4
Tetrahedron
ACCEPTED MANUSCRIPT
7.80 (m, 2H), 7.61 (m, 1H), 7.55 – 7.39 (m, 3H), 5.35 (d, J =
(s), 135.44(s),132.24 (s), 130.23 (s), 129.46 (s), 128.86 (s),
1.5 Hz, 1H), 5.24 (d, J = 1.5 Hz, 1H), 2.12 (s, 3H).
111.54 (s), 63.01 (s), 14.09 (s).19F NMR (376 MHz, CDCl3) δ -
109.23 (s).HRMS (ESI, m/z): Calculated for [C12H10BrFO3]
(M+H)+ 300.9870, found 300.9869.
4.2.13 3,4-dihydronaphthalen-1-yl acetate (1l)
The title compound was isolated as a white solid after
chromatography on silica (hexane:ethyl acetate=10:1). Yield:
90%, 1.69g. 1H NMR (400 MHz, CDCl3) δ 7.19 – 7.12 (m, 3H),
7.10 – 7.06 (m, 1H), 5.69 (m, 1H), 2.85 (m, 2H), 2.44 (m, 2H),
2.28 (s, 3H).
ethyl (E)-2-fluoro-4-(4-iodophenyl)-4-oxobut-2-enoate(3d)
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.5 Hz, 2H), 7.64
(d, J = 8.4 Hz, 2H), 7.06 (d, J = 30.5 Hz, 1H), 4.40 (q, J = 7.1 Hz,
2H), 1.40 (t, J = 7.1 Hz, 3H).13C NMR (101 MHz, CDCl3) δ
187.53 (s),δ 168.30 (s), 151.01 (s), 138.23 (s), 135.97 (s), 125.48
(t, J = 696.7 Hz), 116.18 – 114.06 (m), 111.51 (d, J = 5.1 Hz),
102.41 (s), 63.01 (s), 14.09 (s)19F NMR (376 MHz, CDCl3) δ -
109.18 (s).HRMS (ESI, m/z): Calculated for [C12H10IFO3]
(M+H)+ 348.9731, found 348.9731.
4.2.14 (E)-1,2-diphenylvinyl acetate (1m)
The title compound was isolated as a white solid after
chromatography on silica (hexane:ethyl acetate=20:1). Yield:
85%, 2.02g. 1H NMR (400 MHz, CDCl3) δ 7.51 (m, 4H), 7.38 –
7.28 (m, 5H), 7.23 (m, 1H), 6.68 (s, 1H), 2.27 (s, 3H).
ethyl-2-fluoro-4-(4-methoxyphenyl)-4-oxobut-2-enoate(3e,
Z:E=1:1)
4.2.15 1-(4-(trifluoromethyl)phenyl)vinyl acetate (1n)
1H NMR (400 MHz, CDCl3) δ 7.92 (m, 4H), 7.08 (d, J = 31.3
Hz, 1H), 7.01 – 6.90 (m, 4H), 6.63 (d, J = 16.9 Hz, 1H), 4.39 (m,
2H), 4.14 (m, 2H), 3.89 (d, J = 3.0 Hz, 6H), 1.39 (m, 3H), 1.08
(m, 3H).13C NMR (101 MHz, CDCl3) δ 189.70 – 187.98 (m),
189.70 – 184.07 (m), 164.32 (d, J = 12.9 Hz), 160.48 (s), 160.13
(s), 159.55 (s), 159.18 (s), 152.90 (s), 152.06 (s), 150.08 (s),
149.36 (s), 131.32 (s), 129.74 (s), 129.48 (s), 116.89 (d, J = 14.5
Hz), 114.08 (d, J = 4.5 Hz), 112.58 (d, J = 6.1 Hz), 62.79 (s),
62.44 (s), 55.60 (d, J = 1.4 Hz), 14.10 (s), 13.55 (s).19F NMR
(376 MHz, CDCl3) δ -111.98 (s), -115.61 (s).Calculated for
[C12H14FO4] (M+H)+ 253.0871, found 253.0874.
The title compound was isolated as a yellow oil after
chromatography on silica (hexane:ethyl acetate=15:1). Yield:
90%, 2.07g. 1H NMR (400 MHz, CDCl3) δ 7.72 – 7.56 (m, 3H),
7.48 (t, J = 7.8 Hz, 1H), 5.55 (d, J = 2.5 Hz, 1H), 5.14 (d, J = 2.5
Hz, 1H), 2.30 (s, 3H).
4.2.16 General procedure 2: systhesis of compound 3a-o
An oven-dried Schlenk tube (10 mL) was equipped with a
magnetic stir bar, 1a-o(0.1mmol, 1.0equiv), b(0.2mmol,
2.0equiv), Na2CO3(0.2mmol,
2.0equiv), fac-[Ir(ppy)3]
(0.001mmol, 1.0mol %) in CH3CN (1.2 mL) and H2O(0.2ml)
were irradiated with two 45W light bulbs for 24h at room
temperature which were filled with Argon. The tube was placed
in the central of the two 45W light bulbs, and the resulting
solution was stirred at ambient temperature under visible- light
irradiation for 24h. After the reaction finished, the crude mixture
were diluted by ethyl acetate and brine and dried by MgSO4.
Then the organic layer was filtered and concentrated. The
residue was purified by chromatography on silica gel to afford
the 3a-3n.
ethyl (E)-2-fluoro-4-oxo-4-(p-tolyl)but-2-enoate (3f)
1H NMR (400 MHz, CDCl3) δ 7.84 (m, J = 8.3, 2.2 Hz, 4H),
7.29 (m, J = 12.9, 5.1 Hz, 4H), 7.10 (d, J = 31.0 Hz, 1H), 6.64 (d,
J = 16.8 Hz, 1H), 4.39 (m, J = 7.1 Hz, 2H), 4.13 (m, J = 7.1 Hz,
2H), 2.43 (d, J = 2.7 Hz, 6H), 1.39 (m, J = 7.1 Hz, 3H), 1.07 (m, J
= 7.1 Hz, 3H).13C NMR (101 MHz, CDCl3) δ 187.82, 160.09,
152.27, 145.06, 134.24, 129.57, 129.54, 129.06, 128.98, 128.29,
116.91, 116.76, 112.38, 112.33, 62.83, 62.48, 21.81, 14.10,
13.52.19F NMR (377 MHz, CDCl3) δ -105.28, -105.99, -112.08,
-112.76. Calculated for [C13H13FO3] (M+H)+ 237.0921,
found237.0923.
ethyl (E)-2-fluoro-4-oxo-4-phenylbut-2-enoate (3a)
1H NMR (400 MHz, CDCl3) δ 7.95 (m, 2H), 7.63 (m, 1H),
7.51 (m, 2H), 7.13 (d, J = 30.8 Hz, 1H), 4.40 (m, 2H), 1.40 (m,
3H).13C NMR (101 MHz, CDCl3) δ 188.22 (s), 160.37 (s),
160.02 (s), 153.55 (s), 150.71 (s), 136.69 (s), 134.07 (s), 128.84
(d, J = 6.3 Hz), 128.15 (s), 112.09 (d, J = 5.3 Hz), 62.90 (s),
14.10 (s).19F NMR (376 MHz, CDCl3) δ -110.40 (s).HRMS
(ESI, m/z): Calculated for [C12H11FO3] (M+H)+ 223.0765,
found 223.0764.
ethyl (E)-2-fluoro-4-oxo-4-(m-tolyl)but-2-enoate (3g)
1H NMR (400 MHz, CDCl3) δ 7.74 (m, 4H), 7.40 (m, 4H),
7.12 (d, J = 30.8 Hz, 1H), 6.65 (d, J = 16.7 Hz, 1H), 4.40 (m,
2H), 4.14 (m, 2H), 2.43 (d, J = 4.6 Hz, 6H), 1.40 (m, 3H), 1.08
(m, 3H).13C NMR (101 MHz, CDCl3) δ 188.36, 160.41, 150.57,
143.38, 138.79, 136.72, 134.88, 133.04, 130.70, 129.28, 128.70,
126.10, 116.77, 114.83, 112.27, 101.59, 62.86, 62.50, 29.71,
21.32, 14.09, 13.51.19F NMR (376 MHz, CDCl3) δ -110.91 (s), -
115.01 (s). Calculated for [C13H13FO3] (M+H)+237.0921,
found237.0921.
ethyl (E)-2-fluoro-4-(4-fluorophenyl)-4-oxobut-2-enoate (3b)
ethyl (E)-2-fluoro-4-oxo-4-(o-tolyl)but-2-enoate (3h, Z/E 2:1)
1H NMR (400 MHz, CDCl3) δ 7.98 (m, 2H), 7.18 (m, 2H),
7.08 (d, J = 30.8 Hz, 1H), 4.40 (m 2H), 1.40 (m, 3H).13C NMR
(101 MHz, CDCl3) δ 186.66 (s), 167.59 (s), 160.23 (s), 159.88
(s), 153.58 (s), 150.74 (s), 131.56 (d, J = 9.6 Hz), 116.22 (s),
116.00 (s), 111.87 (d, J = 5.6 Hz), 62.93 (s), 14.07 (s).19F NMR
(376 MHz, CDCl3) δ -103.15 (s), -109.99 (s).HRMS (ESI, m/z):
Calculated for [C12H10F2O3] (M+H)+ 241.0671, found
241.0670.
1H NMR (400 MHz, CDCl3) δ 7.71 (m, 2H), 7.63 (m, 1H),
7.47 – 7.39 (m, 3H), 7.31 – 7.26 (m, 6H), 6.97 (d, J = 18.7 Hz,
1H), 6.66 (d, J = 17.1 Hz, 2H), 4.43 – 4.32 (m, 2H), 4.12 (m,
4H), 2.64 (s, 6H), 2.55 (s, 3H), 1.43 – 1.35 (m, 3H), 1.10 (m,
6H).13C NMR (101 MHz, CDCl3) δ 191.18 (s), 159.19 (s),
140.34 (s), 138.99 (s), 135.65 (s), 132.69 (s), 132.27 (s), 132.05
(s), 131.21 (s), 129.87 (s), 125.79 (d, J = 11.6 Hz), 118.49 (d, J =
14.2 Hz), 114.56 (s), 62.82 (s), 62.39 (s), 21.76 (s), 21.07 (s),
14.06 (s), 13.56 (s).19F NMR (376 MHz, CDCl3) δ -110.97 (s), -
115.87 (s). Calculated for [C13H13FO3] (M+H)+237.0921,
found237.0919.
ethyl (E)-4-(4-bromophenyl)-2-fluoro-4-oxobut-2-enoate (3c)
1H NMR (400 MHz, CDCl3) δ 7.80 (m, 2H), 7.65 (m, 2H),
7.07 (d, J = 30.5 Hz, 1H), 4.40 (m, 2H), 1.40 (m, 3H).13C NMR
(101 MHz, CDCl3) δ 187.21 (s), 159.85 (s), 153.86 (s), 151.00
ethyl (E)-4-(2,4-dimethylphenyl)-2-fluoro-4-oxobut-2-enoate (3i)