C.-Y. Lee et al. / Tetrahedron 68 (2012) 5898e5907
5905
7bl was obtained by recrystallization from Hex/MeOH. Mp
239e241 ꢁC (dec) (Hex/MeOH); 1H NMR (DMSO-d6, 400 MHz)
2.34
reaction was purified by flash column chromatography (Hex/
EtOAc¼9:1, Rf¼0.25) to give the product (8ae, 29%). Mp 164e165 ꢁC;
d
(s, 3H, CH3), 3.10 (s, 3H, CH3), 7.14e7.22 (m, 2H), 7.31 (s, 1H, C]CH),
7.47 (d, 1H, J¼7.6 Hz), 8.19 (d, 1H, J¼7.6 Hz), 8.39 (d, 1H, J¼2.0 Hz),
1H NMR (DMSO-d6, 400 MHz)
d 4.98 (s, 2H, CH2), 7.07e7.09 (m, 2H),
7.22e7.28 (m, 4H), 7.48e7.60 (m, 5H), 7.73 (d, 2H, J¼7.4 Hz), 8.33 (d,
11.92 (bs, 1H, NH); 13C NMR (DMSO-d6, 100 MHz)
d
15.3 (CH3), 26.2
2H, J¼8.4 Hz); 13C NMR (DMSO-d6,100 MHz)
d 44.5 (CH2),126.1 (CH),
(CH3), 111.1, 112.1 (CH),119.4 (CH),119.6 (CH), 120.7 (CH), 122.5 (CH),
126.7, 132.7 (CH), 134.0, 136.4, 159.3, 169.2; MS (EI) m/z 56 (18), 239
(100) (Mþ); HRMS Calcd for C14H13N3O: 239.1059. Found 239.1060.
126.3 (CH),127.4 (CH),128.3 (CH),128.7 (CH),128.8 (CH),128.9 (CH),
131.7 (CH), 132.9, 133.8 (CH), 135.1, 136.6, 138.8, 163.1, 170.6; MS (EI)
m/z 91 (100), 372 (88) (Mþ), 374 (29) (Mþ2); HRMS (EI) Calcd for
C23H17N2OCl:372.1029. Found 372.1031.
4-Benzylidene-1-benzyl-2-phenylimidazol-5-one (8aa). Compound
8aa was prepared by the general procedure E. The reaction was
purified by flash column chromatography (Hex/EtOAc¼9:1,
Rf¼0.20) to give the product (8aa, 54%). An analytical sample of 8aa
was obtained by recrystallization from Hex/EtOAc. Mp 138e139 ꢁC
4-(4-Bromobenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8af). Compound 8af was prepared by the general procedure E. The
reaction was purified by flash column chromatography (Hex/
EtOAc¼9:1, Rf¼0.25) to give the product (8af, 44%). Mp 166e168 ꢁC;
(Hex/EtOAc); 1H NMR (DMSO-d6, 400 MHz)
d
4.98 (s, 2H, CH2),
7.07e7.09 (m, 2H), 7.27e7.28 (m, 4H), 7.46e7.51 (m, 6H), 7.73e7.75
(m, 2H), 8.31e8.33 (m, 2H); 13C NMR (DMSO-d6, 100 MHz)
44.5
1H NMR (DMSO-d6, 400 MHz)
d 4.98 (s, 2H, CH2), 7.08 (d, 2H,
J¼8.0 Hz), 7.23e7.31 (m, 4H), 7.49e7.53 (m, 2H), 7.58e7.60 (m, 1H),
d
7.69e7.75 (m, 4H), 8.26 (d, 2H, J¼8.0 Hz); 13C NMR (DMSO-d6,
(CH2), 126.3 (CH), 127.4 (CH), 127.8 (CH), 128.3 (CH), 128.7 (CH),
128.8 (CH), 129.0, 130.5 (CH), 131.6 (CH), 132.4 (CH), 134.0, 136.6,
138.5, 162.7, 170.7; MS (EI) m/z 338 (100) (Mþ); HRMS Calcd for
C23H18N2O: 338.1419. Found 338.1416.
100 MHz) d 44.5 (CH2), 124.1, 126.2 (CH), 126.3 (CH), 127.3 (CH), 128.3
(CH), 128.7 (CH), 128.8 (CH), 131.7 (CH), 131.8 (CH), 133.2, 134.0 (CH),
136.5,138.9,163.2,170.6; MS (EI) m/z 91 (100), 416 (32) (Mþ), 418 (34)
(Mþ2); HRMS (EI) Calcd for C23H17N2OBr:416.0524. Found 416.0528.
4-(4-Methoxybenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8ab). Compound 8ab was prepared by the general procedure E.
The reaction was purified by flash column chromatography (Hex/
EtOAc¼9:1, Rf¼0.13) to give the product (8ab, 15%). Mp 160e162 ꢁC;
4-(4-Nitrobenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8ag). Compound 8ag was prepared by the general procedure E.
The reaction was purified by flash column chromatography (Hex/
EtOAc¼8:2, Rf¼0.27) to give the product (8ag, 63%). An analytical
sample of 8ag was obtained by recrystallization from Hex/MeOH.
1H NMR (DMSO-d6, 400 MHz)
d 3.83 (s, 3H, OCH3), 4.98 (s, 2H, CH2),
7.05e7.08 (m, 4H), 7.22e7.30 (m, 4H), 7.48e7.51 (m, 2H), 7.55e7.57
Mp 188e190 ꢁC (Hex/MeOH); 1H NMR (DMSO-d6, 400 MHz)
d 4.99
(m, 1H), 7.73 (d, 2H, J¼7.4 Hz), 8.31 (d, 2H, J¼8.7 Hz); 13C NMR
(s, 2H, CH2), 7.10 (d, 2H, J¼7.7 Hz), 7.24e7.31 (m, 3H), 7.36 (s, 1H, C]
(DMSO-d6,100 MHz) d 44.4 (CH2), 55.4 (CH3),114.5 (CH),126.3 (CH),
CH), 7.51e7.62 (m, 3H), 7.77 (d, 2H, J¼7.3 Hz), 8.29 (d, 2H, J¼8.8 Hz),
126.8, 127.3 (CH), 128.0 (CH), 128.3 (CH), 128.7 (CH), 128.8 (CH),
129.1 (CH), 131.4 (CH), 134.4 (CH), 136.5, 136.8, 161.2, 161.3, 170.6;
MS (EI) m/z 91 (57) 368 (100) (Mþ); HRMS (EI) Calcd for
C24H20N2O2:368.1525. Found 368.1519.
8.54 (d, 2H, J¼8.8 Hz); 13C NMR (DMSO-d6, 100 MHz)
d 44.7 (CH2),
123.7 (CH), 124.2 (CH), 126.3 (CH), 127.4 (CH), 128.46 (CH), 128.52,
128.7, 128.8 (CH), 132.1 (CH), 132.9 (CH), 136.4, 140.4, 141.0, 147.4,
165.0, 170.6; MS (EI) m/z 91 (18), 383 (100) (Mþ); HRMS Calcd for
C23H17N3O3: 383.1270. Found 383.1274.
4-(4-Dimethylaminobenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8ac). Compound 8ac was prepared by the general procedure E.
The reaction was purified by flash column chromatography (CH2Cl2,
Rf¼0.38) to give the product (8ac, 42%). An analytical sample of 8ac
was obtained by recrystallization from EtOAc. Mp 195e197 ꢁC
Methyl 2-(2-acetamido-3-phenylacrylamido)acetate (N-AceDPhee
GlyeOMe)56,68 (13). Compound 13 was prepared by the general
procedure C. The reaction was purified by flash column chroma-
tography (EtOAc, Rf¼0.20) to give the product as a solid (13, 93%). Mp
(EtOAc); 1H NMR (DMSO-d6, 400 MHz)
d
3.03 (s, 6H, CH3), 4.98 (s,
128e132 ꢁC; 1H NMR (DMSO-d6, 400 MHz)
d 2.00 (s, 3H, CH3), 3.64
2H, CH2), 6.79 (d, 2H, J¼8.4 Hz), 7.06 (d, 2H, J¼7.3 Hz), 7.16 (s, 1H),
7.22 (d, 1H, J¼7.2 Hz), 7.26e7.30 (m, 2H), 7.46e7.48 (m, 2H), 7.53 (d,
1H, J¼6.5 Hz), 7.70 (d, 2H, J¼7.5 Hz), 8.18 (d, 2H, J¼8.2 Hz); 13C NMR
(s, 3H, OCH3), 3.89 (d, 2H, J¼5.8 Hz, CH2), 7.13 (s, 1H, C]CH),
7.33e7.35 (m, 1H), 7.38e7.42 (m, 2H), 7.55 (d, 2H, J¼7.6 Hz), 8.39 (t,
1H, J¼5.7 Hz, NH), 9.44 (s, 1H, NH); 13C NMR (DMSO-d6, 100 MHz)
(DMSO-d6, 100 MHz)
d
40.1 (CH3), 44.8 (CH2), 112.3 (CH), 122.0,
d 22.8 (CH3), 41.2 (CH2), 51.6 (CH3),128.5 (CH),128.7 (CH),128.9 (CH),
126.8 (CH),127.7 (CH),128.6 (CH),129.1 (CH),129.2 (CH),130.0 (CH),
131.4 (CH), 134.5, 135.0 (CH), 137.6, 152.2, 159.1, 170.8; MS (EI) m/z
91 (40), 290 (55), 381 (100) (Mþ); HRMS Calcd for C25H23N3O:
381.1841. Found 381.1842.
129.3,134.0,165.3,169.4,170.2; MS (EI) m/z 234 (100), 276 (22) (Mþ).
Methyl 2-(2-acetamido-3-(4-acetoxyphenyl)acrylamido)acetate (N-
AceD
Tyr(OAc)eGlyeOMe)56 (14). Compound 14 was prepared by
the general procedure C. The reaction was purified by flash column
chromatography (Hex/EtOAc¼2:8, Rf¼0.08) to give the product as
a solid (14, 70%). Mp 110e114 ꢁC (dec); 1H NMR (DMSO-d6,
4-(4-Hydroxybenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8ad). Compound 8ad was prepared by the general procedure E.
The reaction was purified by flash column chromatography (Hex/
EtOAc¼7:3, Rf¼0.18) to give the product (8ad, 40%). An analytical
sample of 8ad was obtained by recrystallization from Hex/EtOAc.
400 MHz)
d 2.00 (s, 3H, CH3), 2.26 (s, 3H, OAc), 3.63 (s, 3H, OCH3),
3.88 (d, 2H, J¼5.8 Hz, CH2), 7.13 (s, 1H, C]CH), 7.15 (d, 2H, J¼8.6 Hz),
7.58 (d, 2H, J¼8.6 Hz), 8.43 (t,1H, J¼5.8 Hz, NH), 9.48 (s,1H, NH); 13C
Mp 248e250 ꢁC (Hex/EtOAc); 1H NMR (DMSO-d6, 400 MHz)
d
4.97
NMR (DMSO-d6, 100 MHz) d 21.0 (CH3), 23.0 (CH3), 41.4 (CH2), 51.9
(s, 2H, CH2), 6.88 (d, 2H, J¼8.8 Hz), 7.06 (d, 2H, J¼6.8 Hz), 7.19e7.30
(CH3), 122.2 (CH), 128.3 (CH), 129.3, 130.8 (CH), 131.7, 150.7, 165.6,
169.4, 169.9, 170.5; MS (EI) m/z 203 (23), 250 (39), 274 (100), 316
(50), 317 (22), 334 (18) (Mþ).
(m, 4H), 7.47e7.58 (m, 3H), 7.71 (d, 2H, J¼7.2 Hz), 8.20 (d, 2H,
J¼8.8 Hz), 10.33 (bs, 1H, OH); 13C NMR (DMSO-d6, 100 MHz)
d 44.8
(CH2), 116.5 (CH), 125.8, 126.7 (CH), 127.8 (CH), 128.7 (CH), 129.16
(CH), 129.24 (CH), 129.7, 131.8 (CH), 135.3 (CH), 136.2, 137.3, 160.7,
161.1, 171.1; MS (EI) m/z 354 (100) (Mþ); HRMS Calcd for
C23H18N2O2: 354.1368. Found 154.1377.
Methyl 2-(2-acetamido-3-(4-acetoxyphenyl)acrylamido)propionate
(N-AceD
Tyr(OAc)eAlaeOMe)69e71 (15). Compound 15 was pre-
pared by the general procedure C. The reaction was purified by flash
column chromatography (Hex/EtOAc¼1:9, Rf¼0.15) to give the
product as a solid (15, 40%). Mp 141e144 ꢁC (dec); 1H NMR (DMSO-
4-(4-Chlorobenzylidene)-1-benzyl-2-phenylimidazol-5-one
(8ae). Compound 8ae was prepared by the general procedure E. The
d6, 400 MHz)
d
1.32 (d, 3H, J¼7.2 Hz, CH3), 1.99 (s, 3H, CH3), 2.26 (s,