10.1002/ejoc.201800948
European Journal of Organic Chemistry
FULL PAPER
washed with water (20 mL) and brine (20 mL), and dried over Na2SO4,
and concentrated in vacuo to give a crude of 285 mg as a white solid
material. Purification by short-plugged column chromatography (SiO2,
toluene/EtOAc = 9/1) yield 112 mg of 2 in 37% as white solid powders.
For data of 2: 1H NMR (400 MHz, CDCl3) 7.84-7.81 (m, 4H), 7.54-7.51 (m,
4H), 7.47 (s, 2H), 7.40 (s, 2H), 7.24 (s, 2H), 7.17 (s, 2H), 5.74 (t, J = 8.2
35.9, 32.3, 31.5, 30.9 , 30.3, 30.1, (many peaks are overlapped), 30.0
(many peaks are overlapped), 29.7, 28.23, 28.19, 23.0 (many peaks are
overlapped), 14.4 (many peaks are overlapped) ppm; 31P NMR (162 MHz,
CDCl3) 127.3, -13.5ppm; MS (DART-TOF) m/z: 1283 [M+NH4]+; IR
(neat): 2917, 2849, 1487, 1451, 1308, 1281, 1034, 961 cm-1; HRMS
(DART-TOF) calcd for C76H118NO11P2: 1282.8175 [M+NH4]+, Found :
1282.8215.
3
3
Hz, 2H), 4.59-4.55 (m, 2H), 4.09 (d, JPH = 11.4 Hz, 3H), 3.94 (d, JPH
=
8.8 Hz, 3H), 2.36-2.20 (m, 8H), 1.45-1.28 (m, 72H), 0.91-0.87 (m, 12H)
ppm; 13C NMR (100 MHz, CDCl3) 153.0, 152.9, 152.8 (d, JCP = 1.4 Hz),
152.6, 148.0 (d, JCP = 5.0 Hz), 146.2 (d, JCP = 6.7 Hz), 140.13, 140.09,
137.3, 137.2, 134.7, 134.1 (d, JCP = 3.8 Hz), 129.8, 129.7, 128.5, 128.3,
123.3, 122.8, 118.0, 117.1, 56.1 (d, JCP = 6.2 Hz), 50.2 (d, JCP = 2.1 Hz),
36.2, 36.1, 34.3, 32.3 (many peaks are overlapped), 31.9, 31.6, 30.1
(many peaks are overlapped), 29.7 (many peaks are overlapped), 28.33,
28.28, 23.0 (many peaks are overlapped), 14.5 (many peaks are
overlapped) ppm; 31P NMR (162 MHz, CDCl3) 127.3, -13.5 ppm; MS
(DART-TOF) m/z: 1494 [MH]+; IR (neat): 2917, 2849, 1479, 1399, 1328,
1025 cm-1; HRMS (DART-TOF) calcd for C90H119N4O11P2: 1493.8345
[MH]+, Found : 1493.8427; Anal. Calcd for C90H118N4O11P2: C, 72.36; H,
7.96; N, 3.75. Found: C, 72.35; H, 7.87; N, 3.78.
Synthesis of 2•AuCl: (Scheme 2). Under an argon atmosphere, to a 10
mL one-neck round-bottomed flask charged with a solution of 2 (75 mg,
0.05 mmol) in toluene (0.5 mL) was added AuCl•S(CH3)2 (18 mg, 0.06
mmol). After stirred at room temperature for 30 min, the reaction mixture
was concentrated in vacuo to give a crude product. The crude was
purified by short-plugged column chromatography (20 mL of
hexane/EtOAc 2/1) to yield 2•AuCl of 75 mg in 86% as white solid
materials. For data of 2•AuCl: 1H NMR (400 MHz, CDCl3) 7.93 (dd, J =
7.8, 1.8 Hz, 2H), 7.83 (dd, J = 7.7, 2.0 Hz, 2H), 7.58-7.51 (m, 6H), 7.43 (s,
2H), 7.22 (s, 4H), 5.78 (t, J = 8.1 Hz, 2H), 4.59 (t, J = 7.9 Hz, 1H), 4.51 (t,
J = 8.0 Hz, 1H), 4.13 (d, 3JPH = 13.9 Hz, 3H), 4.09 (d, 3JPH = 11.4 Hz, 3H),
2.31-2.25 (m, 8H), 1.45-1.27 (m, 72H), 0.92-0.86 (m, 12H) ppm; 13C
NMR (100 MHz, CDCl3) 153.1 (d, JCP = 1.7 Hz), 152.9 (d, JCP = 1.7 Hz),
152.34, 152.30, 146.3 (d, JCP = 6.9 Hz), 144.5 (d, JCP = 3.6 Hz), 140.12,
140.09, 137.3, 136.4, 135.7 (d, JCP = 2.6 Hz), 134.4 (d, JCP = 3.6 Hz),
130.2 (two peaks are overlapped), 129.0, 128.2, 123.5, 123.0, 117.8 (d,
JCP = 4.1 Hz), 117.5 (d, JCP = 4.1 Hz), 55.5 (d, JCP = 6.2 Hz), 54.8 (d, JCP
= 2.1 Hz), 36.1, 36.0, 34.3, 32.3 (many peaks are overlapped), 32.2
(many peaks are overlapped), 31.4, 31.1, 30.0 (many peaks are
overlapped), 29.7 (many peaks are overlapped), 28.2, 23.0 (many peaks
are overlapped), 14.5 (many peaks are overlapped) ppm; 31P NMR (162
MHz, CDCl3) 109.9, -13.5 ppm; MS (ESI) m/z: 1748 [M+Na]+; IR (neat):
2917, 2849, 1479, 1399, 1328, 1041 cm-1; HRMS (ESI) calcd for
C90H118AuClN4O11P2Na: 1747.7519 [M+Na]+, Found: 1747.7491.
Synthesis of 5: (Scheme 2). Under an argon atmosphere, to a solution
of the parent bis-phosphite (174 mg, 0.13 mmol) in toluene (5.2 mL) at 0
ºC was slowly added a cooled-toluene solution of mCPBA (75%, 30 mg,
0.13 mmol). After stirred at 0 ºC for 1 h, the reaction was quenched with
saturated aqueous NaHCO3 (2.6 mL), and stirred at ambient temperature
for 45 min. The mixture was transferred into a separatory funnel, and
washed with water (10 mL) and brine (10 mL), and dried over Na2SO4,
and concentrated in vacuo to give a crude of 167 mg as a white solid
material.
Purification
by
silica-gel
column
chromatography
(toluene/EtOAc = 2/1) yielded 5 of 86 mg in 48% as white powders. For
data of 5: 1H NMR (400 MHz, CDCl3) 8.03 (d, J = 2.6 Hz, 2H), 8.01 (d, J
= 2.6 Hz, 2H), 7.32 (s, 2H), 7.26 (s, 2H), 7.24 (s, 2H), 7.17 (s, 2H), 5.72 (t,
J = 8.2 Hz, 2H), 4.57-4.54 (m, 2H), 4.07 (d, 3JPH = 11.4 Hz, 3H), 3.91 (d,
3JPH = 9.0 Hz, 3H), 2.28-2.18 (m, 8H), 1.14-1.27 (m, 72H), 0.91-0.87 (m,
12H) ppm; 13C NMR (100 MHz, CDCl3) 154.7, 154.5, 153.1 (d, JCP = 1.7
Hz), 152.9, 148.0 (d, JCP = 5.2 Hz), 146.2 (d, JCP = 6.7 Hz), 140.4, 140.2,
137.4 (d, JCP = 2.6 Hz), 137.3 (d, JCP = 2.2 Hz), 134.8, 134.1 (d, JCP = 3.6
Hz), 123.5, 123.0, 117.9 (d, JCP = 2.4 Hz), 117.1 (d, JCP = 3.6 Hz), 56.1 (d,
JCP = 6.0 Hz), 50.3 (d, JCP = 1.4 Hz), 36.2, 36.1, 34.1, 32.3 (many peaks
are overlapped), 32.0, 31.7, 30.1 (many peaks are overlapped), 29.8
(many peaks are overlapped), 28.30, 28.29, 28.2, 23.0 (many peaks are
overlapped), 14.5 (many peaks are overlapped) ppm; 31P NMR (162 MHz,
CDCl3) 128.0, -13.5 ppm; MS (MALDI-TOF) m/z: 1394 [MH]+; IR (neat):
2925, 2853, 1479, 1395, 1296, 1137, 1029 cm-1; HRMS (MALDI-TOF)
calcd for C82H115N4O11P2: 1393.8032 [MH]+, Found : 1393.8079.
Synthesis of 5•AuCl: (Scheme 2). Under a nitrogen atmosphere, to a
solution of 5 (70 mg, 0.05 mmol) in toluene (0.5 mL) was added
AuCl•S(CH3)2 (18 mg, 0.06 mmol). After stirred at room temperature for
0.5 h, the reaction mixture was concentrated in vacuo to give a crude
product as a white solid material. Purification by short-plugged silica-gel
column chromatography (eluent, CH2Cl2) afforded 71 mg of 5•AuCl in
87% yield as white powders. For data of 5•AuCl: 1H NMR (400 MHz,
CDCl3) 8.11 (d, J = 2.5 Hz, 2H), 8.04 (d, J = 2.5 Hz, 2H), 7.38 (s, 2H),
7.32 (s, 2H), 7.23 (s, 2H), 7.22 (s, 2H), 5.76 (t, J = 8.2 Hz, 2H), 4.58 (t, J
= 7.8 Hz, 1H), 4.47 (t, J = 7.8 Hz, 1H), 4.10 (d, 3JPH = 9.3 Hz, 3H), 4.07 (d,
3JPH = 6.7 Hz, 3H), 2.30-2.22 (m, 8H), 1.45-1.26 (m, 72H), 0.91-0.86 (m,
12H) ppm; 13C NMR (100 MHz, CDCl3) 153.8, 153.7, 153.1, 152.9, 145.9
(d, JCP = 6.7 Hz), 144.2, (d, JCP = 2.9 Hz), 140.8 140.4, 137.0, 136.3,
135.4 (d, JCP = 2.2 Hz), 134.1 (d, JCP = 2.9 Hz), 123.4, 122.9, 117.7 (d,
JCP = 3.8 Hz), 117.2 (d, JCP = 4.1 Hz), 55.8 (d, JCP = 6.0 Hz), 55.0, 35.8,
35.7, 33.7, 32.0 (many peaks are overlapped), 31.1, 30.9, 29.7 (many
peaks are overlapped), 29.65 (many peaks are overlapped), 29.63, 29.4,
27.9, 22.7 (many peaks are overlapped), 14.1 (many peaks are
overlapped) ppm; 31P NMR (162 MHz, CDCl3) 109.8, -13.1 ppm; MS
(ESI) m/z: 1648 [M+Na]+; IR (neat): 2917, 2849, 1479, 1399, 1276, 1141,
1038, 894 cm-1; HRMS (ESI) calcd for C82H114AuClN4O11P2Na:
1647.7206 [M+Na]+, Found : 1647.7184.
Synthesis of 6: (Scheme 2). Under an argon atmosphere, to a solution
of the parent bis-phosphite (592 mg, 0.47 mmol) in toluene (18.8 mL) at 0
ºC was slowly added cooled-toluene solution of mCPBA (75%, 198 mg,
047 mmol). The reaction was quenched with saturated aqueous NaHCO3
(9.4 mL), and stirred at ambient temperature for 35 min. The mixture was
transferred into a separatory funnel, and washed with water (10 mL) and
brine (10 mL), and dried over Na2SO4, and concentrated in vacuo to give
a crude of 594 mg as a white solid material. Purification by silica-gel
column chromatography (toluene/EtOAc = 4/1) yielded 192 mg of 6 in
32% as white powders. For data of 6: 1H NMR (400 MHz, CDCl3) 7.13 (s,
2H), 7.09 (s, 2H), 6.65 (s, 2H), 6.60 (s, 2H), 5.66 (d, J = 7.3 Hz, 2H), 4.74
(t, J = 8.1 Hz, 2H), 4.66 (d, J = 7.3 Hz, 2H), 4.60-4.55 (m, 2H), 4.05 (d,
3JPH = 11.4 Hz, 3H), 3.90 (d, 3JPH = 9.1 Hz, 3H), 2.23-2.18 (m, 8H), 1.42-
1.27 (m, 72H), 0.90-0.87 (m, 12H) ppm; 13C NMR (100 MHz, CDCl3)
155.7 (d, JCP = 1.4 Hz), 155.4, 147.3 (d, JCP = 4.8 Hz), 145.6 (d, JCP = 7.4
Hz), 139.8 , 137.5 , 137.2, 134.1 (d, JCP = 3.8 Hz), 121.7, 121.2, 117.7,
116.7 (d, JCP = 4.1 Hz), 99.4, 56.0 (d, JCP = 6.0 Hz), 50.2, 36.5, 36.1,
Synthesis of 6•AuCl: (Scheme 2). Under a nitrogen atmosphere, to a
solution of 6 (63 mg, 0.05 mmol) in toluene (0.5 mL) was added
AuCl•S(CH3)2 (18 mg, 0.06 mmol). After stirred at room temperature for
0.5 h, the reaction mixture was concentrated in vacuo to give a crude
product as a white solid material. Purification by short-plugged silica-gel
column chromatography (eluent, CH2Cl2) afforded 68 mg of 6•AuCl in
89% yield as white powders. For data of 6•AuCl: 1H NMR (400 MHz,
CDCl3) 7.15 (s, 2H), 7.14 (s, 2H), 6.72 (s, 4H), 5.64 (d, J = 7.4 Hz, 2H),
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