Full Paper
7.12–7.00 (m, 11 H), 5.45 (d, J = 6.1 Hz, 1 H), 5.00 (d, J = 6.1 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 165.6, 137.7, 134.4, 132.1,
129.1, 128.9, 128.2, 128.1, 127.8, 127.1 (2 C), 124.0, 117.2, 60.4,
60.3 ppm. trans-3c: H NMR (400 MHz, CDCl3): δ = 7.43–7.24 (m, 14
H), 7.10–7.03 (m, 1 H), 4.95 (d, J = 2.4 Hz, 1 H), 4.28 (d, J = 2.4 Hz,
3-Cyclohexyl-1,4-diphenylazetidin-2-one (3g):[21] Compound 3g
was prepared according to General Procedure A (reaction time:
24 h). The residue was purified by flash chromatography (AcOEt/
Hex, 3:97) to afford a white solid (65.0 mg, 21 %). 1H NMR indicated
the ratio of diastereomers as cis/trans = 78:22. HPLC analysis (Daicel
1
1 H) ppm. The spectroscopic data are in agreement with those re- Chiralpak IA column, eluent: iPrOH/Hex, 2:98, flow rate: 1.0 mL/min,
ported.[13e]
λ = 254 nm): cis isomer: 19.9 min (major), 15.5 min (minor); trans
isomer: 13.7 min (major), 17.4 min (minor); cis ee 60 %, trans ee
47 %. cis-3g: [α]D25 = +48.9 (c = 1.03, CHCl3, ee 60 %); m.p. 157–
158 °C. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.30 (m, 5 H), 7.28–7.24
(m, 2 H), 7.23–7.17 (m, 2 H), 7.02–6.96 (m, 1 H), 5.12 (d, J = 5.79 Hz,
1 H), 3.30 (dd, J1 = 11.1, J2 = 5.8 Hz, 1 H), 2.25–2.20 (m, 1 H), 1.71–
1.64 (m, 1 H), 1.54–1.44 (m, 2 H), 1.43–1.35 (m, 1 H), 1.22–1.04 (m,
4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.4, 137.6, 135.2, 128.9,
128.5, 128.3, 127.6, 123.5, 117.1, 60.4, 58.3, 34.8, 31.1, 30.7, 26.1,
25.6, 25.4 ppm. trans-3g: [α]D25 = +25.8 (c = 0.53, CHCl3, ee 47 %);
1,4-Diphenyl-3-(3,4,5-trimethoxyphenyl)azetidin-2-one
(3d):
Compound 3d was prepared according to General Procedure A (re-
action time: 48 h). The residue was purified by flash chromatogra-
phy (AcOEt/toluene, 1:9) to afford a white solid (217.5 mg, 56 %).
1H NMR indicated the ratio of diastereomers as cis/trans = 90:10.
HPLC analysis (Daicel Chiralpack IA column, eluent: iPrOH/Hex,
20:80, flow 0.6 mL/min, λ = 254 nm): cis isomer: 19.1 min (major),
33.5 min (minor); cis ee = 2 %. cis-3d: m.p. 155–157 °C. IR (CHCl3):
ν = 1747, 1462 cm–1. H NMR (400 MHz, CDCl3): δ = 7.43–7.39 (m,
1
1
˜
m.p. 114–115 °C. H NMR (400 MHz, CDCl3): δ = 7.36–7.20 (m, 9 H),
2 H), 7.31–7.25 (m, 2 H), 7.17–7.01 (m, 6 H), 6.24 (s, 2 H), 5.44 (d, J =
6.1 Hz, 1 H), 4.92 (d, J = 6.1 Hz, 1 H), 3.70 (s, 3 H), 3.66 (s, 6 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 165.5, 152.8, 137.7, 137.2, 134.6,
129.1, 128.3, 128.1, 127.6, 127.2, 124.1, 117.2, 106.2, 60.7, 60.3, 60.0,
56.0 (2 C) ppm. trans-3d: Selected signals: 1H NMR (400 MHz, CDCl3):
δ = 4.20 (d, J = 2.5 Hz, 1 H) ppm. HRMS (ESI): calcd. for C24H23NO4Na
[M + Na]+ 412.1525; found 412.1521.
7.04–6.98 (m, 1 H), 7.76 (d, J = 2.4 Hz, 1 H), 7.93 (dd, J1 = 8.2, J2 =
2.4 Hz, 1 H), 2.12–2.02 (m, 1 H), 1.95–1.83 (m, 2 H), 1.80–1.66 (m, 3
H), 1.36–1.10 (m, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.4,
138.5, 137.8, 129.1, 129.0, 128.1, 125.9, 123.6, 116.9, 66.3, 58.8, 38.3,
30.9, 30.7, 26.2, 25.9, 25.8 ppm. The spectroscopic data are in agree-
ment with those reported.[21]
3-(Cyclohex-1-en-1-yl)-1,4-diphenylazetidin-2-one
(3h):[13f]
3-(2-Methoxyphenyl)-1,4-diphenylazetidin-2-one (3e): Com-
pound 3e was prepared according to General Procedure A (reaction
time: 24 h). The residue was purified by flash chromatography
(AcOEt/Hex, 7:93) to afford a yellow solid (58.0 mg, 18 %). H NMR
indicated the ratio of diastereomers as cis/trans = 83:17. HPLC analy-
sis (Daicel Chiralpak IA column, eluent: iPrOH/Hex, 7:93, flow 1.0 mL/
Compound 3h was prepared according to General Procedure A (re-
action time: 48 h). The residue was purified by flash chromatogra-
1
phy (AcOEt/Hex, 5:95) to afford a yellow solid (212.0 mg, 70 %). H
1
NMR indicated the ratio of diastereomers cis/trans = 91:9. HPLC
analysis (Daicel Chiralpak IB column, eluent: iPrOH/Hex, 5:95, flow
rate: 1.0 mL/min, λ = 254 nm): cis isomer: 6.4 min (major), 10.7 min
(minor); cis ee 10 %. cis 3h: 1H NMR (400 MHz, CDCl3): δ = 7.32–7.36
(m, 2 H), 7.31–7.27 (m, 3 H), 7.26–7.20 (m, 4 H), 7.05–7.00 (m, 1 H),
6.88–7.83 (m, 1 H), 5.21 (d, J = 5.9 Hz, 1 H), 4.18 (d, J = 5.9 Hz, 1 H),
2.01–1.90 (m, 1 H), 1.84–173 (m, 1 H), 1.58–1.48 (m, 1 H), 1.35–1.20
(m, 3 H), 1.19–1.08 (m, 1 H), 0.99–0.87 (m, 1 H) ppm. trans 3h:
min, λ = 210 nm): cis isomer: 19.8 min (major), 22.4 min (minor); cis
1
ee 11 %; m.p. 126–128 °C. IR (CHCl3): ν = 1743, 1496 cm–1. H NMR
˜
(400 MHz, CDCl3): δ = 7.43 (d, J = 7.5 Hz, 1 H), 7.39 (d, J = 7.8 Hz,
2 H), 7.24 (t, J = 7.8 Hz, 2 H), 7.07–7.00 (m, 7 H), 6.77 (t, J = 7.5 Hz,
1 H), 6.46 (d, J = 8.2 Hz, 1 H), 5.42 (d, J = 5.9 Hz, 1 H), 5.14 (d, J =
5.9 Hz, 1 H), 3.58 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.1,
156.4, 137.8, 134.7, 129.1, 129.0, 128.7, 127.6, 127.5, 127.1, 123.8,
121.2, 120.0, 117.2, 109.4, 60.2, 56.0, 54.7 ppm. trans-3e: Selected
signals: 1H NMR (400 MHz, CDCl3): δ = 4.94 (d, J = 2.4 Hz, 1 H), 4.33
(d, J = 2.4 Hz, 1 H) ppm. HRMS (ESI): calcd. for C22H19NO2Na [M +
Na]+ 352.1313; found 352.1315.
1
Selected signals: H NMR (400 MHz, CDCl3): δ = 5.78 (m, 1 H), 4.81
(d, J = 2.6 Hz, 1 H), 3.62 (m, 1 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 165.9, 137.7, 134.7, 128.9, 128.0, 127.9, 127.6, 127.5, 123.8, 117.1,
61.8, 59.3, 28.0, 25.0, 22.0, 21.7 ppm. The spectroscopic data are in
agreement with those reported.[13f]
3-Cyclopropyl-1,4-diphenylazetidin-2-one (3i):[22] Compound 3i
was prepared according to General Procedure A (reaction time: 3 h).
3-Butyl-1,4-diphenylazetidin-2-one (3f):[9a] Compound 3f was
prepared according to General Procedure A (reaction time: 3 h). The The residue was purified by flash chromatography (AcOEt/Hex, 5:95)
residue was purified by flash chromatography (AcOEt/Hex, 5:95) to to afford a white solid (101.0 mg, 38 %). 1H NMR indicated the ratio
1
afford a white solid (41.4 mg, 15 %). H NMR indicated the ratio of
diastereomers as cis/trans = 67:33. HPLC analysis (Daicel Chiralpak
IB column, eluent: iPrOH/Hex, 1:99, flow 1.0 mL/min, λ = 254 nm):
cis isomer: 7.7 min (major), 14.3 min (minor); trans isomer: 9.4 min
of diastereomers cis/trans = 58:42. HPLC analysis (Daicel Chiralpak
IB column, eluent: iPrOH/Hex, 5:95, flow rate: 1.0 mL/min, λ =
254 nm): cis isomer: 11.1 min (major), 6.7 min (minor); cis ee 43 %.
HPLC: Daicel Chiralpak IA column (eluent: iPrOH/Hex, 1:99, flow rate:
1.0 mL/min, λ = 254 nm): trans isomer: 18.3 min (major), 20.9 min
(major), 6.9 min (minor); cis ee 42 %, trans ee 34 %. trans-3f: [α]D25
+33.6 (c = 1.01, CHCl3, ee 34 %); m.p. 82–85 °C. H NMR (400 MHz,
CDCl3): δ = 7.38–7.20 (m, 9 H), 7.07–6.99 (m, 1 H), 4.65 (d, J = 2.4 Hz, m.p. 127–129 °C. H NMR (400 MHz, CDCl3): δ = 7.38–7.20 (m, 9 H),
=
1
(minor); trans ee 21 %. cis-3i: [α]D25 = +91.9 (c = 0.40, CHCl3, ee 43 %);
1
1 H), 3.11–3.05 (m, 1 H), 2.01–1.91 (m, 1 H), 1.88–1.77 (m, 1 H), 1.54–
1.43 (m, 2 H), 1.40–1.30 (m, 2 H), 0.91 (t, J = 7.3 Hz, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 168.0, 138.3, 137.8, 124.1, 129.0, 128.3,
7.05–6.99 (m, 1 H), 4.75 (d, J = 2.4 Hz, 1 H), 2.84 (dd, J1 = 7.8, J2 =
2.4 Hz, 1 H), 1.24–1.15 (m, 1 H), 0.72–0.64 (m, 1 H), 0.64–0.56 (m, 1
H), 0.50–0.41 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.6,
125.8, 123.7, 116.9, 61.2, 60.7, 29.3, 28.6, 22.6, 13.8 ppm. cis-3f: 138.1, 137.7, 129.1, 129.0, 128.3, 125.7, 123.7, 117.0, 63.9, 61.1, 9.4,
[α]D25 = +57.6 (c = 1.06, CHCl3, ee 42 %); m.p. 107–109 °C. 1H NMR 3.1, 2.4 ppm. trans-3i: [α]D25 = 13.3 (c = 0.42, CHCl3, ee = 21 %); m.p.
(400 MHz, CDCl3): δ = 7.28–7.20 (m, 9 H), 7.05–6.99 (m, 1 H), 5.17
(d, J = 5.9 Hz, 1 H), 3.54 (dt, J1 = 7.8, J2 = 5.9 Hz, 1 H), 1.53–1.43 (m,
1 H), 1.35–1.25 (m, 1 H), 1.20–1.04 (m, 4 H), 0.72 (t, J = 6.9 Hz, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.2, 137.7, 135.1, 129.0,
128.6, 128.2, 127.2, 123.6, 117.1, 58.3, 54.7, 29.3, 24.9, 22.3,
13.6 ppm.
143–144 °C. 1H NMR (400 MHz, CDCl3): δ = 7.38–7.21 (m, 9 H), 7.07–
7.01 (m, 1 H), 5.17 (d, J = 5.9 Hz, 1 H), 3.17–3.09 (m, 1 H), 0.49–0.40
(m, 3 H), 0.20–0.09 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
166.7, 137.8, 135.7, 129.0, 128.5, 127.9, 127.0, 123.7, 117.2, 59.5, 58.7,
6.8, 3.8, 2.6 ppm. The spectroscopic data are in agreement with
those reported.[22]
Eur. J. Org. Chem. 2016, 2212–2219
2217
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim