4120
S. Mangelinckx et al. / Tetrahedron 66 (2010) 4115–4124
(dd,1H, J¼11.56 Hz, 4.68 Hz, CHN), 5.46 (br s,1H, NH), 6.89–6.94 (m,
3.30 (dd, 1H, J¼10.73 Hz, 7.15 Hz, CH(H)I), 3.36 (dd, 1H, J¼10.73 Hz,
4.95 Hz, CH(H)I), 3.82 (s, 3H, CH3O), 4.25 (dddd, 1H, J¼9.1 Hz,
7.15 Hz, 4.95 Hz, 3.03 Hz, CHO), 4.69–4.73 (m, 1H, CHN), 5.54 (br s,
1H, NH), 6.90–6.95 (m, 2H, Ar–H), 7.20–7.25 (m, 2H, Ar–H). 13C NMR
2H, Ar–H), 7.23–7.28 (m, 2H, Ar–H). 13C NMR (75 MHz, CDCl3):
d
¼32.6, 35.4, 54.7, 55.5, 75.8,114.6,127.5,132.1,153.0, 160.0. IR (ATR,
cmꢀ1):
n
¼3222 (NH), 3116, 1694 (C]O). MS (ES, MþHþ, pos): m/z
300/302 (MþHþ, 100). Anal. Calcd for C12H14BrNO3: C, 48.02; H,
(75 MHz, CDCl3):
d
¼5.3, 34.5, 51.7, 55.5, 72.8, 114.5, 127.0, 133.1,
4.70; N, 4.67. Found: C, 48.34; H, 4.36; N, 4.55.
153.3, 159.6. IR (ATR, cmꢀ1):
n
¼3245 (NH), 1664 (C]O). MS (ES,
MþHþ, pos): m/z 348 (MþHþ, 100). Anal. Calcd for C12H14INO3: C,
4.2.6. trans-6-(Bromomethyl)-4-(4-methoxyphenyl)-1,3-oxazinan-2-
one (10b). Isolated by column chromatography (diethyl ether).
White crystals; mp: 146.0–148.0 ꢁC; yield 11%. 1H NMR (300 MHz,
41.52; H, 4.06; N, 4.03. Found: C, 41.52; H, 3.70; N, 3.94.
4.2.11. 4-Phenyl-6-(phenylselanylmethyl)-1,3-oxazinan-2-one
(10e). Mixture of cis- and trans-isomer in a ratio 54/46, crystallized
from diethyl ether/hexane. Amorphous white solid; mp: 127.4–
CDCl3):
d
¼2.13 (dddd, 1H, J¼14.0 Hz, 4.1 Hz, 3.0 Hz, 1.0 Hz, 5-
CH(H)), 2.36 (ddd, 1H, J¼13.9 Hz, 9.2 Hz, 5.6 Hz, 5-CH(H)), 3.48 (dd,
1H, J¼10.7 Hz, 6.9 Hz, CH(H)Br), 3.53 (dd, 1H, J¼10.7 Hz, 5.0 Hz,
CH(H)Br), 3.82 (s, 3H, CH3O), 4.43 (dddd, 1H, J¼9.3 Hz, 6.8 Hz,
4.8 Hz, 2.7 Hz, CHO), 4.74 (m, 1H, CHN), 5.41 (br s, 1H, NH), 6.90–
6.95 (m, 2H, Ar–H), 7.21–7.24 (m, 2H, Ar–H). 13C NMR (75 MHz,
129.4 ꢁC; yield 79%. 1H NMR (300 MHz, CDCl3):
d¼1.75 (dt, 1H,
J¼13.76 Hz, 11.56 Hz, 5-CH(H)cis), 2.23–2.27 (m, 2H, 5-CH(H)trans),
2.51 (ddt, 1H, J¼13.76 Hz, 4.68 Hz, 1.8 Hz, 5-CH(H)cis), 2.95 (dd, 1H,
J¼12.80 Hz, 9.2 Hz, CH(H)Setrans), 2.98 (dd, 1H, J¼12.93 Hz, 8.53 Hz,
CH(H)Secis), 3.24 (dd, 1H, J¼12.93 Hz, 4.68 Hz, CH(H)Setrans), 3.33
(dd, 1H, J¼12.93 Hz, 4.68 Hz, CH(H)Secis), 4.24–4.34 (m, 1H, CHO-
trans), 4.50 (dddd,1H, J¼11.39 Hz, 8.6 Hz, 4.7 Hz, 2.0 Hz, CHOcis), 4.56
(dd, 1H, J¼11.42 Hz, 4.5 Hz, CHNcis), 4.64–4.68 (m, 1H, CHNtrans),
5.32 (br s, 1H, NHcis), 5.60 (br s, 1H, NHtrans), 7.16–7.54 (m, 20H, Ar–
CDCl3):
d
¼32.2, 32.9, 51.8, 55.5, 72.5, 114.5, 127.0, 133.1, 153.1, 159.6.
IR (ATR, cmꢀ1):
n
¼3242 (NH), 3125, 1674 (C]O). MS (ES, MþHþ,
pos): m/z 300/302 (MþHþ, 100). Anal. Calcd for C12H14BrNO3: C,
48.02; H, 4.70; N, 4.67. Found: C, 48.40; H, 4.58; N, 4.58.
4.2.7. cis-6-(Iodomethyl)-4-phenyl-1,3-oxazinan-2-one
(10c). Isolated bycolumn chromatography (diethyl ether). Colourless
crystals; mp: 181.5–183.5 ꢁC; yield 31%. 1H NMR (300 MHz, CDCl3):
Hcisþtrans). 13C NMR (75 MHz, CDCl3):
¼30.6, 31.2, 33.4, 36.2, 52.6,
d
55.6, 73.5, 76.7 (overlap with signal from CDCl3), 125.9, 126.2, 127.7,
127.9, 128.2, 128.8, 129.1, 129.3, 129.4, 129.5, 132.9, 134.0, 140.5,
d
¼1.80 (dt, 1H, J¼13.76 Hz, 11.56 Hz, 5-CH(H)), 2.52 (ddt, 1H,
141.5, 153.6, 153.7. IR (ATR, cmꢀ1):
n
¼3211 (NH), 3109, 1686 (C]O).
J¼13.76 Hz, 4.40 Hz, 1.93 Hz, 5-CH(H)), 3.29 (dd, 1H, J¼10.46 Hz,
7.43 Hz, CH(H)I), 3.43 (dd, 1H, J¼10.46 Hz, 4.40 Hz, CH(H)I), 4.44
(dddd, 1H, J¼11.56 Hz, 7.02 Hz, 4.54 Hz, 2.3 Hz, CHO), 4.63 (dd, 1H,
J¼11.56 Hz, 4.68 Hz, CHN), 5.25(br s,1H, NH), 7.31–7.45 (m, 5H, C6H5).
MS (ES, MþHþ, pos): m/z 348/346 (MþHþ, 100). Anal. Calcd for
C17H17NO2Se: C, 58.96; H, 4.95; N, 4.04. Found: C, 59.08; H, 4.56;
N, 4.02.
13C NMR (75 MHz, CDCl3):
d¼5.5, 36.9, 55.2, 76.1, 126.2, 129.0, 129.3,
4.2.12. 4-(Methoxyphenyl)-6-(phenylselanylmethyl)-1,3-oxazinan-2-
one (10f). Mixture of cis- and trans-isomer in a ratio 58/42, crys-
tallized from diethyl ether/hexane. Amorphous white solid; mp:
140.2, 153.1. IR (ATR, cmꢀ1):
n¼3223 (NH), 3121, 1696 (C]O). MS (ES,
MþHþ, pos): m/z 318 (MþHþ, 100). Anal. Calcd for C11H12INO2: C,
41.66; H, 3.81; N, 4.42. Found: C, 41.52; H, 3.45; N, 4.29.
93.1–95.1 ꢁC; yield 85%. 1H NMR (300 MHz, CDCl3):
d¼1.74 (dt, 1H,
J¼13.76 Hz, 11.56 Hz, 5-CH(H)cis), 2.18–2.24 (m, 2H, 5-CH(H)trans),
2.47 (ddt, 1H, J¼13.76 Hz, 4.40 Hz, 1.9 Hz, 5-CH(H)cis), 2.97 (dd, 1H,
J¼12.80 Hz, 9.2 Hz, CH(H)Setrans), 2.98 (dd, 1H, J¼13.07 Hz, 8.4 Hz,
CH(H)Secis), 3.26 (dd,1H, J¼12.80 Hz, 4.5 Hz, CH(H)Setrans), 3.33 (dd,
1H, J¼12.93 Hz, 4.68 Hz, CH(H)Secis), 3.81 (s, 3H, CH3Ocis), 3.82 (s,
3H, CH3Otrans), 4.27–4.35 (m, 1H, CHOtrans), 4.44–4.53 (m, 1H,
CHOcis), 4.51 (dd, 1H, J¼11.28 Hz, 4.3 Hz, CHNcis), 4.57–4.62 (m, 1H,
CHNtrans), 5.15 (br s, 1H, NHcis), 5.38 (br s, 1H, NHtrans), 6.86–7.54 (m,
4.2.8. trans-6-(Iodomethyl)-4-phenyl-1,3-oxazinan-2-one
(10c). Isolated by column chromatography (diethyl ether). Amor-
phous white solid; mp: 158.0–160.0 ꢁC; yield 16%.1H NMR (300 MHz,
CDCl3):
d
¼2.20 (dddd, 1H, J¼13.9 Hz, 4.0 Hz, 3.0 Hz, 1.0 Hz, 5-CH(H)),
2.37 (ddd, 1H, J¼13.9 Hz, 9.2 Hz, 5.8 Hz, 5-CH(H)), 3.31 (dd, 1H,
J¼10.73 Hz, 6.88 Hz, CH(H)I), 3.36 (dd, 1H, J¼10.73 Hz, 4.95 Hz,
CH(H)I),4.24(dddd,1H, J¼9.2 Hz, 7.1 Hz,5.0 Hz,3.0 Hz,CHO), 4.76(dt,
1H, J¼5.8 Hz, 3.6 Hz, CHN), 5.40(brs,1H, NH), 7.30–7.45(m, 5H, C6H5).
18H, Ar–Hcisþtrans). 13C NMR (75 MHz, CDCl3):
¼30.6, 31.3, 33.4,
d
13C NMR (75 MHz, CDCl3):
d¼5.3, 34.4, 52.3, 72.7, 125.8, 128.4, 129.2,
36.3, 51.9, 55.0, 55.5, 73.6, 76.6, 114.3, 114.5, 127.1, 127.4, 127.6, 127.9,
128.6, 129.2, 129.4, 129.5, 132.4, 132.8, 133.5, 133.9, 153.8, 153.9,
141.2, 153.2. IR (ATR, cmꢀ1):
n¼3322 (NH), 1662 (C]O). MS (ES,
MþHþ, pos): m/z 318 (MþHþ, 100). Anal. Calcd for C11H12INO2: C,
159.4, 159.9. IR (ATR, cmꢀ1):
n
¼3225 (NH), 3102, 1685 (C]O). MS
41.66; H, 3.81; N, 4.42. Found: C, 41.99; H, 3.50; N, 4.33.
(ES, MþHþ, pos): m/z 378/376 (MþHþ, 100). Anal. Calcd for
C18H19NO3Se: C, 57.45; H, 5.09; N, 3.72. Found: C, 57.46; H, 5.10;
N, 3.72.
4.2.9. cis-6-(Iodomethyl)-4-(4-methoxyphenyl)-1,3-oxazinan-2-one
(10d). Isolated by column chromatography (diethyl ether). White
amorphous solid; mp: 159.4–161.4 ꢁC; yield 29%. 1H NMR (300 MHz,
4.2.13. Alternative procedure for the preparation of 4-aryl-1,3-ox-
azinan-2-ones 10. To a solution of homoallylamine 9 (1 mmol) in
dichloromethane (20 mL) at 0 ꢁC, TBDMSOTf (0.79 g, 3 mmol) and
2,6-lutidine (0.43 g, 4 mmol) were added. After stirring for 2 h at
0 ꢁC, a solution of electrophile (2.44 mmol) in freshly distilled dry
dichloromethane (10 mL) was added dropwise and the mixture was
stirred at 0 ꢁC under nitrogen atmosphere for 16–24 h. After typical
workup, the mixture was purified by column chromatography
(EtOAc) to afford 4-aryl-1,3-oxazinan-2-ones 10 as a mixture of
trans- and cis-isomers.
CDCl3):
d
¼1.78 (dt, 1H, J¼14.03 Hz, 11.4 Hz, 5-CH(H)), 2.47 (dddd, 1H,
J¼13.76 Hz, 4.40 Hz, 2.0 Hz, 2.0 Hz, 5-CH(H)), 3.28 (dd,1H, J¼10.59 Hz,
7.3 Hz, CH(H)I), 3.43 (dd, 1H, J¼10.59 Hz, 4.5 Hz, CH(H)I), 3.82 (s, 3H,
CH3O), 4.41 (dddd, 1H, J¼11.28 Hz, 7.1 Hz, 4.6 Hz, 2.0 Hz, CHO), 4.57
(dd, 1H, J¼11.56 Hz, 4.40 Hz, CHN), 5.31 (br s, 1H, NH), 6.89–6.94 (m,
2H, Ar–H), 7.23–7.28 (m, 2H, Ar–H). 13C NMR (75 MHz, CDCl3):
d¼5.7,
37.0, 54.6, 55.5, 76.0, 114.6, 127.5, 132.1, 153.3, 160.0. IR (ATR, cmꢀ1):
n
¼3249(NH), 3113,1682(C]O). MS(ES, MþHþ, pos):m/z348 (MþHþ,
100). Anal. Calcd for C12H14INO3: C, 41.52; H, 4.06; N, 4.03. Found: C,
41.56; H, 3.75; N, 4.01.
4.2.14. General procedure for the preparation of benzyl N-benzyl-N-
(1-phenyl-3-butenyl)carbamates 11. Benzyl bromide (60 mmol) was
added to a solution of sodium iodide in acetone (80 mL). The
mixture was stirred for 24 h in the dark at room temperature,
quenched with water (50 mL) and extracted with Et2O (2ꢂ100 mL).
The combined organic layers were dried (MgSO4), filtered and
4.2.10. trans-6-(Iodomethyl)-4-(4-methoxyphenyl)-1,3-oxazinan-2-
one (10d). Isolated by column chromatography (diethyl ether).
Amorphous white solid; mp: 157.2–159.2 ꢁC; yield 7%. 1H NMR
(300 MHz, CDCl3):
d¼2.16 (dddd, 1H, J¼13.9 Hz, 4.2 Hz, 3.1 Hz,
0.9 Hz, 5-CH(H)), 2.33 (ddd, 1H, J¼14.1 Hz, 8.9 Hz, 5.4 Hz, 5-CH(H)),