Article
Chang et al.
rial, 2-methoxybenzaldehyde (1b) (2.72 g, 20.0 mmol), was used.
The yield of isolated 3f (yellow solid) is 40% (1.39 g, 3.99 mmol).
tate and water were added and the organic phase was collected
from separatory funnel. Subsequently, the separation of pure
product was performed by column chromatography. The yield of
isolated 4a (white solid) is 58% (0.79 g, 2.32 mmol).
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‡ Spectroscopic data for 3e. H NMR(CDCl3, /ppm):
7.40-7.25 (m, 10H, Ar), 6.80-6.70 (m, 4H, Ar), 4.32 (s, 4H,
Benzylic), 3.65(b, 2H); 13C NMR(CDCl3, /ppm): 139.4, 137.1,
128.6, 127.8, 127.2, 119.4, 111.9 (Aromatic), 48.7 (Benzylic). ‡
Similar procedures were applied to the preparations of 4b
and 4c from corresponding 3b (1.42 g, 4.0 mmol) and 3c (1.51 g,
4.0 mmol). The yields of purified 4b (yellow liquid) and 4c (white
solid) are 35% (0.56 g, 1.40 mmol) and 75% (1.27 g, 3.00 mmol),
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Spectroscopic data for 3f. H NMR(CDCl3, /ppm): 7.31-7.23
(m, 4H, Ar), 6.93-6.88 (m, 4H, Ar), 6.77-6.71 (m, 4H, Ar), 4.31
(s, 4H, Benzylic), 3.88 (b, 2H), 3.83 (s, 6H, OMe); 13C NMR
(CDCl3, /ppm): 157.4, 137.6, 129.1, 128.2, 127.5, 120.5, 119.2,
112.4, 110.2 (Aromatic), 55.2 (Benzylic), 44.1 (OMe).
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respectively. ‡ Spectroscopic data for 4a. H NMR(CDCl3,
/ppm): 7.52 (d, JP-H = 604.7 Hz, 1H, P-H), 7.41 (d, J = 10.0 Hz,
2H, Ar), 7.34-7.22 (m, 8H, Ar), 4.40-4.04 (m, 4H, Benzylic),
3.00-2.80 (m, 2H), 1.84-1.66 (m, 4H), 1.26-1.01 (m, 4H); 13C
NMR (CDCl3, /ppm): 138.3,138.1, 128.5, 128.4, 128.1, 127.9,
127.3, 127.2 (Aromatic), 63.1, 62.7 (Benzylic), 46.5, 45.9 (CH),
29.3, 28.6 (CH2), 24.1, 24.0 (CH2); 31P NMR(CDCl3, /ppm): 20.8
General procedure for the synthesis of 3g-3h: Similar
procedures for the preparation of 3f are applicable for making 3g
and 3h. The corresponding 2-pyridinecarboxaldehyde (1d) (2.14
g, 20.0 mmol) was firstly used to prepare 2h. Further reaction
with NaBH4 (0.79 g, 21.0 mmol) and workup followed to produce
3h (yellow solid) in 35% yield (1.02 g, 3.52 mmol). Similar pro-
cedures were applied to the preparation of 3g. The corresponding
mesitaldehyde (1c) (2.95 mL, 20.0 mmol) was used. Due to se-
vere steric hindrance, only one side of amine is formed. The yield
of isolated 3g (yellow solid) is 68% (1.63 g, 6.79 mmol).
‡ Spectroscopic data for 3g. 1H NMR(CDCl3, /ppm): 6.94
(s, 2H, Ar), 6.93 (d, J = 4.0 Hz, 1H, Ar), 6.86 (d, J = 8.0 Hz, 1H,
Ar), 6.74 (d, J = 4.0 Hz, 2H, Ar), 4.22 (s, 2H, Benzylic), 3.23 (b,
3H), 2.39 (s, 6H), 2.33 (s, 3H); 13C NMR(CDCl3, /ppm): 138.0,
137.6, 137.2, 134.2, 132.3, 129.0, 120.6, 118.5, 116.1, 111.3, (Ar-
omatic), 42.5 (Benzylic), 20.9 (Mes), 19.4 (Mes). ‡ Spectro-
scopic data for 3h. 1H NMR (CDCl3, /ppm): 8.59 (d, J = 4.2 Hz,
2H, Ar), 7.63 (t, J = 7.6 Hz, 2H, Ar), 7.36 (d, J = 7.6 Hz, 2H, Ar),
7.17 (t, J = 6.0 Hz, 2H, Ar), 6.75 (quin., J = 4.0 Hz, 2H, Ar), 6.66
(quin., J = 4.0 Hz, 2H, Ar), 4.55 (b, 2H), 4.49 (s, 2H, Benzylic);
13C NMR(CDCl3, /ppm): 158.8, 149.2, 136.9, 136.6, 122.0,
121.6, 119.3, 112.1 (Aromatic), 49.8 (Benzylic).
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(d, JP-H = 605.8 Hz). ‡ Spectroscopic data for 4b. H NMR
(CDCl3, /ppm): 7.39 (d, JP-H = 614.7 Hz, 1H, P-H), 7.41 (q, J = 7.2
Hz, 2H, Ar), 7.23 (quin. J = 8.4 Hz, 2H, Ar), 6.95-6.82 (m, 4H,
Ar), 4.54 (t, J = 15.2 Hz, 1H, Benzylic), 4.35 (q, J = 8.4 Hz, 1H,
Benzylic), 4.19 (t., J = 16.8 Hz, 1H, Benzylic), 3.87 (d, J = 13.2
Hz, 1H, Benzylic), 3.83 (s, 3H, OMe), 3.81 (s, 3H, OMe), 3.04 (t,
J = 11.4 Hz, 1H), 2.79 (t, J = 10.2 Hz, 1H), 2.01 (d, J = 10.4 Hz,
1H), 1.88 (d, J = 11.4 Hz, 1H), 1.70 (t, J = 12.8 Hz, 2H), 1.29-1.14
(m, 3H), 1.07-1.01 (m, 1H); 13C NMR(CDCl3, /ppm): 157.0,
156.9, 129.8, 128.9, 128.4, 128.0, 127.6, 126.2, 120.3, 120.1,
110.1, 110.0 (Aromatic), 64.4, 62.4 (Benzylic), 55.1, 55.0 (OMe),
41.2, 10.1 (CH), 29.4, 28.5 (CH2), 24.3, 24.1 (CH2); 31P NMR
(CDCl3, /ppm): 22.3 (d, JP-H = 615.0 Hz). ‡ Spectroscopic data
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for 4c. H NMR (CDCl3, /ppm): 6.57 (d, JP-H = 609.2 Hz, 1H,
P-H), 6.79 (s, 2H, Ar), 6.79 (s, 2H, Ar), 4.17-4.08 (m, 2H,
Benzylic), 3.95-3.86 (m, 2H, Benzylic), 3.11 (t, J = 10.4 Hz, 1H),
2.85 (t, J = 9.8 Hz, 1H), 2.36 (s, 6H), 2.33 (s, 6H), 2.22 (s, 3H),
2.21 (s, 3H), 2.01 (d, J = 10.4 Hz, 1H), 2.07 (d, J = 11.2 Hz, 1H),
1.96 (s, 1H), 1.79 (s,1H), 1.35-1.15 (m, 5 H); 13C NMR (CDCl3,
/ppm): 137.9, 137.7, 137.5, 137.0, 129.8, 129.4, 129.2, 129.1 (Ar-
omatic), 66.1, 63.7 (Benzylic), 42.8, 41.7 (CH), 29.3, 28.9 (CH2),
24.4, 24.3, (CH2), 20.9, 20.8 (Mes), 20.3, 20.2 (Mes); 31P NMR
(CDCl3, /ppm): 19.4 (d, JP-H = 609.6 Hz). Compound 4c has been
communicated elsewhere.
General procedure for the synthesis of 4a-4c: The proce-
dures for the preparation of 4a-4c were modified from literature.32
Into a 100 mL round flask with stir bar was placed 3a (1.17 g, 4.0
mmol). The air was pumped out and backfilled with nitrogen gas
before 8 mL of toluene was added. Three molar equivalents of
triethylamine (1.66 mL, 12.0 mmol) was injected and then the
flask was placed in ice-water bath. Under nitrogen, 5 mL of tolu-
ene and 1.5 molar equivalents of phosphorus trichloride (0.35
mL, 6.0 mmol) were added to another 100 mL flask. At 0 °C, the
content of the latter flask was transferred to the first one slowly
through cannular needle and stirred for 3 hours at that tempera-
ture. Certain amount of hexane was added to salt out ionic com-
pounds. Participate was filtrated out and followed by hydrolysis
of the filtrated solution with water for 5 minutes. More ether ace-
General procedure for the synthesis of Pd(OAc)2 (3a) and
Pd(OAc)2 (3c): Into a 10 mL Schlenk flask was placed 3a (0.035 g,
0.1 mmol) and Pd(OAc)2 (0.022 g, 0.1 mmol) with 1 mLof CH2Cl2.
The solution was stirred at 25 °C for 12 hours. Yellow color and
column shape crystals were formed and determined by x-ray dif-
fraction methods as Pd(OAc)2 (3a). The same procedures are appli-
cable to the preparation of 3c_Pd from its corresponding 3c.
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‡ Spectroscopic data for Pd(OAc)2(3a). H NMR (d6-
364
© 2016 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2016, 63, 353-367