L-LYSINE–CATALYZED KNOEVENAGEL CONDENSATION
1625
=
J ¼ 11.7 Hz), 7.41 d (2H, Ph, J ¼ 1.9 Hz), 7.34–7.33 m (3H, Ph), 7.14 d (1H, PhCH ,
=
J ¼ 15.4 Hz), 6.90 dd (1H, PhCH CH-CH, J1 ¼ 11.8 Hz, J2 ¼ 15.3 Hz), 4.18 q (2H,
OCH2, J ¼ 7.1 Hz), 1.13 t (3H, CH3, J ¼ 7.1 Hz). 13C NMR spectrum, dC, ppm:
192.7, 164.7, 150.3, 146.1, 145.8, 142.1, 135.1, 130.1, 129.8, 129.6, 128.8, 127.8,
123.8, 122.3, 61.4, 13.9. HRMS-ESI: m=z [M þ Na]þ calcd. for C20H17NO5Na
374.0999; found 374.1001.
(2E,4E)-Ethyl(2-(p-nitrobenzoyl)-5-(p-methoxyphenyl))-2,4-pentadieno-
1
ate (p11). Yellow solid, mp 143–145 ꢁC. H NMR spectrum, d, ppm: 8.32 d (2H,
p-nitrophenyl, J ¼ 8.1 Hz), 8.02 d (2H, p-nitrophenyl, J ¼ 8.2 Hz), 7.78 d (1H,
=
R3CH CR4R5, J ¼ 11.8 Hz), 7.38 d (2H, p-methoxyphenyl, J ¼ 8.2 Hz), 7.10 d
=
=
(1H, PhCH , J ¼ 15.3 Hz), 6.87–6.77 m (3H, p-methoxyphenyl and PhCH CH-
CH), 4.17 q (2H, OCH2, J ¼ 6.9 Hz), 3.82 (3H, s, OCH3), 1.12 t (3H, CH3,
J ¼ 7.0 Hz). 13C NMR spectrum, dC, ppm: 192.9, 165.0, 161.4, 150.3, 147.0, 145.9,
142.5, 129.8, 129.6, 128.1, 123.8, 123.6, 120.4, 114.4, 61.3, 55.4, 14.0. HRMS-ESI:
m=z [M þ Na]þ calcd. for C21H19NO6Na 404.1105; found 404.1107.
Diethyl-2-((E)-3-p-tolylallylidene) malonate (p14). Yellow solid, mp
1
ꢁ
=
61–66 C. H NMR spectrum, d, ppm: 7.53 d (1H, R3CH CR4R5, J ¼ 11.5 Hz),
=
7.40 d (2H, p-tolyl, J ¼ 7.8 Hz), 7.34–7.22 m (1H, p-tolylCH CH-CH), 7.18 d (2H,
=
p-tolyl, J ¼ 7.2 Hz), 7.02 d (1H, p-tolylCH , J ¼ 15.4 Hz), 4.37 q (2H, OCH2,
J ¼ 7.1 Hz), 4.28 q (2H, OCH2, J ¼ 7.0 Hz), 2.37 s (3H, p-tolylCH3), 1.38 t (3H,
CH3, J ¼ 7.1 Hz), 1.33 t (3H, CH3, J ¼ 7.0 Hz). 13C NMR spectrum, dC, ppm:
165.4, 164.8, 145.6, 144.7, 140.2, 132.9, 129.5, 127.8, 124.2, 122.3, 61.2, 21.4, 14.2.
HRMS: m=z [M þ Na]þ calcd. for C17H20O4Na 311.1254; found 311.1255.
(2E,4E)-Ethyl(2-benzoyl-5-p-tolyl)-2,4-pentadienoate (p15). Yellow solid,
1
mp 71–75 ꢁC. H NMR spectrum, d, ppm: 7.91 d (2H, phenyl, J ¼ 8.0 Hz), 7.70 d
=
(1H, R3CH CR4R5, J ¼ 11.7 Hz), 7.59–7.45 m (3H, phenyl), 7.28 d (2H, p-tolyl,
=
J ¼ 8.1 Hz), 7.11 d (2H, p-tolyl, J ¼ 7.7 Hz), 7.02 d (1H, p-tolylCH , J ¼ 15.4 Hz),
=
6.78 dd (1H, p-tolylCH CH-CH, J1 ¼ 11.8 Hz, J2 ¼ 15.1 Hz), 4.18 q (2H, OCH2,
J ¼ 7.1 Hz), 2.32 s (3H, p-tolylCH3), 1.13 t (3H, CH3, J ¼ 7.1 Hz). 13C NMR spec-
trum, dC, ppm: 194.4, 165.2, 144.4, 144.1, 140.0, 137.2, 133.5, 132.7, 130.6, 129.5,
129.1, 128.6, 127.6, 121.9, 61.0, 21.4, 13.9. HRMS-ESI: m=z [M þ Na]þ calcd. for
C21H20O3Na 343.1305; found 343.1307.
(2E,4E)-Ethyl(2-p-nitrobenzoyl-5-p-tolyl)-2,4-pentadienoate (p16). Yel-
1
low solid, mp 131–134 ꢁC. H NMR spectrum, d, ppm: 8.32 d (2H, p-nitrophenyl,
=
J ¼ 8.5 Hz), 8.03 d (2H, p-nitrophenyl, J ¼ 8.4 Hz), 7.78 d (1H, R3CH CR4R5,
J ¼ 11.7 Hz), 7.32 d (2H, p-tolyl, J ¼ 7.8 Hz), 7.13 d (2H, p-tolyl, J ¼ 7.3 Hz), 7.09
=
=
(1H, p-tolylCH ), 6.87 dd (1H, p-tolylCH CH-CH, J1 ¼ 11.9 Hz, J2 ¼ 14.9 Hz),
4.17 q (2H, OCH2, J ¼ 7.0 Hz), 2.34 s (3H, p-tolylCH3), 1.12 t (3H, CH3, J ¼ 7.1 Hz).
13C NMR spectrum, dC, ppm: 192.8, 164.8, 150.2, 146.6, 146.0, 142.2, 140.6, 132.4,
129.7, 129.6, 128.8, 127.8, 123.8, 121.4, 61.3, 21.4, 13.9. HRMS-ESI: m=z [M þ Na]þ
calcd. for C21H19NO5Na 388.1155; found 388.1148.
Diethyl-2-((E)-3-p-chlorophenylallylidene)malonate (p19). White solid,
1
ꢁ
=
mp 75–76 C. H NMR spectrum, d, ppm: 7.50 d (1H, R3CH CR4R5, J ¼ 11.5 Hz),
7.43 d (2H, p-chlorophenyl, J ¼ 8.4 Hz), 7.34 d (2H, p-chlorophenyl, J ¼ 8.4 Hz), 7.23