6296 Organometallics, Vol. 29, No. 23, 2010
Makino et al.
1
as a colorless solid: mp 113.5-114.3 °C; H NMR (600 MHz,
Imidazolinium Salt 14. To a solution of 13 (220 mg, 0.30 mmol)
inHC(OEt)3 (6 mL) was addedNH4Cl (18 mg, 0.33 mmol), and the
mixture was heated at 120 °C for 20 h. All volatiles was removed
under reduced pressure, and CH2Cl2 (10 mL) and 5% aqueous
NaHCO3 (10 mL) were added to the residue. The organic layer was
separated, and the aqueous layer was extracted with CH2Cl2. The
combined organic layer was dried over MgSO4, and the filtrate was
concentrated. The product was purified by recrystallization from
CH2Cl2/diethyl ether to afford 14 (194 mg, 83%) as colorless
powder: mp 241.0-242.0 °C; 1H NMR (300 MHz, CDCl3) 9.62 (s,
1H), 7.53-7.44 (m, 3H), 7.35-7.31 (m, 4H), 7.22-7.14 (m, 8H),
4.88 (s, 4H), 3.95 (t, J = 9.6 Hz, 2H), 3.09 (septet, J = 6.6 Hz, 2H),
2.98 (septet, J = 6.6 Hz, 2H), 2.47 (t, J = 9.6 Hz, 2H), 1.42 (d, J =
6.6 Hz, 6H), 1.35 (d, J = 6.6 Hz, 6H), 1.23 (d, J = 6.9 Hz, 6H), 0.90
(d, J=6.9 Hz, 6H); 13C NMR (75 MHz, CDCl3) 165.5, 160.2,
148.3, 147.9, 146.7, 145.7, 141.6, 140.9, 132.3, 131.5, 130.5, 129.5,
129.3, 129.2, 129.0, 128.9, 127.7, 127.0, 126.4, 125.5, 125.0, 124.9,
123.7, 123.6, 67.4, 55.8, 55.2, 52.3, 34.9, 30.9, 29.1, 25.3, 25.0, 23.4,
23.3; IR (KBr) 3397, 2964, 1632, 1431, 1399, 1262 cm-1; HR-MS
(FAB) calcd for C51H58N3O2 ([M - Cl]þ) 744.4529, found
744.4528.
AgCl Complex 15-Cl. A mixture of 14 (78 mg, 0.1 mmol) and
Ag2O (14 mg, 0.06 mmol) in CH2Cl2 was stirred for 21 h at room
temperature. The resulting precipitate was filtrated off, and the
filtrate was concentrated. Ag complex 15-Cl was obtained (89 mg,
quant) as a colorless solid and used without further purification.
Suitable crystals for the X-ray crystal structural analysis were
obtained by recrystallization from CH2Cl2/diethyl ether: mp
295.0-296.3 °C; 1H NMR (600 MHz, CDCl3) 7.51-7.45 (m, 4H),
7.38 (t, J = 7.2 Hz, 1H), 7.33 (dd, J = 7.8, 1.8 Hz, 1H), 7.30 (d, J =
8.4 Hz, 2H), 7.23-7.14 (m, 5H), 7.15-7.12 (m, 2H), 4.34 (t, J =
9.6 Hz, 2H), 4.14-4.11 (m, 2H), 4.04-4.00 (m, 2H), 3.94 (t, J =
9.6 Hz, 2H), 3.04 (septet, J =7.2 Hz, 2H), 2.93 (septet, J =7.2 Hz,
2H), 1.74 (s, 6H), 1.34 (d, J =7.2 Hz, 6H), 1.32 (d, J =7.2 Hz,
6H), 1.27 (d, J =6.6 Hz, 6H), 1.01 (d, J = 6.6 Hz, 6H); 13C NMR
(150 MHz, CDCl3) 207.4 (dd, JC-Ag = 259, 223 Hz), 164.4, 147.9,
147.5, 146.5, 145.8, 141.4, 139.5, 134.6, 133.3, 131.7, 130.6, 130.2,
130.0, 129.5, 129.39, 129.37, 128.1, 127.1, 126.0, 125.7, 125.2,
125.1, 124.6, 123.27, 123.26, 67.3, 54.9, 54.5 (d, 3JC-Ag = 8.8 Hz),
53.8 (d, 3JC-Ag=8.8 Hz), 34.7, 31.8, 28.79, 28.76, 25.4, 24.0, 23.5;
IR (KBr) 2962, 1646, 1491, 1397, 1364, 1273, 1219 cm-1; HR-MS
(ESI) calcd 852.3503 ([M - Cl]þ), found 852.3487. Anal. Calcd for
C51H57AgClN3O2: C, 69.03; H, 6.47; N, 4.74. Found: C, 69.03; H,
6.79; N, 4.32.
AgPF6 Complex 15-PF6. To a solution of 15-Cl (89 mg, 0.1 mmol)
in CH2Cl2 (5 mL) was added an excess amount of KPF6 and water
(3 mL), and the biphasic solution was stirred for 6 h. The organic
layer was separated and dried over MgSO4. The filtrate was con-
centrated to afford 15-PF6 (100 mg, quant) as a colorless solid.
Suitable crystals for an X-ray structural analysis were obtained
by recrystallization from CH2Cl2/hexane: mp 195.0-196.0 °C; 1H
NMR (300 MHz, CDCl3) 7.52-7.43 (m, 7H), 7.35 (s, 2H), 7.31 (d,
J = 7.8 Hz, 2H), 7.22-7.10 (m, 4H), 4.60 (t, J = 9.9 Hz, 2H), 4.23
(br m, 4H), 3.59 (t, J = 9.9 Hz, 2H), 3.16-3.03 (m, 4H), 1.73 (s,
6H), 1.36 (d, J = 6.6 Hz, 6H), 1.34 (d, J = 6.3 Hz, 6H), 1.32 (d,
J = 6.9 Hz, 6H), 1.04 (d, J = 6.9 Hz, 6H); 13C NMR (150 MHz,
CDCl3) 204.0 (dd, JC-Ag = 265.8, 227.1 Hz), 171.4 (br), 148.6,
147.9, 146.9, 146.5, 143.2, 140.6, 134.3, 133.3, 132.4, 131.5, 130.5,
130.1, 130.0, 129.8, 127.5, 126.7, 126.1, 125.0, 124.8, 123.8, 123.6,
122.8, 69.8, 54.9 (d, 3JC-Ag = 8.8 Hz), 54.0, 53.7 (d, 3JC-Ag = 8.8
Hz), 34.8, 31.1, 28.84, 28.78, 25.5, 25.4, 24.0, 23.6; IR (KBr) 2963,
1634, 1497, 1461, 1400, 1271, 1220, 1109 cm-1. Anal. Calcd for
C51H57AgF6N3O2P: C, 61.45; H, 5.76; N, 4.22. Found: C, 61.18;
H, 5.90; N, 4.13.
CDCl3) 8.02 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 7.8 Hz, 2H), 7.42
(dd, J = 7.8, 1.8 Hz, 1H), 7.39 (dd, J = 7.8, 1.8 Hz, 1H), 7.34
(dd, J = 7.8, 1.8 Hz, 1H), 7.29 (dd, J = 7.8, 1.8 Hz, 1H), 7.18 (t,
J = 7.8 Hz, 1H), 6.93 (t, J = 7.8 Hz, 1H), 4.45 (t, J = 9.6 Hz,
2H), 4.09 (t, J = 9.0 Hz, 2H), 1.65 (s, 6H); 13C NMR (150 MHz,
CDCl3) 164.7, 147.4, 147.2, 140.4, 132.0, 131.3, 130.6, 130.2,
129.2, 129.0, 127.7, 126.4, 125.6, 124.8, 123.9, 123.6, 110.8, 67.6,
55.0, 34.9, 32.1; IR (KBr) 2962, 1644, 1399, 1353, 1239 cm-1
Anal. Calcd for C24H20BrNO2: C, 66.37; H, 4.64; N, 3.22.
Found: C, 66.57; H, 4.84; N, 3.17.
Boronate 12. To a suspension of N-(4-iodo-2,6-diisopropyl)-
N0-(2,6-diisopropyl)oxamide7a (7.48 g, 14 mmol) and NaBH4
(3.18 g, 84 mmol) in anhydrous THF (120 mL) was slowly added
.
BF3 OEt2 (13.8 mL, 112 mmol) at ambient temperature. The
3
mixture was stirred for 1 h at ambient temperature, and then the
mixture was heated to reflux for 18 h. The mixture was quenched
with MeOH (12 mL) and concentrated HCl (3 mL) at 0 °C. All
volatiles were removed by evaporation, and aqueous NaOH (1 M,
150 mL) was added to the residue. The mixture was extracted with
diethyl ether (100 mL ꢀ 3), and the combined organic layer was
dried over MgSO4 and evaporated. The crude product was puri-
fied by column chromatography (silica gel, hexane/AcOEt (25:1))
to afford N-(4-iodo-2,6-diisopropylphenyl)-N0-(2,6-diisopro-
pylphenyl)ethylenediamine (6.46 g, 67%) as a colorless solid:
1
mp 63.8-65.0 °C; H NMR (300 MHz, CDCl3) 7.36 (s, 2H),
7.12-7.03 (m, 3H), 3.36-3.21 (m, 6H), 3.11 (s, 4H), 1.24 (d, J =
6.9 Hz, 12H), 1.21 (d, J = 6.9 Hz, 12H); 13C NMR (150 MHz,
CDCl3) 145.0, 143.3, 143.0, 142.5, 133.0, 124.0, 123.6, 88.4, 52.1,
27.7, 24.2, 24.0; IR (KBr) 3370, 2963, 2866, 1444, 1247, 1191 cm-1
.
Anal. Calcd for C26H39IN2: C, 61.65; H, 7.76; N, 5.53. Found: C,
61.69; H, 7.72; N, 5.27.
To a suspension of N-(4-iodo-2,6-diisopropylphenyl)-N0-(2,6-
diisopropylphenyl)ethylenediamine (2.28 g, 4.5 mmol) and Pd-
(dppf)Cl2 (97.8 mg, 0.135 mmol) in anhydrous dioxane (20 mL)
were added pinacolborane (1.9 mL, 6.75 mmol) and NEt3 (1.9 mL,
13.5 mmol). After the mixture was heated at 80 °C for 12 h, water
(20 mL) was added. The product was extracted with diethyl ether
(20 mL ꢀ 2), and the organic layer was dried over MgSO4. The
filtrate was concentrated, and the product was purified by column
chromatography (silica gel, hexane/AcOEt (25:1)) to afford 12
(1.68 g, 74%) as a colorless solid: mp 125.8-126.0 °C; 1H NMR
(300 MHz) 7.56 (s, 2H), 7.12-7.03 (m, 3H), 3.37-3.26 (m, 4H),
3.18-3.14 (m, 4H), 1.32 (s, 12H), 1.27 (d, J= 6.9 Hz, 12H), 1.23 (d,
J = 6.9 Hz, 12H); 13C NMR (75 MHz, CDCl3) 146.7, 143.1, 142.5,
140.7, 130.4, 123.9, 123.6, 83.4, 52.2, 52.0, 27.9, 27.4, 24.8, 24.2,
24.1; IR (KBr) 3356, 2961, 1604, 1459, 1374, 1312, 1194 cm-1
Anal. Calcd for C32H51BN2O2: C, 75.87; H, 10.15; N, 5.53. Found:
C, 75.89; H, 10.23; N, 5.47.
.
Compound 13. A mixture of 12 (217 mg, 0.50 mmol), 5 (279 mg,
0.55 mmol), Pd(PPh3)4 (58 mg, 0.050 mmol), K2CO3 (83 mg, 0.60
mmol), DME (3.6 mL), and water (1.2 mL) was heated at 100 °C
for 68 h. Water (20 mL) and diethyl ether (10 mL) were added. The
organic layer was separated, and the aqueous layer was extracted
with diethyl ether. The combined organic layer was dried over
MgSO4, and the filtrate was concentrated. The crude product was
purified by column chromatography (silica gel, hexane/AcOEt
(4:1)) to afford 13 (312 mg, 85%) as colorless solid: mp 75.0-
77.0 °C; 1H NMR (600 MHz, CDCl3) 7.49 (d, J = 8.4 Hz, 2H),
7.44-7.42 (m, 2H), 7.22 (d, J = 8.4 Hz, 2H), 7.20-7.12 (m, 6H),
7.08-7.07 (m, 3H), 4.34 (t, J = 9.6 Hz, 2H), 3.98 (t, J = 9.6 Hz,
2H), 3.43 (septet, J = 6.6 Hz, 2H), 3.31 (septet, J = 6.6 Hz, 2H),
3.24 (t, J = 6.6 Hz, 2H), 3.19 (t, J = 6.6 Hz, 2H), 1.72 (s, 6H), 1.28
(d, J = 6.6 Hz, 12H), 1.07 (d, J = 7.2 Hz, 12H); 13C NMR (150
MHz, CDCl3) 164.6, 148.3, 148.0, 143.6, 142.6, 142.5, 142.3, 140.6,
133.7, 131.74, 131.70, 130.8, 129.2, 129.0, 128.6, 127.4, 125.6, 125.2,
125.0, 124.1, 123.62, 123.57, 123.1, 122.9, 67.3, 54.9, 52.9, 52.1, 34.8,
31.7, 27.8, 27.7, 24.3, 24.1, 24.0; IR (KBr) 2960, 1645, 1428, 1399,
1228 cm-1. Anal. Calcd for C50H59N3O2:C, 81.81;H, 8.10;N, 5.72.
Found: C, 81.86; H, 8.22; N, 5.58.
Pd Complex 16. A suspension of 15-Cl (89 mg, 0.10 mmol) and
Pd(PhCN)2Cl2 (42 mg, 0.11 mmol) in 1,4-dioxane (3 mL) was
heated at 100 °C for 20 h. The resulting precipitate was filtrated
off, and the filtrate was concentrated. The product was purified
by column chromatography (silica gel, Hex/AcOEt (5:1)) to
afford 16 (77 mg, 84%) as a yellow powder. Suitable crystals