The Journal of Organic Chemistry
Article
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-5-methoxyphenyl)-
propanoic Acid Schiff Base Complex 3g. Red solid (107 mg, yield
96%, (S)(2S)/(S)(2R) = 91:9). (S)(2S)-3g: mp 236−238 °C; [α]D25
+1992 (c 0.05, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.25 (d, J = 8.8
Hz, 1H), 8.03 (d, J = 8.7 Hz, 2H), 7.52−7.43 (m, 2H), 7.41 (d, J = 8.8
Hz, 1H), 7.35−7.28 (m, 3H), 7.24 (d, J = 7.3 Hz, 1H), 7.18−7.09
(m,2H), 6.72 (dd, J = 8.8, 3.0 Hz, 1H), 6.68−6.62 (m, 2H), 6.59 (dd, J
= 8.8, 1.5 Hz, 2H), 4.34 (d, J = 12.7 Hz, 1H), 4.29 (dd, J = 6.9, 5.4 Hz,
1H), 3.61 (s, 3H), 3.58−3.47 (m, 3H), 3.42 (dd, J = 10.6, 6.5 Hz, 1H),
3.33−3.25 (m, 1H), 3.18−3.08 (m, 1H), 2.70−2.59 (m, 1H), 2.55−
2.43 (m, 1H), 2.09−1.94 (m, 2H). 13C NMR (125 MHz, CDCl3): δ
179.6, 177.5, 170.7, 158.6, 142.3, 136.1, 133.2, 133.1, 133.1, 132.8,
131.9, 131.0, 129.1, 128.4, 128.4, 128.3, 127.5, 127.1, 125.8, 122.9,
120.1, 115.9, 115.7, 70.8, 70.1, 62.7, 56.7, 54.9, 41.2, 30.4, 23.2. LRMS
(ESI) m/z: [M + H]+ found 696. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C35H32BrNaN3NiO4 718.0827; Found 718.0821. The dr was
determined by LC-MS with an Eclipse XDB-C18 column (150 mm ×
4.6 mm, 5 μm) (MeOH/H2O = 80/20, flow rate 1.0 mL/min, λ = 214
nm), tmajor = 4.803 min, tminor = 6.418 min, dr = 91:9.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-5-cyanophenyl)-
propanoic Acid Schiff Base Complex 3h. Red solid (107 mg, yield
96%, (S)(2S)/(S)(2R) = 94:6). (S)(2S)-3h: mp 111−114 °C; [α]D25
+2017 (c 0.06, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.18 (d, J = 8.6
Hz, 1H), 8.05 (d, J = 7.5 Hz, 2H), 7.65 (d, J = 8.3 Hz, 1H), 7.61−7.54
(m, 2H), 7.45 (td, J = 7.4, 2.0 Hz, 1H), 7.39−7.30 (m, 4H), 7.21−7.13
(m, 2H), 7.07 (d, J = 2.0 Hz, 1H), 6.94 (d, J = 7.6 Hz, 1H), 6.71−6.62
(m, 2H), 4.38 (d, J = 12.7 Hz, 1H), 4.25 (t, J = 8.0 Hz, 1H), 3.74 (dd, J
= 13.6, 8.0 Hz, 1H), 3.55 (d, J = 12.7 Hz, 1H), 3.47 (dd, J = 10.9, 5.9
Hz, 1H), 3.39 (dd, J = 10.3, 6.5 Hz, 1H), 3.35−3.19 (m, 2H), 2.71−
2.60 (m, 1H), 2.58−2.46 (m, 1H), 2.17−2.02 (m, 2H). 13C NMR (125
MHz, CDCl3): δ 179.8, 176.6, 170.9, 142.1, 137.3, 134.4, 133.4, 133.1,
133.0, 132.7, 132.2, 131.3, 131.0, 130.2, 129.5, 128.9, 128.8, 128.5, 128.
5, 127.2, 125.7, 123.2, 120.3, 117.2, 111.5, 69.8, 69.8, 62.8, 56.7, 40.5,
30.4, 23.5. LRMS (ESI) m/z: [M + H]+ found 691. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C35H29BrNaN4NiO3 713.0674; Found
713.0657. The dr was determined by LC-MS with an Eclipse XDB-C18
column (150 mm × 4.6 mm, 5 μm) (MeOH/H2O = 80/20, flow rate
1.0 mL/min, λ = 214 nm), tmajor = 3.232 min, tminor = 4.261 min, dr =
94:6.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-5-nitrophenyl)-
propanoic Acid Schiff Base Complex 3i. Red solid (109 mg, yield
95%, (S)(2S)/(S)(2R) = 94:6). (S)(2S)-3i: mp 127−129 °C; [α]D25
+1971 (c 0.06, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.14 (d, J = 8.6
Hz, 1H), 8.08 (d, J = 7.5 Hz, 2H), 7.91 (dd, J = 8.7, 2.7 Hz, 1H), 7.67
(d, J = 8.8 Hz, 1H), 7.62−7.55 (m, 2H), 7.52 (d, J = 2.7 Hz, 1H), 7.47−
7.41 (m, 1H), 7.38−7.31 (m, 3H), 7.22−7.14 (m, 2H), 6.89 (d, J = 7.5
Hz, 1H), 6.72−6.64 (m, 2H), 4.40 (d, J = 12.7 Hz, 1H), 4.25 (dd, J =
8.7, 5.9 Hz, 1H), 3.94 (dd, J = 13.5, 8.8 Hz, 1H), 3.62−3.52 (m, 2H),
3.52−3.44 (m, 2H), 3.33 (dd, J = 13.5, 5.9 Hz, 1H), 2.77−2.67 (m,
1H), 2.62−2.50 (m, 1H), 2.26−2.17 (m, 1H), 2.14−2.04 (m, 1H). 13C
NMR (125 MHz, CDCl3): δ 179.8, 176.5, 170.8, 146.7, 142.1, 137.3,
133.3, 133.0, 132.8, 132.8, 132.2, 131.8, 131.0, 129.7, 128.9, 128.7,
128.5, 128.5, 127.2, 127.1, 125.8, 125.5, 123.3, 122.8, 120.4, 69.8, 69.7,
62.8, 56.8, 41.0, 30.4, 23.6. LRMS (ESI) m/z: [M + H]+ found 711.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C34H29BrNaN4NiO5
733.0572; Found 733.0573. The dr was determined by LC-MS with an
Eclipse XDB-C18 column (150 mm × 4.6 mm, 5 μm) (MeOH/H2O =
MHz, CDCl3): δ 179.7, 177.0, 171.0, 142.3, 137.2, 133.5, 133.3, 133.2,
133.1, 132.8, 132.1, 131.5, 131.0, 129.3, 128.6, 128.6, 128.4, 127.2,
127.1, 125.7, 123.0, 123.0, 120.2, 70.4, 70.0, 62.7, 56.7, 40.4, 30.4, 23.2.
LRMS (ESI) m/z: [M + H]+ found 700. HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C34H29BrClNaN3NiO3 722.0332; Found 722.0335. The
dr was determined by LC-MS with an Eclipse XDB-C18 column (150
mm × 4.6 mm, 5 μm) (MeOH/H2O = 75/25, flow rate 1.0 mL/min, λ
= 214 nm), tmajor = 9.537 min, tminor = 15.995 min, dr = 95:5.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-4,5-difluorophenyl)-
propanoic Acid Schiff Base Complex 3k. Red solid (107 mg, yield
95%, (S)(2S)/(S)(2R) = 95:5). (S)(2S)-3k: mp 106−108 °C; [α]D25
+2107 (c 0.05, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.21 (d, J = 8.6
Hz, 1H), 8.05 (d, J = 7.5 Hz, 2H), 7.59−7.50 (m, 2H), 7.45−7.36 (m,
2H), 7.33 (t, J = 7.6 Hz, 2H), 7.29 (d, J = 7.0 Hz, 1H), 7.21−7.12 (m,
2H), 6.91 (d, J = 7.5 Hz, 1H), 6.80 (dd, J = 10.7, 8.1 Hz, 1H), 6.70−
6.61 (m, 2H), 4.36 (d, J = 12.6 Hz, 1H), 4.24 (t, J = 6.4 Hz, 1H), 3.60−
3.50 (m, 2H), 3.45 (dd, J = 10.7, 6.1 Hz, 1H), 3.35 (dd, J = 9.1, 6.3 Hz,
1H), 3.26−3.13 (m, 2H), 2.71−2.59 (m, 1H), 2.58−2.46 (m, 1H),
2.12−2.01 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 179.7, 176.9,
170.9, 142.2, 133.1, 132.7, 132.3, 132.2, 132.2, 132.1, 131.0, 129.4,
128.5, 128.4, 127.9 (dd, J = 187.1, 14.2 Hz), 125.7, 123.1, 120.4 (dd, J =
181.0, 19.5 Hz), 120.3, 118.3, 118.3, 118.3, 70.1, 69.9, 62.8, 56.7, 40.1,
30.4, 23.2. LRMS (ESI) m/z: [M + H]+ found 702. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C34H28BrF2NaN3NiO3 724.0533; Found
724.0530. The dr was determined by LC-MS with an Eclipse XDB-C18
column (150 mm × 4.6 mm, 5 μm) (MeOH/H2O = 80/20, flow rate
1.0 mL/min, λ = 214 nm), tmajor = 4.898 min, tminor = 7.089 min, dr =
95:5.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-4,5-dimethoxy-
phenyl)propanoic Acid Schiff Base Complex 3l. Red solid (115
mg, yield 99%, (S)(2S)/(S)(2R) = 91:9). (S)(2S)-3l: mp 93−95 °C;
[α]2D5 +1662 (c 0.05, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.25 (d, J
= 8.7 Hz, 1H), 8.04 (d, J = 7.7 Hz, 2H), 7.52−7.42 (m, 2H), 7.34−7.28
(m, 3H), 7.24 (d, J = 7.4 Hz, 1H), 7.17−7.10 (m, 2H), 7.02 (s, 1H),
6.67−6.56 (m, 4H), 4.33 (d, J = 12.6 Hz, 1H), 4.26 (dd, J = 7.0, 4.9 Hz,
1H), 3.87 (s, 3H), 3.64 (s, 3H), 3.58−3.48 (m, 2H), 3.46−3.39 (m,
2H), 3.33−3.23 (m, 1H), 3.15−3.01 (m, 1H), 2.70−2.57 (m, 1H),
2.55−2.44 (m, 1H), 2.10−1.93 (m, 2H). 13C NMR (125 MHz,
CDCl3): δ 179.5, 177.7, 170.7, 148.4, 148.0, 142.3, 133.2, 133.2, 132.8,
131.9, 131.0, 129.0, 128.4, 128.3, 127.5, 127.1, 127.1, 125.8, 122.8,
120.1, 115.2, 114.8, 113.6, 71.0, 70.1, 62.8, 56.7, 55.7, 55.5, 40.5, 30.5,
23.0. LRMS (ESI) m/z: [M + H]+ found 726. HRMS (ESI-TOF) m/z:
[M + Na]+ Calcd for C36H34BrNaN3NiO5 748.0933; Found 748.0955.
The dr was determined by LC-MS with an Eclipse XDB-C18 column
(150 mm × 4.6 mm, 5 μm) (MeOH/H2O = 80/20, flow rate 1.0 mL/
min, λ = 214 nm), tmajor = 3.766 min, tminor = 4.634 min, dr = 91:9.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromopyridin-3-yl)propanoic
Acid Schiff Base Complex 3m. Red solid (106 mg, yield 99%,
(S)(2S)/(S)(2R) = 93:7). (S)(2S)-3m: mp 117−120 °C; [α]2D5 +2173
(c 0.06, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.31(dd, J = 4.7, 2.0
Hz, 1H), 8.23 (d, J = 8.7 Hz, 1H), 8.04 (d, J = 7.5 Hz, 2H), 7.57−7.47
(m, 2H), 7.43 (dd, J = 7.5, 2.0 Hz, 1H), 7.38 (td, J = 7.4, 1.7 Hz, 1H),
7.33 (t, J = 7.6 Hz, 2H), 7.29−7.27 (m, 1H), 7.22−7.11 (m, 3H), 6.76
(d, J = 7.9 Hz, 1H), 6.69−6.64 (m,1H), 6.61 (dd, J = 8.0, 1.5 Hz, 1H),
4.42−4.27 (m, 2H), 3.61−3.48 (m, 2H), 3.43 (dd, J = 10.7, 6.3 Hz,1H),
3.34 (dd, J = 13.9, 6.7 Hz, 1H), 3.26 (dd, J = 9.3, 6.4 Hz, 1H), 3.13−
2.97 (m, 1H), 2.76−2.64 (m, 1H), 2.57−2.44 (m, 1H), 2.07−1.95 (m,
2H). 13C NMR (125 MHz, CDCl3): δ 179.7, 177.0, 171.0, 148.4, 144.7,
142.2, 139.9, 133.2, 133.1, 133.0, 132.7, 132.1, 131.0, 129.4, 128.7,
128.7, 128.5, 128.4, 127.0, 125.7, 123.1, 122.6, 120.2, 70.0, 69.7, 62.7,
56.6, 40.1, 30.3, 23.3. LRMS (ESI) m/z: [M + H]+ found 667. HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C33H29BrNaN4NiO3 689.0674;
Found 689.0685. The dr was determined by LC-MS with an Eclipse
XDB-C18 column (150 mm × 4.6 mm, 5 μm) (MeOH/H2O = 80/20,
flow rate 1.0 mL/min, λ = 214 nm), tmajor = 2.674 min, tminor = 3.096
min, dr = 93:7.
80/20, flow rate 1.0 mL/min, λ = 214 nm), tmajor = 3.784 min, tminor
=
5.376 min, dr = 94:6.
Ni(II)-(S)-BPB/(S)-2-amino-3-(2-bromo-5-chlorophenyl)-
propanoic Acid Schiff Base Complex 3j. Red solid (111 mg, yield
99%, (S)(2S)/(S)(2R) = 95:5). (S)(2S)-3j: mp 99−101 °C; [α]D25
+1991 (c 0.05, CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.24 (d, J = 8.7
Hz, 1H), 8.04 (d, J = 7.5 Hz, 2H), 7.53 (t, J = 8.7 Hz, 2H), 7.49 (d, J =
8.7 Hz, 1H), 7.38 (t, J = 8.7 Hz, 1H), 7.32 (t, J = 7.6 Hz, 2H), 7.29−
7.27 (m, 1H), 7.20−7.09 (m, 3H), 6.96 (d, J = 2.5 Hz, 1H), 6.84 (d, J =
7.7 Hz, 1H), 6.70−6.60 (m, 2H), 4.35 (d, J = 12.7 Hz, 1H), 4.26 (t, J =
6.2 Hz, 1H), 3.53 (dt, J = 13.7, 3.7 Hz, 2H), 3.43 (dd, J = 10.7, 6.4 Hz,
1H), 3.33 (dd, J = 13.9, 5.8 Hz, 2H), 3.18−3.05 (m, 1H), 2.65−2.56
(m, 1H), 2.53−2.44 (m, 1H), 2.09−1.98 (m, 2H). 13C NMR (125
Ni(II)-(S)-BPB/(S)-2-amino-4-(2-bromophenyl)butanoic Acid
Schiff Base Complex 3n. Red solid (872 mg, yield 80%, (S)(2S)/
(S)(2R) = 94:6). (S)(2S)-3n: mp 85−88 °C; [α]2D5 +2131 (c 0.06,
CHCl3). 1H NMR (500 MHz, CDCl3): δ 8.14 (d, J = 9.1 Hz, 1H), 8.07
7877
dx.doi.org/10.1021/jo501571j | J. Org. Chem. 2014, 79, 7872−7879