10.1002/adsc.201801058
Advanced Synthesis & Catalysis
(dd, J = 8.5, 2.4 Hz, 1H), 6.82 – 6.72 (m, 1H), 6.51 (dd, J
= 15.6, 1.5 Hz, 1H), 3.83 (s, 3H), 1.96 (dd, J = 6.8, 1.5 Hz,
(E)-1-(5-bromothiophen-2-yl)but-2-en-1-one
(2r)
Prepared according to general procedure to afford as
3H). 13C NMR (100 MHz, CDCl3): δ = 193.9, 161.4, 147.0, yellow solid (75% yield). Rf = 0.40 (EtOAc / hexanes
o
1
133.2, 131.8, 130.8, 120.9, 118.9, 113.1, 55.8, 18.7.
HRMS (ESI) for C11H12BrO2 [M+H+]: Calcd: 255.0015;
Found: 255.0026. IR (KBr): 2968, 2926, 1655, 1623, 1586,
1565, 1450, 1391, 1048, 1039, 806 cm-1.
1:10). m. p. = 260 – 261 C. H NMR (400 MHz, CDCl3):
δ = 7.48 (d, J = 4.0 Hz, 1H), 7.21 – 7.06 (m, 2H), 6.73
(ddd, J = 15.1, 3.2, 1.6 Hz, 1H), 1.99 (dd, J = 6.9, 1.6 Hz,
3H). 13C NMR (100 MHz, CDCl3): δ = 181.2, 146.8, 145.1,
131.9, 131.4, 126.1, 122.7, 18.7. HRMS (ESI) for
C8H8BrOS [M+H+]: Calcd: 230.9474; Found: 230.9479. IR
(KBr): 3054, 2965, 2917, 2851, 1669, 1620, 1439, 1293,
969, 920, 804, 782 cm-1.
[19]
(E)-1-mesitylbut-2-en-1-one (2k)
Prepared according
to general procedure to afford as colorless oil (82% yield).
1
Rf = 0.55 (EtOAc / hexanes 1:10). H NMR (400 MHz,
CDCl3): δ = 6.76 (s, 2H), 6.49 – 6.35 (m, 1H), 6.33 – 6.15
(m, 1H), 2.21 (s, 3H), 2.06 (s, 6H), 1.87 – 1.80 (m, 3H).
13C NMR (100 MHz, CDCl3): δ = 201.7, 148.0, 138.3,
137.3, 134.2, 134.0, 128.3, 21.2, 19.3, 18.6. HRMS (ESI)
for C13H17O [M+H+]: Calcd: 189.1274; Found: 189.1276.
IR (KBr): 2958, 2922, 2857, 1653, 1440, 1274, 1095, 1064,
1024, 974, 852, 800 cm-1.
General procedure for preparation of 4: A seal tube
containing Ketones 3 (0.5 mmol) and Pd(OAc)2 (10
mol %), was evacuated and filled with dioxygen gas using
an oxygen containing balloon. Then, DMSO (5 mL),
trifluoroacetic acid (TFA) (1.0 mmol) were sequentially
added to the system via syringe under an oxygen
atmosphere. The reaction mixture was stirred at 80 oC until
completion of the reaction (TLC). Then the reaction was
cooled to RT and partitioned between water and ethyl
acetate. The layers were separated and the organic layer
was washed with aqueous saturated brine solution, dried
over Na2SO4, filtered and concentrated under reduced
pressure. Purification by flash chromatography afforded
the 4.
[21]
(E)-1-phenylpent-2-en-1-one (2l)
Prepared according
Rf = 0.39 (EtOAc / hexanes 1:10). H NMR (400 MHz,
CDCl3): δ = 7.90 – 7.80 (m, 2H), 7.52 – 7.45 (m, 1H), 7.39
(t, J = 7.5 Hz, 2H), 7.04 (dt, J = 15.4, 6.4 Hz, 1H), 6.80 (dt,
J = 15.4, 1.6 Hz, 1H), 2.45 – 2.00 (m, 2H), 1.07 (t, J = 7.4
Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 191.3, 151.5,
138.2, 132.7, 128.7, 128.6, 125.1, 26.1, 12.5.
[22]
(E)-4-phenylbut-3-en-2-one (4a)
Prepared according
[27]
to general procedure to afford as colorless oil (96% yield).
3-methyl-1-phenylbut-2-en-1-one (2m)
Prepared
1
Rf = 0.54 (EtOAc / hexanes 1:10). H NMR (400 MHz,
according to general procedure to afford as colorless oil
(53% yield). Rf = 0.55 (EtOAc / hexanes 1:10). H NMR
1
CDCl3): δ = 7.45 – 7.41 (m, 3H), 7.31 (d, J = 2.8 Hz, 3H),
6.63 (d, J = 16.3 Hz, 1H), 2.29 (s, 3H). 13C NMR (100
MHz, CDCl3): δ = 198.5, 143.5, 134.5, 130.6, 129.0, 128.3,
127.2, 27.6.
(400 MHz, CDCl3): δ = 7.89 – 7.82 (m, 2H), 7.48 – 7.43
(m, 1H), 7.38 (t, J = 7.4 Hz, 2H), 6.72 – 6.64 (m, 1H), 2.14
(d, J = 0.9 Hz, 3H), 1.95 (d, J = 0.9 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 191.7, 156.8, 139.4, 132.4, 128.6,
128.3, 121.3, 28.1, 21.3.
[24]
(E)-4-(2-fluorophenyl)but-3-en-2-one (4b)
Prepared
according to general procedure to afford as yellow oil (98%
yield). Rf = 0.59 (EtOAc / hexanes 1:10). H NMR (400
1
[19]
(E)-2-methyl-1-(p-tolyl)but-2-en-1-one (2n)
Prepared
MHz, CDCl3): δ = 7.68 (d, J = 16.5 Hz, 1H), 7.58 (td, J =
7.6, 1.7 Hz, 1H), 7.41 – 7.34 (m, 1H), 7.22 – 7.09 (m, 2H),
6.79 (d, J = 16.5 Hz, 1H), 2.40 (s, 3H). 13C NMR (100
MHz, CDCl3): δ = 198.4, 161.4 (d, J = 253.7 Hz), 135.7,
132.0 (d, J = 8.8 Hz), 129.2, 128.71 (d, J = 2.3 Hz), 124.6
(d, J = 3.6 Hz), 122.5 (d, J = 11.5 Hz,), 116.2 (d, J = 21.8
Hz). 27.5.
according to general procedure to afford as colorless oil
(65% yield). Rf = 0.57 (EtOAc / hexanes 1:10). H NMR
1
(400 MHz, CDCl3): δ = 7.47 (d, J = 8.1 Hz, 2H), 7.14 (d, J
= 7.9 Hz, 2H), 6.30 (qd, J = 6.9, 1.3 Hz, 1H), 2.33 (s, 3H),
1.89 (s, 3H), 1.80 (dd, J = 6.9, 0.8 Hz, 3H). 13C NMR (100
MHz, CDCl3): δ = 198.7, 141.9, 140.4, 137.7, 135.96,
129.5, 128.7, 21.51, 14.7, 12.3.
[23]
[28]
(E)-4-(3-fluorophenyl)but-3-en-2-one (4c)
Prepared
(E)-2-ethyl-1-(p-tolyl)but-2-en-1-one (2o)
Prepared
according to general procedure to afford as light yellow oil
(96% yield). Rf = 0.48 (EtOAc / hexanes 1:10). H NMR
according to general procedure to afford as colorless oil
(61% yield). Rf = 0.56 (EtOAc / hexanes 1:10). H NMR
(400 MHz, CDCl3): δ = 7.58 (d, J = 8.0 Hz, 2H), 7.23 (d, J
= 7.9 Hz, 2H), 6.28 (q, J = 7.0 Hz, 1H), 2.51 (q, J = 7.5 Hz,
2H), 2.42 (s, 3H), 1.90 (d, J = 7.0 Hz, 3H), 1.07 (t, J = 7.5
Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 198.8, 143.8,
142.1, 139.1, 136.5, 129.6, 128.8, 21.7, 20.0, 14.3, 13.3.
1
1
(400 MHz, CDCl3): δ = 7.39 (d, J = 16.3 Hz, 1H), 7.33 –
7.21 (m, 2H), 7.20 – 7.14 (m, 1H), 7.02 (t, J = 8.2 Hz, 1H),
6.62 (d, J = 16.3 Hz, 1H), 2.31 (d, J = 1.7 Hz, 3H). 13C
NMR (100 MHz, CDCl3): δ = 198.2, 163.1 (d, J = 246.9
Hz), 142.0 (d, J = 2.7 Hz), 136.8 (d, J = 7.7 Hz), 130.6 (d,
J = 8.3 Hz), 128.3, 124.4 (d, J = 2.8 Hz), 117.5 (d, J = 21.5
Hz), 114.5 (d, J = 21.9 Hz), 27.9.
[19]
(E)-1-(naphthalen-1-yl)but-2-en-1-one (2p)
Prepared
according to general procedure to afford as colorless oil
(76% yield). Rf = 0.54 (EtOAc / hexanes 1:10). H NMR
[22]
1
(E)-4-(4-fluorophenyl)but-3-en-2-one (4d)
Prepared
according to general procedure to afford as yellow oil (97%
yield). Rf = 0.55 (EtOAc / hexanes 1:10). H NMR (400
(400 MHz, CDCl3): δ = 8.31 – 8.23 (m, 1H), 7.97 (d, J =
8.2 Hz, 1H), 7.90 (dd, J = 6.8, 2.5 Hz, 1H), 7.67 (dd, J =
7.0, 0.8 Hz, 1H), 7.61 – 7.47 (m, 3H), 6.88 (dq, J = 15.5,
6.8 Hz, 1H), 6.70 (dd, J = 15.6, 1.4 Hz, 1H), 1.99 (dd, J =
6.8, 1.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 196.3,
147.1, 137.0, 133.9, 132.9, 131.4, 130.6, 128.5, 127.4,
127.03, 126.5, 125.7, 124.5, 18.7.
1
MHz, CDCl3): δ = 1H NMR (400 MHz, CDCl3) δ 7.58 –
7.51 (m, 2H), 7.48 (d, J = 16.3 Hz, 1H), 7.09 (t, J = 8.6 Hz,
2H), 6.65 (d, J = 16.3 Hz, 1H), 2.38 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 198.3, 164.1 (d, J = 251.7 Hz),
142.2, 130.8, 130.7, 130.3 (d, J = 8.6 Hz), 127.0, 126.9,
116.3 (d, J = 22.0 Hz). 27.7.
[29]
(E)-1-(naphthalen-2-yl)but-2-en-1-one (2q)
Prepared
[22]
(E)-4-(3-chlorophenyl)but-3-en-2-one (4e)
Prepared
according to general procedure to afford as colorless oil
(78% yield). Rf = 0.53 (EtOAc / hexanes 1:10). H NMR
1
according to general procedure to afford as light yellow oil
1
(97% yield). Rf = 0.51 (EtOAc / hexanes 1:10). H NMR
(400 MHz, CDCl3): δ = 8.44 (s, 1H), 8.02 (dd, J = 8.6, 1.6
Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.94 – 7.86 (m, 2H),
7.64 – 7.51 (m, 2H), 7.20 – 7.04 (m, 2H), 2.05 (d, J = 5.8
Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 190.7, 145.1,
135.6, 135.4, 132.7, 130.1, 129.6, 128.6, 128.4, 127.9,
127.7, 126.8, 124.68, 18.8.
(400 MHz, CDCl3): δ = 7.54 – 7.14 (m, 5H), 6.62 (d, J =
16.3 Hz, 1H), 2.30 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
= 198.05, 141.69, 136.35, 135.03, 130.40, 130.28, 128.22,
128.02, 126.48, 27.84.
[22]
(E)-4-(4-chlorophenyl)but-3-en-2-one (4f)
Prepared
according to general procedure to afford as yellow oil (95%
yield). Rf = 0.50 (EtOAc / hexanes 1:10). H NMR (400
1
6
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