.8 (-C(ꢀ=ꢀO)CH2CH2-), 31.6 (-CHPh), 37.3 (-OCHCH2-),
1516 (Ar, Cꢀ=ꢀO), 1241 (C-O-C), 832 cm-1 (Ar, C-H); 1H NMR: δ 2.05 (s, 3H, 79.8 (-OCHCH2-), 126.1, 128.4, 128.5, 140.7 (-Ph), 177.1 (-C(ꢀ=ꢀO)O-). HRMS
+
-OC(ꢀ=ꢀO)CH3), 2.14 (m, 2H, -NHC(ꢀ=ꢀO)CH2CH2-), 2.24 (m, 2H, -NHC(ꢀ=ꢀO) (FI). Calcd for C12H15O2 (M) : m/z 190.0994. Found: m/z 190.0977.
CH2-), 2.79 (d, 3H, J ꢀ=ꢀ 4.6 Hz, -NHCH3), 3.80 (s, 3H, -PhOCH3), 5.54 (s,
1H, -NH-), 5.71 (t, 1H, J ꢀ=ꢀ 5.0 Hz, -CHOC(ꢀ=ꢀO)CH3), 6.87 (d, 2H, J ꢀ=ꢀ 8.7
Hz, -Ph-), 7.26 (d, 2H, J ꢀ=ꢀ 6.9 Hz, -Ph-); 13C NMR: δ 21.3 (-OC(ꢀ=ꢀO)CH3),
26.3 (-NHCH3), 31.8 (-C(ꢀ=ꢀO)CH2-), 32.6 (-CH2-), 55.3 (-PhOCH3), 75.1
(-CHOC(ꢀ=ꢀO)CH3), 113.9, 127.9, 131.9, 159.4 (-Ph-), 170.5 (-OC(ꢀ=ꢀO)CH3),
4-(p-Anisyl)-γ-butyrolactone (3g, 4g)ꢁColorless oil; Rfꢀ=ꢀ0.10 (eluent:
n-hexane-EtOAc, 4:1, v/v); IR: 3037 (Ar, C-H), 2956 (CH3), 2937 (CH2), 1773
(-OCꢀ=ꢀO), 1613, 1517 (Ar, Cꢀ=ꢀC), 1176 (C-O-C), 837 cm-1 (Ar, C-H); 1H NMR: δ
2.20 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-), 2.57–2.71 (m, 3H, -OC(ꢀ=ꢀO)CH2CH2-), 3.28
(s, 3H, -PhOCH3), 5.47 (t, 1H, J ꢀ=ꢀ 7.4 Hz, -C(ꢀ=ꢀO)CH2CH2CH(O-)Ph-), 6.92 (d,
2H, J ꢀ=ꢀ 8.6 Hz, -Ph-), 7.27 (d, 2H, J ꢀ=ꢀ 7.4 Hz, -Ph-); 13C NMR: δ 29.2 (-C(ꢀ=ꢀO)
CH2CH2-), 30.9 (-C(ꢀ=ꢀO)CH2CH2-), 55.3 (-PhOCH3), 81.3 (-OCHPh-), 114.1,
126.9, 131.3, 165.3 (-Ph-), 177.1 (-C(ꢀ=ꢀO)O-). HRMS (FI). Calcd for C11H13O3
+
172.4 (-NHC(ꢀ=ꢀO)-). HRMS (FD). Calcd for C14H20NO4 (M) : m/z 265.1314.
Found: m/z 265.1313.
7-Methyl-γ-octalactone (3a, 4a)ꢁColorless oil; Rfꢀ=ꢀ0.25 (eluent:
n-Hexane-EtOAc, 4:1, v/v); IR: 2951 (CH3), 2868 (CH2), 1776 (-OCꢀ=ꢀO),
+
(M) : m/z 192.0786. Found: m/z 192.0758.
1
1184 cm-1 (C-O-C); H NMR: δ 0.90 (d, 6H, J ꢀ=ꢀ 6.3 Hz, -CH(CH3)2), 1.24
(m, 1H, -CH2CH(CH3)2), 1.36 (m, 1H, -CH2CH(CH3)2), 1.52–1.66 (m,
2H, -CH2CH2CH(CH3)2), 1.74 (m, 1H, -CH2CH2CH(CH3)2), 1.86 (m, 1H,
-OC(ꢀ=ꢀO)CH2CH2-), 2.33 (m, 1H, -OC(ꢀ=ꢀO)CH2CH2-), 2.54 (t, 2H, J ꢀ=ꢀ 8.0
Hz, -OC(ꢀ=ꢀO)CH2CH2-), 4.47 (quint, 1H, J ꢀ=ꢀ 6.3, 7.4 Hz, -OCH(CH2-)CH2-);
13C NMR: δ 22.4 (-CH(CH3)2), 27.8 (-CH(CH3)2), 28.0 (-C(ꢀ=ꢀO)CH2CH2-),
28.8 (-C(ꢀ=ꢀO)CH2CH2-), 33.4 (-CHCH2CH2-), 34.1 (-CH2CH(CH3)2-), 81.3
General procedure for Novozym 435-catalyzed hydrolysis
Racemic N-methyl-4-acetoxyalkanamides rac-2a– g were prepared
almost quantitatively from N-methyl-4-hydroxyalkanamides rac-
1a– g by acetylation using acetic anhydride [30]. Briefly, a mixture
of racemic N-methy-5-acetoxyalkanamide (rac-2a– g, 1.0 mmol),
methanol (3.0 mmol, 0.10 g), Novozym 435 (0.4 g), and diethyl ether
+
(-OCHCH2-), 177.26 (-C(ꢀ=ꢀO)O-). HRMS (FI). Calcd for C9H17O2 (M+H) :
m/z 157.1229. Found: m/z 157.1202.
4-Phenyl-γ-butyrolactone (3c, 4c)ꢁColorless oil; Rfꢀ=ꢀ0.15 (elu- (20 mL) was stirred at 40°C for a period specified in Table 3, then fil-
ent: n-hexane-EtOAc, 4:1, v/v); IR: 3033 (Ar, C-H), 2950 (CH2), 1776 tered to remove Novozym 435, and concentrated. The purification of
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