The Journal of Organic Chemistry
ARTICLE
121.3, 123.2, 123.9, 126.1, 126.7, 126.9, 128.0, 128.3, 128.7, 128.9, 129.9,
130.4, 132.2, 134.2, 135.1, 135.9, 137.7, 138.1, 140.4, 143.2, 145.5, 152.4,
167.1, 169.3, 173.0 ppm. MS (EI, m/z): 531 [M]+. HRMS (EI): calcd for
C30H23N3NiO3 [M]+ 531.1093; found 531.1092.
131.0, 134.3, 134.8, 135.2, 135.5, 135.6, 136.5, 140.5, 141.1, 143.3, 145.4,
152.4, 159.5, 166.7, 169.3, 173.3 ppm. MS (EI, m/z): 568 [M]+. HRMS
(EI): calcd for C32H22N4NiO3 [M]+ 568.1045; found 568.1053.
Ni(II)-PABP/2-(Aminomethylene)butanoic Acid Schiff
Base Complex 4o. Dark-red solid. Mp 182À184 °C. 1H NMR
(CDCl3, 300 MHz): δ 8.53 (d, J = 8.4 Hz, 1H), 8.27 (d, J = 5.1 Hz,
1H), 8.01À7.96 (m, 1H), 7.90 (d, J = 7.8 Hz, 1H), 7.57À7.45 (m, 4H),
7.39À7.34 (m, 1H), 7.12 (d, J = 6.6 Hz, 2H), 6.80 (d, J = 4.5 Hz, 2H),
6.32 (s, 1H), 2.19 (q, J = 7.2 Hz, 2H), 0.88 (t, J = 7.2 Hz, 3H) ppm. 13C
NMR (CDCl3, 100 MHz): δ 12.7, 24.7, 121.3, 123.2, 123.9, 126.7,
128.2, 128.9, 129.3, 130.8, 134.1, 135.1, 136.1, 138.4, 140.4, 143.2, 145.6,
152.5, 172.6 ppm. MS (EI, m/z): 455 [M]+. HRMS (EI): calcd for
C24H19N3NiO3 [M]+ 455.0780; found 455.0787.
Ni(II)-PABP/2-(Aminomethylene)-6,6,6-trifluorohexanoic
Acid Schiff Base Complex 4p. Dark-red solid. Mp 215À217 °C. 1H
NMR (CDCl3, 300 MHz): δ 8.54 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 4.2 Hz,
1H), 8.00 (t, J = 7.5 Hz, 1H), 7.91 (d, J = 6.9 Hz, 1H), 7.56À7.47
(m, 5H), 7.40À7.34 (m, 1H), 7.12 (d, J = 6.6 Hz, 2H), 6.80 (d, J = 6.0
Hz, 2H), 6.35 (s, 1H), 2.19 (t, J = 7.5 Hz, 2H), 2.04À1.95 (m, 2H),
1.66À1.61 (m, 2H) ppm. 13C NMR (CDCl3, 100 MHz): δ 21.2, 30.5,
33.2, 121.4, 123.2, 124.0, 126.8, 128.0, 129.1, 131.0, 134.4, 135.3, 136.0,
139.5, 140.5, 143.4, 145.5, 152.4, 166.7, 169.4, 173.3 ppm. MS (EI, m/z):
537 [M]+. HRMS (EI): calcd for C26H20F3N3NiO3 [M]+ 537.0810;
found 537.0823.
Ni(II)-PABP/2-(Aminomethylene)hexanoic Acid Schiff Base
Complex 4q. Dark-red solid. Mp 167À170 °C. 1H NMR (CDCl3, 300
MHz): δ 8.53 (d, J = 8.4 Hz, 1H), 8.28 (d, J = 4.2 Hz, 1H), 8.01À7.96
(m, 1H), 7.90 (d, J = 7.5 Hz, 1H), 7.57À7.48 (m, 4H), 7.38À7.35
(m, 1H), 7.11 (d, J = 6.6 Hz, 2H), 6.81À6.76 (m, 2H), 6.27 (s, 1H), 2.12
(t, J = 6.6 Hz, 2H), 1.67À1.63 (m, 2H), 0.95À0.86 (m, 2H), 0.81
(t, J = 6.9 Hz, 3H) ppm. 13C NMR (CDCl3, 125 MHz): δ 13.9, 22.5,
30.7, 31.4, 121.3, 123.2, 123.9, 126.7, 128.3, 129.0, 129.3, 130.8, 134.2,
135.2, 136.1, 138.6, 140.5, 143.2, 145.6, 152.6, 169.4, 172.5 ppm. MS
(ESI, m/z): 484 [M + H]+. HRMS (EI): calcd for C26H24N3NiO3
[M + H]+ 484.1171; found 484.1147.
Ni(II)-PABP/3-Amino-2-(4-methylbenzyl)acrylic Acid Schiff
Base Complex 4i. Dark-red solid. Mp 69À71 °C. 1H NMR (CDCl3,
300 MHz): δ 8.51 (d, J = 6.0 Hz, 1H), 8.28 (d, J = 5.4 Hz, 1H), 7.98
(t, J = 7.2 Hz, 1H), 7.89 (d, J = 7.5 Hz, 1H), 7.50À7.44 (m, 2H),
7.40À7.30 (m, 3H), 6.94À6.83 (m, 6H), 6.77À6.71 (m, 2H), 5.95
(s, 1H), 3.46 (s, 2H), 2.25 (s, 3H) ppm. 13C NMR (CDCl3, 100 MHz):
δ 21.0, 36.7, 121.3, 123.2, 123.9, 126.7, 128.0, 128.9, 129.0, 129.1, 130.3,
132.2, 134.2, 135.1, 135.5, 136.0, 140.4, 143.2, 145.6, 152.5, 167.0, 169.4,
173.1 ppm. MS (EI, m/z): 531 [M]+. HRMS (EI): calcd for C30H23-
N3NiO3 [M]+ 531.1093; found 531.1086.
Ni(II)-PABP/3-Amino-2-(2,5-dimethylbenzyl)acrylic Acid
1
Schiff Base Complex 4j. Dark-red solid. Mp 89À90 °C. H NMR
(CDCl3, 300 MHz): δ 8.50 (d, J = 8.7 Hz, 1H), 8.32 (d, J = 5.1 Hz, 1H),
8.00 (t, J = 7.5 Hz, 1H), 7.90 (d, J = 7.5 Hz, 1H), 7.51À7.47 (m, 1H),
7.41À7.38 (m, 1H), 7.35À7.27 (m, 3H), 6.85 (d, J = 7.2 Hz, 2H),
6.80À6.65 (m, 5H), 5.67 (s, 1H), 3.48 (s, 2H), 2.16 (s, 3H), 2.06 (s, 3H)
ppm. 13C NMR (CDCl3, 100 MHz): δ 19.0, 20.9, 34.6, 121.2, 123.2,
123.9, 126.7, 127.1, 127.9, 128.4, 128.6, 130.1, 130.6, 131.3, 132.9, 134.1,
135.1, 135.8, 135.9, 140.5, 143.1, 145.5, 152.4, 167.0, 169.3, 173.0 ppm.
MS (EI, m/z): 545 [M]+. HRMS (EI): calcd for C31H25N3NiO3 [M]+
545.1249; found 545.1250.
Ni(II)-PABP/3-Amino-2-(2,4,6-trimethylbenzyl)acrylic Acid
Schiff Base Complex 4k. Dark-red solid. Mp 123À125 °C. 1H
NMR (CDCl3, 300 MHz): δ 8.49 (d, J = 8.7 Hz, 1H), 8.36 (d, J = 5.4 Hz,
1H), 8.02À7.98 (m, 1H), 7.90 (d, J = 7.8 Hz, 1H), 7.53À7.48 (m, 1H),
7.38À7.23 (m, 4H), 6.79À6.65 (m, 4H), 6.55 (s, 2H), 5.52 (s, 1H), 3.51
(s, 2H), 2.16 (s, 3H), 2.05 (s, 6H) ppm. 13C NMR (CDCl3, 100 MHz):
δ 19.0, 20.7, 30.4, 121.2, 123.2, 123.9, 126.7, 127.8, 128.0, 128.7, 129.7,
130.1, 131.4, 134.1, 135.1, 135.2, 135.9, 136.0, 138.6, 140.5, 143.0, 145.5,
152.4, 167.1, 169.4, 173.0 ppm. MS (EI, m/z): 559 [M]+. HRMS (EI):
calcd for C32H27N3NiO3 [M]+ 559.1406; found 559.1415.
Ni(II)-PABP/3-Amino-2-(naphthalen-1-ylmethyl)acrylic Acid
Schiff Base Complex 4l. Dark-red solid. Mp 130À132 °C. 1H NMR
(CDCl3, 300 MHz): δ 8.46 (d, J = 8.4 Hz, 1H), 8.35 (d, J = 5.1 Hz, 1H),
8.00 (t, J = 7.5 Hz, 1H), 7.89 (d, J = 7.5 Hz, 1H), 7.80 (t, J = 9.0 Hz, 2H),
7.57À7.46 (m, 4H), 7.31À7.27 (m, 1H), 7.18À7.05 (m, 3H), 6.77
(t, J = 7.8 Hz, 2H), 6.69 (t, J = 7.5 Hz, 1H), 6.56 (d, J = 7.5 Hz, 1H),
6.46 (d, J= 7.5 Hz, 2H), 5.63 (s, 1H), 4.03 (s, 2H) ppm. 13CNMR(CDCl3,
100 MHz): δ 34.0, 121.2, 123.1, 123.9, 124.4, 125.1, 125.6, 126.1, 126.7,
127.1, 127.6, 128.0, 128.5, 129.7, 131.6, 133.9, 134.0, 134.3, 135.1, 140.5,
140.6, 143.1, 145.5, 152.5, 166.8, 169.3, 173.1 ppm. MS (EI, m/z): 567 [M]+.
HRMS (EI): calcd for C33H23N3NiO3 [M]+ 567.1093; found 567.1097.
Ni(II)-PABP/3-Amino-2-(bis(4-fluorophenyl)methyl)acrylic
Acid Schiff Base Complex 4m. Dark-red solid. Mp 150À153 °C. 1H
NMR (CDCl3, 300 MHz): δ 8.54 (d, J = 9.0 Hz, 1H), 8.21 (d, J = 5.7 Hz,
1H), 8.00À7.97 (m, 1H), 7.92 (d, J = 7.8 Hz, 1H), 7.48À7.32 (m, 4H),
7.29À7.23 (m, 1H), 7.02À6.97 (m, 4H), 6.86À6.68 (m, 8H), 5.86
(s, 1H), 5.48 (s, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ 49.9, 115,2,
115.4, 121.4, 123.3, 124.0, 126.9, 127.8, 128.5, 128.9, 130.0, 130.1, 130.3,
134.4, 134.5, 135.3, 135.8, 137.4, 140.6, 142.7, 143.4, 145.6, 152.4,160.2,
162.7, 166.1, 169.5, 174.2 ppm. MS (EI, m/z): 629 [M]+. HRMS (EI):
calcd for C35H23F2N3NiO3 [M]+ 629.1061; found 629.1069.
Ni(II)-PABP/2-(Aminomethylene)-4-methylpentanoic Acid
Schiff Base Complex 4r. Dark-red solid. Mp 132À135 °C. 1H NMR
(CDCl3, 300 MHz): δ 8.53 (d, J = 8.7 Hz, 1H), 8.27 (br, 1H), 8.02À
7.96 (m, 1H), 7.90 (d, J = 7.5 Hz, 1H), 7.56À7.48 (m, 4H), 7.38À7.33
(m, 1H), 7.12 (d, J = 8.4 Hz, 2H), 6.80À6.75 (m, 2H), 6.26
(s, 1H), 1.96 (d, J = 6.6 Hz, 2H), 1.87À1.79 (m, 1H), 0.81 (d, J = 6.6 Hz,
3H) ppm. 13C NMR (CDCl3, 125 MHz): δ 22.6, 27.6, 41.0, 121.3, 123.2,
123.9, 126.8, 128.3, 129.0, 129.3, 130.7, 134.2, 135.2, 136.1, 139.3, 140.5,
143.2, 145.6, 152.5, 169.4, 172.6 ppm. MS (ESI, m/z):484[M+H]+.HRMS
(EI): calcd for C26H24N3NiO3 [M + H]+ 484.1171; found 484.1160.
Ni(II)-PABP/2-(Aminomethylene)heptanoic Acid Schiff
Base Complex 4s. Dark-red solid. Mp 82À84 °C. 1H NMR (CDCl3,
300 MHz): δ 8.53 (d, J = 8.4 Hz, 1H), 8.27 (d, J = 5.4 Hz, 1H),
8.02À7.96 (m, 1H), 7.90 (d, J = 7.5 Hz, 1H), 7.57À7.48 (m, 4H),
7.39À7.35 (m, 1H), 7.11 (d, J = 8.7 Hz, 2H), 6.80À6.76 (m, 2H), 6.27
(s, 1H), 2.11 (t, J = 6.9 Hz, 2H), 1.33À1.17 (m, 6H), 0.82 (t, J = 6.0 Hz,
3H) ppm. 13C NMR (CDCl3, 125 MHz): δ 14.0, 22.4, 28.3, 31.5, 31.6,
121.3, 123.2, 123.9, 128.3, 129.0, 129.3, 130.7, 135.2, 136.2, 138.7, 140.5,
143.2, 145.6, 152.6, 169.4, 172.5 ppm. MS (ESI, m/z): 498 [M + H]+.
HRMS (EI): calcd for C27H26N3NiO3 [M + H]+ 498.1328; found
498.1325.
Ni(II)-PABP/3-Amino-2-(quinolin-2-ylmethyl)acrylic Acid
Schiff Base Complex 4n. Dark-red solid. Mp 75À78 °C. 1H NMR
(CDCl3, 300 MHz): δ 8.50 (d, J = 8.1 Hz, 1H), 8.26 (d, J = 5.4 Hz, 1H),
7.99À7.95 (m, 2H), 7.90À7.84 (m, 2H), 7.76 (d, J = 8.4 Hz, 1H),
7.69À7.63 (m, 1H), 7.53À7.44 (m, 2H), 7.37À7.29 (m, 2H), 7.14À7.04
(m, 3H), 6.84À6.66 (m, 4H), 6.27 (s, 1H), 3.88 (s, 2H) ppm. 13C NMR
(CDCl3, 100 MHz): δ 40.0, 121.2, 121.4, 122.1, 123.2, 123.9, 125.9,
126.7, 126.8, 127.4, 128.0, 128.5, 128.8, 128.9, 129.0, 129.2, 129.9, 130.3,
Procedure for the Synthesis of 5a. In a hydrogenation flask was
placedcompound4a and10mLofmethanolbefore theaddition ofRaney-
Ni suspended in 10 mL of water. The resulting mixture was pressurized to
hydrogen and mechanically stirred at room temperature for 1 h. The
reaction mixture was filtered and the filtrate was concentrated in a rotary
evaporator to afford the crude product. The crude residue was purified by
column chromatography on silica gel (dichloromethane/methanol =
50/1) to give 5a as a red solid in 78% yield.
6654
dx.doi.org/10.1021/jo200971k |J. Org. Chem. 2011, 76, 6649–6656