CHEN ET AL.
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instrument (Thermo) or an Elementar vario EL CUBE
(CHN‐OS Rapid, Germany). The Suzuki–Miyaura cross‐
coupling reactions were analyzed using GC‐MS with a
Bruker SCION 436 SQ instrument equipped with a
Bruker BR‐5ms column. The MS detector was configured
with an electronic impact ionization source.
for 0.5 h. The solution was filtered through a pad of
Celite, and the filtrate was removed from the solvent to
afford a pale yellow solid of the desired compound in
1
86% yield (0.74 g). H NMR (400 MHz, CDCl3, δ, ppm):
2.18 (s, CH3, 6H), 2.37 (s, CH3, 12H), 2.43 (s, CH3, 6H),
3.63 (s, NCH, 4H), 7.04 (s, NCH2, 2H), 7.11 (s, ArH,
4H), 7.13 (d, J = 7 .6Hz, ArH, 2H), 7.19 (t, J = 7 .4Hz,
ArH, 1H), 7.56 (d, J = 7 .2Hz, ArH, 2H). 13C{1H} NMR
(100 MHz, CDCl3, δ, ppm): 19.3 (s, CH3), 21.2 (s, CH3),
49.7 (s, CH3), 65.1 (s, NCH2), 124.2, 127.5, 127.9, 129.1,
130.7 (s, CH, aromatic), 135.3, 136.5, 139.0, 151.2, 147.0
(s, C aromatic), 153.6 (s, Ccarbene). Anal. Calcd for
C30H37Cl2N3Pd (%): C, 58.40; H, 6.05; N, 6.81. Found
2.2 | Synthesis of complexes 1–6
Complex 1. 1H NMR (CDCl3,
(%):
C,
58.49;
H,
6.45;
N,
6.75.
Synthesis of 4. The procedure
400 MHz, δ, ppm): 1.05 (d, J = 6.8 Hz, CH3, 12H), 1.37
(d, J = 6 .8Hz, CH3, 12H), 2.12 (s, N (CH3)2, 6H), 3.14
(septet, J = 6 .8Hz, CH, 4H), 3.60 (s, N (CH2), 2H), 6.99
(t, J = 7 .6Hz, ArH, 2H), 7.07 (s, CH¼CH, 2H), 7.12 (t,
J = 7 .6Hz, ArH, 1H), 7.39 (t, J = 7 .2Hz, ArH, 6H), 7.54
(t, J = 7 .6Hz, ArH, 2H). 13C{1H} NMR (CDCl3,
100 MHz, δ, ppm): 22.9 (s, iPr), 26.4 (s, iPr), 28.6 (s,
CHiPr), 49.6 (s, N (CH3)2), 65.0 (s, CH2N(CH3)2), 124.0,
125, 127.3, 128.0, 130.0, 131.0 (s, CH aromatic), 134.9,
for the preparation of 4 was similar to that used for 3
but with [Pd(μ‐Cl)Cl (SIMes)]2 (97 mg, 0.7 mmol) and
N,N‐dimethylbenzylamine (0.03 ml, 1.4 mmol), and
2 ml of DCM. A pale yellow solid was obtained in 78%
1
yield (97 mg). H NMR (400 MHz, CDCl3, δ, ppm): 2.09
(s, CH3, 6H), 2.37 (s, CH3, 6H), 2.56 (s, CH3, 12H), 3.99
(s, N (CH2), 4H), 6.91 (s, ArH, 1H), 6.98 (s, ArH, 1H),
7.05 (s, ArH, 4H), 7.14 (t, J = 7 .3Hz, ArH, 1H), 7.41 (t,
J = 10.9Hz, ArH, 2H). 13C{1H} NMR (100 MHz, CDCl3,
δ, ppm): 19.5 (s, CH3), 21.1 (s, CH3), 42.4 (s, CH3), 49.5
(s, CH3), 51.1 (s, CH2), 64.9 (s, NCH2), 127.4, 127.8,
129.4, 130.6, 131.2 (s, CH, aromatic), 135.1, 135.3, 137.4,
137.6, 138.2 (s, C aromatic), 183.1 (s, Ccarbene). Anal.
Calcd for C30H39Cl2N3Pd (%): C, 58.21; H, 6.35; N, 6.79.
135.2, 147.0 (s,
C aromatic), 153.6 (s, Ccarbene).
Complex 2. 1H NMR (CDCl3,
Found
(%):
C,
58.55;
H,
6.45;
N,
6.80.
400 MHz, δ, ppm): 1.18 (d, J = 6.8 Hz, CH3, 12H), 1.46
(d, J = 6.4 Hz, CH3, 12H), 2.08 (s, N (CH3)2, 6H), 3.60
(septet, J = 7.3 Hz, CH, 4H), 4.05 (s, N (CH2), 2H), 6.97
(t, J = 7.8 Hz, ArH, 2H), 7.12 (t, J = 7.4 Hz, ArH, 1H),
7.36 (m, ArH + CH2CH2, 8H), 7.49 (t, J = 7.8 Hz, ArH,
2H). 13C{1H} NMR (CDCl3, 100 MHz, δ, ppm): 23.9 (s,
iPr), 27.0 (s, iPr), 28.7 (s, CHiPr), 49.3 (s, N (CH3)2), 53.6
(s, CH2N(CH3)2), 64.9 (s, CH2CH2), 124.4, 127.2, 127.9,
130.9 (s, CH aromatic), 134.7, 135.4, 148.2 (s, C aromatic),
Synthesis of 5. The procedure
for the preparation of 5 was similar to that used for 3 but
with [Pd(μ‐Cl)Cl (IPr*)]2 (1 g, 0.46 mmol) and N,N‐
dimethylbenzylamine (124 mg, 0.92 mmol), and 2 ml
chloroform and reaction time of 6 h. A pale yellow solid
was obtained in 95% yield (1.07 g). 1H NMR (CDCl3,
400 MHz, δ, ppm): 2.18 (s, CH3, 6H), 2.40 (s, N (CH3)2,
6H), 4.00 (s, NCH, 2H), 4.55 (s, CH2, 2H), 6.14 (s, CH
(CH3)2, 4H), 6.74 (s, ArH, 8H), 7.0–7.15 (m, ArH, 15H),
7.17–7.42 (m, ArH, 15H), 7.38–7.62 (q, J = 7.3 Hz, ArH,
10H). 13C{1H} NMR (CDCl3, 100 MHz, δ, ppm): 45.3 (s,
185.1 (s, Ccarbene).
Synthesis
of 3. A vial was charged with [Pd(μ‐Cl)Cl (IMes)]2
(0.68 g, 0.7 mmol) and N,N‐dimethylbenzylamine
(0.21 ml, 1.4 mmol) and dichloromethane (DCM; 2 ml)
as solvent. The solution was stirred at room temperature