Organometallics
Article
4.77 (m, 1H), 2.70−2.64 (m, 2H), 2.45 (s, 3H), 2.34−2.22 (m, 2H),
1.82 (s, 3H), 1.73 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 170.5 (d,
1JCAg = 273 Hz), 170.5 (d, 1JCAg = 239 Hz), 141.2, 138.8, 138.1, 138.1,
136.2, 136.2, 129.6, 129.6, 129.4, 129.4, 129.3, 128.7, 128.7, 128.1,
127.6, 122.6, 116.2, 114.8, 110.2, 110.2, 67.9, 66.7, 31.4, 29.6, 21.6,
Data for 9c. From 8c (133 mg, 0.22 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 110 mg (74%) of
1
9c as a yellow solid. H NMR (400 MHz, CDCl3) δ 7.54−7.46 (m,
2H), 7.36−7.29 (m, 1H), 7.27−7.21 (m, 9H), 7.17−7.08 (m, 2H),
6.89 (d, 3JHH = 9.3 Hz, 1H), 6.72 (dd, 3JHH = 9.3, 6.6 Hz, 1H), 6.64 (s,
1H), 6.37 (d, 3JHH = 6.6 Hz, 1H), 5.55−5.50 (m, 1H), 4.79−4.73 (m,
1H), 3.97 (s, 3H), 2.78−2.74 (m, 1H), 2.66−2.62 (m, 1H), 2.41−2.38
(m, 1H), 2.24−2.18 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 163.8,
161.6, 139.0, 138.9, 131.1, 129.6, 128.7, 128.6, 128.4, 128.0, 127.6,
126.3, 122.5, 116.3, 115.8, 114.9, 108.3, 69.0, 65.3, 56.1, 33.4, 28.4.
HRMS (FAB) m/z calcd for C30H27N3OAu (M − Cl) 642.1820,
19.47, 19.20. [α]20 −150.3 (c, 0.1, CHCl3).
D
Data for 8h. From 7g (100 mg, 0.17 mmol) and Ag2O (85.7 mg
0.37 mmol), the general procedure was applied to yield 95 mg (80%)
of 8h as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.38−7.31 (m,
2H), 7.21−7.15 (m, 10H), 6.93 (d, 3JHH = 9.3 Hz, 1H), 6.74 (dd, 3JHH
3
= 9.3, 6.7 Hz, 1H), 6.69 (s, 1H), 6.34 (d, JHH = 6.7 Hz, 1H), 5.32−
5.27 (m, 1H), 4.75−4.70 (m, 1H), 3.04−2.98 (m, 1H), 2.64−2.78 (m,
2H), 2.30−2.26 (m, 1H), 2.18−2.13 (m, 2H), 2.05−1.98 (m, 1H),
1.38 (d, 3JHH = 6.9 Hz, 6H), 1.19 (d, 3JHH = 6.6 Hz, 3H), 1.05 (d, 3JHH
found 642.1833. [α]20 −73.4 (c, 0.1, CH2Cl2). Mp: 113−115 °C.
D
Data for 9d. From 8d (126 mg, 0.20 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:2 AcOEt/n-hexane) to yield 103 mg (74%) of
3
3
= 6.5 Hz, 3H), 1.00 (d, JHH = 6.6 Hz, 3H), 0.98 (d, JHH = 6.7 Hz,
3H). 13C NMR (125 MHz, CDCl3) δ 171.4 (d, 1JCAg = 273 Hz), 171.4
(d, JCAg = 236 Hz), 151.9, 146.5, 146.4, 138.7, 137.5, 129.58, 129.52,
1
1
9d as a yellow solid. H NMR (400 MHz, CDCl3) δ 7.65−7.56 (m,
128.4, 128.0, 127.4, 127.2, 126.6, 126.2, 122.2, 122.1, 122.0, 116.1,
115.5, 109.1, 109.0, 68.5, 65.8, 34.4, 32.7, 31.1, 30.9, 28.9, 24.9, 24.8,
24.2, 24.1, 24.0. Crystallization was performed at −28 °C by slow
diffusion of pentane in a CH2Cl2 solution of the complex.
2H), 7.55−7.49 (m, 2H), 7.42−7.33 (m, 1H), 7.28−7.16 (m, 9H),
6.88 (d, 3JHH = 9.2 Hz, 1H), 6.73 (dd, 3JHH = 9.2, 6.6 Hz, 1H), 6.63 (s,
1H), 6.37 (d, 3JHH = 6.6 Hz, 1H), 5.55−5.49 (m, 1H), 4.78−4.73 (m,
1H), 2.84−2.71 (m, 1H), 2.66−2.56 (m, 1H), 2.43−2.30 (m, 1H),
2.25−2.14 (m, 1H), 1.49 (s, 9H). 13C NMR (100 MHz, CDCl3) δ
163.7, 153.7, 139.0, 138.7, 130.8, 129.4, 129.2, 128.5, 128.4, 128.2,
127.8, 127.4, 125.9, 122.3, 116.1, 115.5, 107.8, 68.8, 64.9, 34.9, 33.3,
31.4, 28.1. HRMS (FAB) m/z calcd for C33H33N3ClAu (M − Cl)
668.2340, found 668.2346. [α]20D −109.0 (c, 0.1, CH2Cl2). Mp: 108−
110 °C.
Data for 14. From 13 (152 mg, 0.31 mmol), the general procedure
was applied to yield 167 mg (78%) of 14 as a white crystalline solid.
3
1H NMR (400 MHz, CDCl3) δ 7.64 (s, 1H), 7.44 (d, JHH = 9.2 Hz,
3
3
1H), 7.23 (s, 2H), 6.96 (dd, JHH = 9.1, 6.6 Hz, 1H), 6.53 (d, JHH
=
3
6.0 Hz, 1H), 3.04 (hept, JHH = 7.2 Hz, 1H), 2.42−2.40 (m, 6H),
2.39−2.29 (m, 2H), 2.28−2.25 (m, 3H), 1.84−1.68 (m, 6H), 1.41 (d,
3
3
3JHH = 6.9 Hz, 6H), 1.23 (d, JHH = 6.9 Hz, 6H), 1.12 (d, JHH = 6.8
Data for 9e. From 8e (121 mg, 0.17 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 120 mg (90%) of
Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 152.1, 146.7, 138.2, 130.2,
130.1, 127.7, 122.7, 122.0, 116.9, 116.0, 109.0, 108.9, 59.6, 44.7, 35.8,
34.6, 31.3, 29.9, 25.1, 24.4, 24.2. Crystallization was performed at room
temperature by slow diffusion of n-hexane in a CH2Cl2 solution of the
complex.
1
9e as a light−yellow solid. H NMR (400 MHz, CDCl3) δ 8.12 (s,
1H), 7.81 (s, 1H), 7.70 (s, 1H), 7.50−7.43 (m, 2H), 7.32−7.19 (m,
3
3
8H), 7.05 (d, JHH = 9.1 Hz, 1H), 6.83 (s, 1H), 6.81 (dd, JHH = 9.1,
3
General Procedure for Synthesis of Gold Complexes 8a−h
and 15. To a solution of silver(I) complex 8a−h or 14 (0.05−0.24
mmol) in dry CH2Cl2 (20 mL/mmol) was added AuCl(SMe2) (1
equiv), and the mixture was stirred in the darkness, at room
temperature for 3 h. The mixture was filtered through a Celite plug,
the solvent was evaporated in vacuo, and the residue was purified by
flash chromatography. Starting material, yields, solvents used for
chromatography, and characterization data for compounds 9a−h and
15 are as follows.
6.4 Hz, 1H), 6.45 (d, JHH = 6.4 Hz, 1H), 5.62−5.57 (m, 1H), 4.82−
4.77 (m, 1H), 2.74−2.62 (m, 2H), 2.35−2.29 (m, 2H). 13C NMR
2
(100 MHz, CDCl3) δ 163.9, 138.9, 138.5, 135.8, 135.7, 132.2 (q, JCF
= 34.2 Hz), 130.2, 130.2, 129.4, 128.7, 128.3, 127.9, 124.1, 123.2 (q,
1
1JCF = 273.1 Hz), 123.1 (q, JCF = 273.6 Hz), 122.2, 118.1, 117.1,
109.9, 68.9, 66.3, 33.0, 29.6. HRMS (FAB) m/z calcd for
(C31H23N3F6Au−Cl) 748.1462, found 748.1486. [α]20 −106.9 (c,
D
0.1, CH2Cl2). Mp: 104−106 °C.
Data for 9f. From 8f (133 mg, 0.21 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 177 mg (81%) of 9f
Data for 9a. From 8a (138 mg, 0.24 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 104 mg (67%) of
1
3
as a yellow solid. H NMR (400 MHz, CDCl3) δ 7.59 (t, JHH = 8.4
1
9a as a yellow solid. H NMR (400 MHz, CDCl3) δ 7.68−7.63 (m,
Hz, 1H), 7.54−7.48 (m, 2H), 7.30−7.11 (m, 8H), 6.85 (d, 3JHH = 9.3
Hz, 1H), 6.75−6.67 (m, 3H), 6.51 (s, 1H), 6.38 (d, JHH = 6.6 Hz,
1H), 7.62−7.36 (m, 5H), 7.33−7.19 (m, 9H), 6.92 (d, 3JHH = 9.3 Hz,
3
3
3
1H), 6.74 (dd, JHH = 9.3, 6.6 Hz, 1H), 6.67 (s, 1H), 6.38 (d, JHH
=
1H), 5.49−5.45 (m, 1H), 4.72−4.65 (m, 1H), 3.82 (s, 3H), 3.63 (s,
3H), 2.81−2.68 (m, 1H), 2.66−2.54 (m, 1H), 2.39−2.29 (m, 1H),
2.24−2.10 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 162.9, 158.5,
158.4, 132.6, 132.0, 129.5, 128.6, 128.4, 128.3, 128.2, 127.6, 122.6,
117.0, 116.2, 112.0, 107.4, 105.0, 104.7, 68.8, 64.8, 56.1, 56.0, 33.4,
27.7. HRMS (FAB) m/z calcd for C34H37N3O4SAu [M − Cl +
6.6 Hz, 1H), 5.59−5.52 (m, 1H), 4.78−4.73 (m, 1H), 2.87−2.73 (m,
1H), 2.65−2.59 (m, 1H), 2.38−2.32 (m, 1H), 2.24−2.18 (m, 1H). 13C
NMR (100 MHz, CDCl3) δ 163.8, 139.0, 138.8, 134.0, 130.1, 129.7,
129.5, 129.0, 128.7, 128.5, 128.4, 128.0, 127.6, 122.4, 116.5, 115.8,
108.4, 68.8, 65.3, 33.2, 28.5. HRMS (FAB) m/z calcd for
C29H25N3CAu (M − Cl) 612.1714, found 612.1715. [α]20 −135.8
D
thioglycerol (matrix)] 780.2170, found 780.2150. [α]20 −211.4 (c,
D
(c, 0.05, CH2Cl2). Mp: 193−195 °C.
0.02, CH2Cl2). Mp: 130−132 °C.
Data for 9b. From 8b (34 mg, 0.06 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 38 mg (97%) of 9a
as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 7.52−7.41 (m, 2H),
7.39−7.29 (m, 2H), 7.25−7.11 (m, 10H), 6.89 (d, 3JHH = 9.2 Hz, 1H),
6.70 (dd, 3JHH = 9.2, 6.7 Hz, 1H), 6.65 (s, 1H), 6.31 (d, 3JHH = 6.7 Hz,
1H), 5.50−5.46 (m, 1H), 4.76−4.72 (m, 1H), 2.75−2.70 (m, 1H),
2.62−2.55 (m, 1H), 2.32−2.27 (m, 1H), 2.23−2.17 (m, 1H). 13C
Data for 9g. From 8g (134 mg, 0.22 mmol), the general procedure
was applied, and the crude mixture was purified by flash
chromatography (1:3 AcOEt/n-hexane) to yield 100 mg (68%) of
1
9g as a yellow solid. H NMR (400 MHz, CDCl3) δ 7.55−7.46 (m,
3
2H), 7.29−7.13 (m, 8H), 7.10 (s, 1H), 7.07 (s, 1H), 6.92 (d, JHH
=
3
9.2 Hz, 1H), 6.76 (dd, JHH = 9.2, 6.6 Hz, 1H), 6.69 (s, 1H), 6.32 (d,
3JHH = 6.2 Hz, 1H), 5.58−5.50 (m, 1H), 4.82−4.76 (m, 1H), 2.81−
2.68 (m, 1H), 2.65−2.54 (m, 1H), 2.49 (s, 3H), 2.43−2.33 (m, 1H),
2.28−2.15 (m, 1H), 1.98 (s, 3H), 1.84 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 163.0, 140.7, 137.7, 137.0, 136.8, 130.3, 129.1, 128.9, 128.8,
128.6, 128.5, 128.4, 127.9, 127.5, 122.6, 116.2, 115.7, 108.4, 68.5, 65.5,
33.3, 28.7, 21.5, 19.7. HRMS (FAB) m/z calcd for C32H31N3Au (M −
1
NMR (100 MHz, CDCl3) δ 164.2 (d, JCF = 248.8 Hz), 163.9, 138.8,
138.0, 131.8, 130.0, 129.5, 128.7, 128.6, 128.5, 128.1, 127.9, 127.7,
127.4, 122.3, 116.8, 116.4, 116.2, 108.7, 68.9, 65.5, 32.2, 28.6. HRMS
(FAB) m/z calcd for C32H32FN3O2SAu [M − Cl + thioglycerol
(matrix)] 738.1865, found 738.1860. [α]20 −171.8 (c, 0.1, CHCl3).
D
Cl) 654.2184, found 654.2216. [α]20 −211.4 (c, 0.02, CH2Cl2). Mp:
Mp: 121−123 °C. Crystallization was performed at −28 °C by slow
diffusion of pentane in a CH2Cl2 solution of the complex.
D
134−136 °C.
1336
Organometallics 2015, 34, 1328−1338