Palladium-catalyzed carbonylative coupling of tributyl(1-fluorovinyl)stannane with aryl halides and aryl triflates

Article abstract of DOI:10.1246/bcsj.75.2497

We have found that tributyl(1-fluorovinyl)stannane (2) could be readily prepared from the reaction of (1-fluorovinyl)methyldiphenylsilane¹ (1) and bis(tributyltin) oxide in the presence of a catalytic amount of CsF in DMF in good yields. The palladium-catalyzed carbonylative cross-coupling reaction of 2 with aryl iodides bearing various functional groups smoothly proceeded giving the corresponding aryl 1-fluorovinyl ketones in good yields under an atmospheric pressure of carbon monoxide. A similar carbonylative cross-coupling reaction of 2 with aryl triflates was also accomplished in the presence of tetrabutylammonium iodide (Bu₄NI) as an additive.

Full text of DOI:10.1246/bcsj.75.2497

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 2497–2502 (2002) 2497
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
Palladium-Catalyzed Carbonylative Coupling of
Tributyl(1-fluorovinyl)stannane with Aryl Halides and Aryl Triflates
Tributyl(1-fluorovinyl)stannane with Aryl
T. Hanamoto et al.
Takeshi Hanamoto,* Kumiko Handa, and Tomonori Mido
02
97
02
SJA8
09-2673
128
Department of Chemistry and Applied Chemistry, Saga University, Honjyo-machi 1, Saga 840-8502
(Received May 14, 2002)
We have found that tributyl(1-fluorovinyl)stannane (2) could be readily prepared from the reaction of (1-fluorovi-
nyl)methyldiphenylsilane1 (1) and bis(tributyltin) oxide in the presence of a catalytic amount of CsF in DMF in good
yields. The palladium-catalyzed carbonylative cross-coupling reaction of 2 with aryl iodides bearing various functional
groups smoothly proceeded giving the corresponding aryl 1-fluorovinyl ketones in good yields under an atmospheric
pressure of carbon monoxide. A similar carbonylative cross-coupling reaction of 2 with aryl triflates was also accom-
plished in the presence of tetrabutylammonium iodide (Bu4NI) as an additive.
02
02
.3
α,β-Unsaturated ketones are widely employed as dieno-
Results and Discussion
philes in the Diels–Alder reaction or as Michael acceptors in
organic synthesis. The corresponding fluorinated α,β-unsatur-
ated ketones are also considered to be promising reagents for
the preparation of complex fluorinated compounds.2 However,
the use of α-fluorinated α,β-unsaturated ketones seems to be
limited. One of the reasons is considered to be the difficulty of
their general preparation.3 Recently, we reported the efficient
cross-coupling reaction of 1 with aryl iodides.4 As a part of
these investigations, we became interested in the carbonylative
cross-coupling reaction.5 Although the carbonylative cross-
coupling reaction proceeded giving the desired products, the
reaction was sluggish and the yield was not satisfactory.6 We
then focused on the reactivity of 2 for the carbonylative cross-
coupling reaction.7 While the same ketones can be prepared
by the palladium-catalyzed reaction of acid chlorides, the utili-
ty of this route should be limited by the availability of the cor-
responding carboxylic acids. In this article, we report the
preparation of aryl 1-fluorovinyl ketones via the Pd-catalyzed
carbonylative coupling of 2 with aryl iodides and aryl triflates
under an atmospheric pressure of carbon monoxide.8
Preparation of Tributyl(1-fluorovinyl)stannane.
Al-
though 2 is a known compound, we did not find the literature
procedure easy to replicate.3a Therefore, prior to the examina-
tion of the carbonylative coupling, we needed a convenient
method for the synthesis of 2.8a,9 Burton and co-workers have
already found the direct transformation of several fluorinated
vinyl silanes to the corresponding stannanes.10 This prompted
us to apply their method to the preparation of 2. According to
their method, we first examined the reaction of 1 and tributyl-
tin chloride under various conditions, however, no target stan-
nane was produced. Ultimately, we obtained 2 by the reaction
of 1 with bis(tributyltin) oxide in the presence of a catalytic
amount of CsF in DMF at room temperature in 76% yield
(Table 1, entry 3). Ultrasonic irradiation dramatically acceler-
ated the reaction rate (entries 3, 4, and 5), and the reaction was
completed within 10 min. Although spray-dried KF as a fluo-
ride source is also effective for the reaction, it requires a higher
reaction temperature and longer reaction time (entries 1 and 2).
Carbonylative Coupling of 2 with Aryl Iodides.
We
Table 1. Preparation of Tributyl(1-fluorovinyl)stannane
(Bu3Sn)2O
MF
Temp
u.s.
Time
Yield
Entry
b)
equiv
0.6
0.6
0.6
0.6
0.1 equiv
KF
KF
CsF
CsF
°C
100
80
rt
rt
rt
mina)
10
10
10
0
h
3.5
7.5
0
1
0
%
1
2
3
4
5
6
70
71
76
71
69
68
0.5
1.0
CsF
CsF
10
10
rt
72
a) Ultrasound. b) Isolated yield.

2498 Bull. Chem. Soc. Jpn., 75, No. 11 (2002)
Tributyl(1-fluorovinyl)stannane with Aryl
Table 2. Reaction of 2 with 1-Iodo-2,4-dimethylbenzene
under Various Conditions
first examined the reaction of 2 and 1-iodo-2,4-dimethylben-
zene under an atmospheric pressure of carbon monoxide in
DMF to establish the optimum conditions. These results are
shown in Table 2. Under the optimum conditions (entry 2), the
reaction cleanly proceeded giving the corresponding aryl 1-flu-
orovinyl ketone (3a) in quantitative yield. The forced condi-
tions resulted in the decreased yield to some extent (entry 3).
The catalytic activity of several palladium complexes roughly
decreased in the order Pd[PPh3]4 > PdCl2[PPh3]2>>
Pd(OAc)2 (entries 2, 4, and 5). These carbonylative coupling
reactions required the temperature of 80 °C, and no reaction
took place at 50 °C (entries 1 and 2).
Entry Pd (2.5 mol%) Temp/°C
Time/h
Yield/%a)
1
2
3
4
5
Pd[PPh3]4
Pd[PPh3]4
Pd[PPh3]4
PdCl2[PPh3]2
Pd(OAc)2
50
80
100
80
72
2
3
3.5
72
trace
99
85
93
71
Representative results of the carbonylative cross-coupling
reaction of the 2-, 3-, and 4-substituted aryl halides are depict-
ed in Table 3. As expected, the reaction is quite general for the
80
a) Isolated yield.
Table 3. Carbonylative Cross-Coupling Reaction of 2 with Various Aryl Halidesa)
Temp
°C
Time
h
Yieldb)
%
Entry
1
Ar-X
Product
3b
3b
3c
100
80
24
2
23
2
81
3
80
2.5
3
72
4
80
3d
3e
86
5
80
3
64
6
80
2.5
3
3f
86
7
100
100
100
80
3g
71
8
0.5
0.5
2
3h
3i
86
9
77
10
11
12
13
14f)
3j
99
80
3.5
70
18
14
3k
—
72
120
80
0c)
0d),e)
0d),g)
4a
80
4a
a) Unless otherwise noted, the reactions were carried out under the following conditions:
tributyl(1-fluorovinyl)stannane (1.2 equiv) with aryl halides (1.0 equiv) in the presence
of Pd[PPh3]4 (2.5 mol%) in DMF. b) Isolated yield. c) No reaction. d) No CO insertion
reaction occurred. Instead, the corresponding cross-coupling product was obtained (see
text). e) 66% yield. f) Tributyl(1-fluorovinyl)stannane (1.0 equiv) with aryl halides (1.2
equiv) in the presence of Pd[PPh3]4 (2.5 mol%) in DMI. g) 78% yield.

T. Hanamoto et al.
Bull. Chem. Soc. Jpn., 75, No. 11 (2002) 2499
Table 4. Reaction of 2 with 4-Nitrophenyl Triflate under
Various Conditions
Table 5. Carbonylative Cross-Coupling Reaction of 2 with
Vrious Aryl Triflatesa)
Entry
1
Ar-OTf
Time/h Product Yield/%b)
5
3b
3c
75
81
88
2
3
2.5
4
Entry
Additive/equiv
Solvent
Time/h
Yield/%a)
1
2
3
4
5
None
DMF
DMF
NMPb)
DMF
DMF
3.5
3
1
5
5
0
trace
0
57
75
LiCl (3.0)
LiCl (3.0)
Bu4NI (1.2)
Bu4NI (2.5)
3m
4
96
—
—
—
0
0
a) Isolated yield. b) 1-Methyl-2-pyrrolidone.
5c)
6
72
96
substrate bearing not only an electron-withdrawing group (ke-
tone, ester, nitro, and halogen) but also an electron-donating
one (alkyl and ether) on the aromatic ring. The functional
group compatibility of this process as illustrated in these ex-
amples is noteworthy. Even the aryl bromide could be em-
ployed; however, it was less effective compared to the corre-
sponding aryl iodide (entries 1 and 2). The heteroaromatic
bromide did not afford the corresponding ketone under the
forced reaction conditions along with the decomposition of 2
(entry 12). Interestingly, when we employed another heteroar-
omatic bromide bearing an electron-withdrawing group as the
reaction partner, no carbonylation occurred and the simple
cross-coupling product was obtained in good yields (entries 13
and 14).
trace
a) Unless otherwise noted, the reactions were carried out
under the following conditions: tributyl(1-fluorovinyl)stan-
nane (1.2 equiv) with aryl triflates (1.0 equiv) in the pres-
ence of Pd[PPh3]4 (2.5 mol%) and Bu4NI (2.5 equiv) in
DMF at 80 °C. b) Isolated yield. c) Pd[dba]2 + AsPh3 was
n
used instead of Pd[PPh3]4.
action. (2) An electron-donating group on the aromatic ring
retarded the reaction. In order to overcome the second limita-
tion, we employed the catalyst system containing the combina-
tion of Pd[dba]2 and AsPh3 as a more reactive catalyst system13
instead of Pd[PPh3]4; however, no carbonylative product was
observed, while 2 and the triflate were recovered.
Carbonylative Coupling of 2 with Aryl Triflates.
In
light of the above successful carbonylative reaction using aryl
halides, we envisaged that the carbonylative coupling with an
aryl triflate would also be accessible. Since aryl triflates are
readily accessible from the corresponding phenols, the reac-
tion using triflates would expand the scope of our reaction.11
The reaction was first examined using 4-nitrophenyl triflate un-
der conditions similar to those employed for the carbonylative
coupling of aryl halides. However, the treatment of 2 with the
triflate in the presence of 2.5 mol% of Pd[PPh3]4 in DMF re-
sulted in no reaction along with the recovery of 2 and the tri-
flate (Table 4, entry 1). The addition of an inorganic salt like
lithium chloride was less effective for the carbonylative cou-
pling reaction (entries 2 and 3).12 However, the addition of tet-
rabutylammonium iodide (Bu4NI) was very effective for the
reaction, and the reaction in the presence of 2.5 molar amounts
of Bu4NI to the triflate proceeded smoothly to afford the corre-
sponding aryl 1-fluorovinyl ketone in good yield.12d Although
we have no evidence about the real role of Bu4NI, we con-
firmed that no transformation of the triflate into the corre-
sponding aryl iodide occurred during the reaction on the basis
of GC-MS analysis. The added Bu4NI should be essential in
order to assure the formation of the reactive aryliodopalladi-
um(Ⅱ) species. Representative results of the carbonylative
cross-coupling reaction of a variety of aryl triflates in the pres-
ence of Bu4NI are shown in Table 5. When we compared it
with the reactions with aryl iodides, we found that the carbon-
ylative coupling reaction with the triflate has the following fea-
tures; (1) The addition of Bu4NI is essential for a successful re-
Conclusion
We have demonstrated the synthetic utility of 2. This com-
pound is easily prepared from 1 with bis(tributyltin) oxide in
one step. The carbonylative coupling reaction of 2 with vari-
ous aryl halides worked well to give the corresponding aryl 1-
fluorovinyl ketones in good yields. The generality of the reac-
tion was shown to be high with regard to the aryl iodide func-
tionality and the substituted pattern. Although the carbonyla-
tive coupling with aryl triflates proceeded in the presence of
Bu4NI, these reactions require electron-withdrawing groups on
the aromatic rings. Further studies on its synthetic utility are
now in progress in our laboratory.
Experimental
General. Melting points were measured with a Yanagimoto
micro melting point apparatus MP-S3 and are uncorrected. Infra-
red (IR) spectra were recorded on a Perkin Elmer SPECTRUM
2000. 1H NMR and 19F NMR spectra were measured on a JEOL
JNM-AL300. Chemical shifts were given by δ relative to that of
an internal Me4Si (TMS) for 1H NMR spectra and benzylidyne tri-
fluoride (CF3C6H5) for 19F NMR spectra. GC-MS spectra were
obtained with a JEOL JMS-AMII15. HRMS spectra were ob-
tained with a JEOL JMS-HX100A at the institute for fundamental
research of organic chemistry (IFOC), Kyushu University. Ele-
mental analyses were accomplished at the service center for the

2500 Bull. Chem. Soc. Jpn., 75, No. 11 (2002)
Tributyl(1-fluorovinyl)stannane with Aryl
elementary analysis of organic compounds, Kyushu University.
Analytical thin-layer chromatography (TLC) was performed on a
silica gel plate (Merck , Kieselgel 60 F254, 20 × 20 cm, 0.25
mm). DMF, DMI, and NMP were used as a reaction solvent after
distillation from CaH2.
Hz), 5.55 (1H, dd, J = 17.1, 3.7 Hz), 5.61 (1H, dd, J = 42.6, 3.5
Hz), 7.91 (2H, dm, J = 8.3 Hz), 8.15 (2H, dm, J = 8.3 Hz);
19F NMR(CDCl3, 283 MHz) δ −112.71 (1F, ddm, J = 42.8, 16.5
Hz); GC MS m/z 222 (3, M+), 177 (100), 176 (23), 149 (43), 101
(33), 76 (26); HRMS m/z calcd for C12H11FO3 (M): 222.0692,
found: M+, 222.0658. Further purification for elementary analy-
sis resulted in the decomposition of the product.
Tributyl(1-fluorovinyl)stannane (2).
To a solution of 114
(844.5 mg, 3.48 mmol) in DMF (15 mL) were added bis(tributyl-
tin) oxide (1.1 mL, 2.16 mmol) and a catalytic amount of CsF
(53.0 mg 0.35 mmol) at room temperature under a flow of argon.
The whole mixture was irradiated with ultrasonic waves for 10
min. The resulting mixture was quenched with water, extracted
with hexane–ether (3:1), dried with Na2SO4, and concentrated.
The residue was chromatographed on silica gel (hexane as an elu-
ent) to give the desired product 2 as a colorless oil (889.5 mg,
76%): IR (neat) 2959, 2929, 2873, 2855, 1608, 1465, 1129, 904,
and 856 cm−1; 1H NMR (CDCl3, 300 MHz) δ 0.90 (9H, t, J = 7.3
Hz), 0.97–1.05 (6H, m), 1.25–1.40 (6H, m), 1.50–1.65 (6H, m),
4.55 (1H, m, JH-H = 2.8 Hz, JH-F = 67.7 Hz, JH-Sn = 15.0 Hz), 5.31
(1H, m, JH-H = 2.8 Hz, JH-F = 38.4 Hz, JH-Sn = 66.8, 71.0 Hz);
19F NMR(CDCl3, 283 MHz) δ −86.15 (m, dd (84%), J = 38.3,
67.6 Hz, JF-117Sn = 228 (7.6%), JF-119Sn = 234 (8.6%) Hz); GC MS
m/z 279 (4.9), 277 (3.9), 177 (100); Anal. Calcd for C14H29FSn: C,
50.18; H, 8.72%. Found: C, 50.29; H, 8.70%.
2-Fluoro-1-(2-methoxycarbonylphenyl)-2-propen-1-one
(3d). A colorless oil; yield 86%; IR (neat) 2956, 2361, 1722,
1694, 1645, 1598, 1577, 1488, 1437, 1365, 1288, 1198, 1139,
1089, 1043, 988, 971, 937, 830, 761, 729, 701, and 670 cm−1
;
1H NMR (CDCl3, 300 MHz) δ 3.88 (3H, s), 5.29 (1H, dd, J =
43.7, 3.7 Hz), 5.36 (1H, dd, J = 13.9, 3.7 Hz), 7.42 (1H, dd, J =
7.3, 1.5 Hz), 7.58 (1H, dt, J = 1.5, 7.3 Hz), 7.65 (1H, dt, J = 1.5,
7.3 Hz), 8.03 (1H, dd, J = 7.3, 1.5 Hz); 19F NMR(CDCl3, 283
MHz) δ −115.96 (1F, ddm, J = 43.6, 14.2 Hz); GC MS m/z 208
(1, M+), 177 (24), 163 (100), 162 (22), 151 (37), 104 (26), 101
(29), 92 (29), 77 (64), 76 (39), 75 (27), 50 (35); HRMS m/z calcd
for C11H9FO3 (M): 208.0536, found: M+, 208.0544. Further puri-
fication for elementary analysis resulted in the decomposition of
the product.
2-Fluoro-1-(4-nitrophenyl)-2-propen-1-one (3e).
A white
solid; yield 64%; mp 45.8–46.4 °C; IR (KBr) 3110, 3055, 2924,
1844, 1682, 1602, 1532, 1409, 1352, 1296, 1195, 1114, 1012,
Palladium-Catalyzed Carbonylative Coupling Reaction:
General Procedure (Table 2 and 3). 1-(2,4-Dimethylphenyl)-
1
976, 935, 868, 853, 789, 750, 723, 684, and 668 cm−1; H NMR
2-fluoro-2-propen-1-one (3a) (Table 2, Entry 2).
To a solu-
(CDCl3, 300 MHz) δ 5.58 (1H, dd, J = 13.2, 3.7 Hz), 5.68 (1H,
dd, J = 43.1, 3.7 Hz), 8.02 (2H, dt, J = 7.0, 2.0 Hz), 8.34 (2H, dt,
J = 9.2, 2.0 Hz); 19F NMR(CDCl3, 283 MHz) δ −112.91 (1F, dd,
J = 44.6, 1.5 Hz); GC MS m/z 195 (1, M+), 150 (100), 149 (44),
104 (68), 101 (43), 92 (52), 76 (64), 75 (45), 74 (22), 73 (31), 50
(47); Anal. Calcd for C9H6FNO3: C, 56.39; H, 3.10; N, 7.18%.
Found: C, 56.44; H, 3.44; N, 6.99%.
2-Fluoro-1-(4-methoxyphenyl)-2-propen-1-one (3f). A col-
orless oil; yield 86%; IR (neat) 2937, 2843, 1667, 1629, 1602,
1572, 1510, 1463, 1423, 1361, 1313, 1287, 1263, 1206, 1170,
1115, 1030, 986, 968, 934, 846, and 776 cm−1; 1H NMR (CDCl3,
300 MHz) δ 3.89 (3H, s), 5.41 (1H, dd, J = 15.4, 2.8 Hz), 5.54
(1H, dd, J = 45.9, 2.8 Hz), 6.96 (2H, dm, J = 8.6 Hz), 7.92 (2H,
dm, J = 8.3 Hz); 19F NMR(CDCl3, 283 MHz) δ −110.76 (1F,
ddm, J = 45.8, 15.5 Hz); GC MS m/z 181 (2, M+ + 1), 180 (31,
M+), 135 (100), 134 (17), 107 (17), 92 (32), 77 (40), 64 (13), 63
(12); HRMS m/z calcd for C10H9FO2 (M): 180.0587, found: M+,
180.0584. Further purification for elementary analysis resulted in
the decomposition of the product.
tion of 2 (46.2 mg, 0.138 mmol) in DMF (3 mL) were added 1-
iodo-2,4-dimethylbenzene (16 µL, 0.112 mmol) and a catalytic
amount of Pd[PPh3]4 (4.5 mg, 2.5 mol%). After argon was re-
placed with carbon monoxide (balloon), the mixture was heated at
80 °C for 2 h. After the usual workup, column chromatography
(silica gel, hexane–ether = 20:1) of the residue afforded 19.7 mg
of 1-(2,4-dimethylphenyl)-2-fluoro-2-propen-1-one (3a) as a col-
orless oil (99% yield).
1-(2,4-Dimethylphenyl)-2-fluoro-2-propen-1-one (3a).
A
colorless oil; yield 99%; IR (neat) 2926, 1678, 1613, 1450, 1370,
1324, 1203, 1131, 970, 907, 827, and 778 cm−1; 1H NMR (CDCl3,
300 MHz) δ 2.37 (3H, s), 2.38 (3H, s), 5.39 (1H, dd, J = 44.4, 3.4
Hz), 5.53 (1H, dd, J = 14.2, 3.4 Hz), 7.05 (1H, d, J = 7.8 Hz),
7.09 (1H, s), 7.35 (1H, d, J = 7.8 Hz); 19F NMR (CDCl3, 283
MHz) δ −114.03 (1F, ddd, J = 44.3, 13.8, 1.1 Hz); GC MS m/z
179 (9, M+ + 1), 178 (86, M+), 177 (43), 133 (74), 129 (41), 115
(29), 105 (100), 103 (36), 79 (48), 78 (25), 77 (74), 51 (25); Anal.
Calcd for C11H11FO: C, 74.14; H, 6.22%. Found: C, 74.06; H,
6.18%.
2-Fluoro-1-(3-methoxyphenyl)-2-propen-1-one (3g).
A
1-(4-Acetylphenyl)-2-fluoro-2-propen-1-one (3b).
A pale
colorless oil; yield 71%; IR (neat) 2940, 2839, 1675, 1636, 1598,
1582, 1487, 1465, 1431, 1363, 1327, 1290, 1254, 1192, 1168,
1047, 1008, 996, 939, 897, 832, 802, 763, and 687 cm−1; 1H NMR
(CDCl3, 300 MHz) δ 3.86 (3H, s), 5.51 (1H, dd, J = 16.0, 3.3 Hz),
5.57 (1H, dd, J = 44.4, 3.3 Hz), 7.14 (1H, ddd, J = 8.1, 2.8, 1.1
Hz), 7.36–7.47 (3H, m); 19F NMR(CDCl3, 283 MHz) δ −112.10
(1F, ddm, J = 44.2, 15.8 Hz); GC MS m/z 181 (3, M+ + 1), 180
(58, M+), 152 (25), 137 (38), 135 (85), 107 (91), 92 (65), 77
(100), 64 (31); HRMS m/z calcd for C10H9FO2 (M): 180.0587,
found: M+, 180.0586. Further purification for elementary analy-
sis resulted in the decomposition of the product.
yellow oil; yield 81%; IR (neat) 3051, 2926, 1689, 1683, 1641,
1565, 1501, 1427, 1407, 1359, 1285, 1199, 1150, 1076, 1018,
1
989, 959, 936, 854, 774, 713, and 687 cm−1; H NMR (CDCl3,
300 MHz) δ 2.66 (3H, s), 5.55 (1H, dd, J = 15.8, 3.7 Hz), 5.64
(1H, dd, J = 43.9, 3.5 Hz), 7.94 (2H, dm, J = 8.3 Hz), 8.05 (2H,
dm, J = 8.3 Hz); 19F NMR (CDCl3, 283 MHz) δ −112.76 (1F,
ddm, J = 43.8, 16.3 Hz); GC MS m/z 193 (9, M+ + 1), 192 (4,
M+), 177 (100), 147 (10), 101 (48), 91 (11), 76 (16), 75 (11);
HRMS m/z calcd for C11H9FO2 (M): 192.0587, found: M+,
192.0575. Further purification for elementary analysis resulted in
the decomposition of the product.
2-Fluoro-1-(4-methoxymethylphenyl)-2-propen-1-one (3h).
A colorless oil; yield 86%; IR (neat) 2929, 2360, 1672, 1635,
1610, 1415, 1375, 1284, 1198, 1105, 969, 936, 849, and 767
1-(4-Ethoxycarbonylphenyl)-2-fluoro-2-propen-1-one (3c).
A colorless oil; yield 72%; IR (neat) 3051, 2926, 1689, 1683,
1641, 1565, 1501, 1427, 1407, 1359, 1285, 1199, 1150, 1076,
1
cm−1; H NMR (CDCl3, 300 MHz) δ 3.43 (3H, s), 4.53 (2H, s),
1018, 989, 959, 936, 854, 774, 713, and 687 cm−1; H NMR
5.47 (1H, dd, J = 6.4, 3.1 Hz), 5.57 (1H, dd, J = 36.3, 3.3 Hz),
1
(CDCl3, 300 MHz) δ 1.42 (3H, t, J = 7.2 Hz), 4.42 (2H, q, J = 7.2
7.44 (2H, d, J = 7.9 Hz), 7.86 (2H, d, J = 7.7 Hz); 19F NMR

T. Hanamoto et al.
Bull. Chem. Soc. Jpn., 75, No. 11 (2002) 2501
(CDCl3, 283 MHz) δ −112.01 (1F, ddt, J = 45.1, 15.7, 1.5 Hz);
GC MS m/z 194 (24, M+), 149 (24), 134 (37), 133 (33), 121 (43),
91 (32), 90 (35), 89 (100), 77 (29), 73 (33); HRMS m/z calcd for
C11H11FO2 (M): 194.0743, found: M+, 194.0777. Further purifi-
cation for elementary analysis resulted in the decomposition of the
product.
2-Fluoro-1-(4-acethoxymethylphenyl)-2-propen-1-one (3i).
A colorless oil; yield 77%; IR (neat) 2938, 1745, 1675, 1635,
1611, 1417, 1380, 1321, 1284, 1229, 1200, 1179, 1045, 988, 970,
936, 845, and 769 cm−1; 1H NMR (CDCl3, 300 MHz) δ 2.14 (3H,
s), 5.18 (2H, s), 5.50 (1H, dd, J = 15.6, 3.4 Hz), 5.58 (1H, dd, J =
44.4, 3.4 Hz), 7.46 (2H, d, J = 7.8 Hz), 7.88 (2H, d, J = 7.9 Hz);
19F NMR(CDCl3, 283 MHz) δ −112.17 (1F, ddt, J = 44.8, 15.3,
1.6 Hz); GC MS m/z 222 (5, M+), 180 (59), 135 (22), 133 (34),
107 (100), 90 (29), 89 (71), 73 (30); HRMS m/z calcd for
C12H11FO3 (M): 222.0692, found: M+, 222.0698. Further purifi-
cation for elementary analysis resulted in the decomposition of the
product.
2-Fluoro-1-(1-naphthyl)-2-propen-1-one (3m).
IR (neat)
1673, 1636, 1509, 1371, 1318, 1289, 1226, 1172, 1087, 1063,
931, 803, and 780 cm−1; 1H NMR (CDCl3, 300 MHz) δ 5.48 (1H,
dd, J = 44.0, 3.5 Hz), 5.63 (1H, dd, J = 13.9, 3.5 Hz), 7.49–7.62
(3H, m), 7.72 (1H, d, J =7.2 Hz), 7.85–7.94 (1H, m), 8.02 (1H, d,
J = 8.3 Hz), 8.12–8.20 (1H, m); 19F NMR(CDCl3, 283 MHz) δ
−113.98 (1F, dd, J = 43.6, 13.8 Hz); GC MS m/z 201 (0.9, M+
+ 1), 200 (50, M+), 199 (39), 171 (24), 155 (34), 127 (100), 126
(27); HRMS m/z calcd for C13H9FO (M): 200.0637, found: M+,
200.0643. Further purification for elementary analysis resulted in
the decomposition of the product.
We thank Chemetall Japan Co., Ltd. for a gift of CsF, F-
Tech Co., Ltd for a gift of 1,1-difluoroethylene for the prepara-
tion of 1 and Kawaken Fine Chemicals Co., Ltd for a gift of
DMI.
References
1-(2-Ethylphenyl)-2-fluoro-2-propen-1-one (3j).
A color-
less oil; yield 99%; IR (neat) 2938, 1745, 1675, 1635, 1611, 1417,
1380, 1321, 1284, 1229, 1200, 1179, 1045, 988, 970, 936, 845,
and 769 cm−1; 1H NMR (CDCl3, 300 MHz) δ 1.21 (3H, t, J = 7.3
Hz), 2.71 (2H, q, J = 7.3 Hz), 5.37 (1H, dd, J = 44.0, 3.4 Hz),
5.58 (1H, dd, J = 13.7, 3.4 Hz), 7.21–7.46 (4H, m); 19F NMR
(CDCl3, 283 MHz) δ −114.97 (1F, ddm, J = 44.0, 13.6 Hz); GC
MS m/z 178 (13, M+), 163 (44), 143 (24), 133 (33), 132 (33), 131
(22), 129 (26), 115 (100), 105 (22), 103 (25), 79 (20), 77 (38), 51
(16); HRMS m/z calcd for C11H11FO (M): 178.0794, found: M+,
178.0829. Further purification for elementary analysis resulted in
the decomposition of the product.
1-(2-Chlorophenyl)-2-fluoro-2-propen-1-one (3k). A color-
less oil; yield 72%; IR (neat) 2361, 1698, 1642, 1592, 1435, 1300,
1202, 1065, 969, 937, and 747 cm−1; 1H NMR (CDCl3, 300 MHz)
δ 5.43 (1H, dd, J = 43.0, 3.4 Hz), 5.59 (1H, dd, J = 13.2, 3.4 Hz),
7.34–7.46 (4H, m); 19F NMR (CDCl3, 283 MHz) δ −116.72 (1F,
ddm, J = 42.9, 13.1 Hz); GC MS m/z 184 (9, M+), 183 (26), 141
(22), 139 (79), 138 (100), 111 (41), 75 (47), 74 (23); HRMS m/z
calcd for C9H6ClFO (M): 184.0091, found: M+, 184.0056. Fur-
ther purification for elementary analysis resulted in the decompo-
sition of the product.
2-(1-Fluorovinyl)-5-nitropyridine (4a). A white solid; yield
78%; mp 68.3–69.8 °C; IR (KBr) 3141, 1652, 1593, 1525, 1475,
1349, 1276, 1132, 1105, 1018, 926, 899, 859, 780, 767, and 718
cm−1; 1H NMR (CDCl3, 300 MHz) δ 5.25 (1H, dd, J = 16.0, 3.1
Hz), 5.98 (1H, dd, J = 48.1, 3.1 Hz), 7.73 (1H, d, J = 8.6 Hz),
8.55 (1H, dd, J = 8.6, 2.4 Hz), 9.40 (1H, d, J = 1.7 Hz); 19F NMR
(CDCl3, 283 MHz) δ −117.24 (1F, ddd, J = 48.3, 15.9, 1.1 Hz);
GC MS m/z 169 (7, M+ + 1), 168 (100, M+), 167 (20), 122 (55),
102 (25), 95 (76), 75 (69), 51 (26), 50 (20); Anal. Calcd for
C7H5FN2O2: C, 50.01; H, 3.00; N, 16.66%. Found: C, 50.09; H,
3.01, N, 16.63%.
1
We are sorry for the incorrect name of this silane in our
previous paper.4,14
2
M. Hudlicky and A. E. Pavlath, “Chemistry of Organic
Fluorine Compounds Ⅱ,” ACS Monograph 187, Washington, DC
(1995).
3
a) D. P. Matthews, P. P. Waid, J. S. Sabol, and J. R.
McCarthy, Tetrahedron Lett., 35, 5177 (1994). b) T. Satoh, N.
Itoh, K. Onda, Y. Kitoh, and K. Yamakawa, Bull. Chem. Soc. Jpn.,
65, 2800 (1992). c) Y. Bessiere, N. H. S. Dang, and M. Schlosser,
Helv. Chim. Acta, 60, 1739 (1977).
4
281.
5
T. Hanamoto, T. Kobayashi, and M. Kondo, Synlett, 2001,
W. F. Goure, M. E. Wright, P. D. Davis, S. S. Labadie, and
J. K. Stille, J. Am. Chem. Soc., 106, 6417 (1984).
We obtained the corresponding carbonlylative product, 1-
6
(4-acetylphenyl)-2-fluoro-2-propen-1-one, in 11% yield by the re-
action of 1 with 4ꢀ-iodoacetophenone under carbon monoxide at
atmospheric pressure.
7
a) J. K. Stille, Angew. Chem., Int. Ed. Engl., 25, 508
(1986). b) J. K. Stille, Pure Appl. Chem., 57, 1771 (1985). c) T.
G. Crisp, W. J. Scott, and J. K. Stille, J. Am. Chem. Soc., 106,
7500 (1984).
8
To the best of our knowledge, McCarthy’s group has re-
ported only one reaction of (E)-1-fluoro-2-phenyl-1-tributylsta-
nylethene and iodobenzene in the presence of Pd/Cu(ꢁ) under CO
atmosphere. However, they obtained a mixture of the correspond-
ing direct coupling product and the carbonylative product with a
ratio of 2:3. a) C. Chen, K. Wilcoxen, K. Kim, and J. R.
McCarthy, Tetrahedron Lett., 38, 7677 (1997). b) C. Chen, K.
Wilcoxen, Y. Zhu, K. Kim, and J. R. McCarthy, J. Org. Chem., 64,
3476 (1999).
9
Although the related β-substituted (fluorovinyl)stannanes
Palladium-Catalyzed Carbonylative Coupling Reaction:
General Procedure (Table 4 and 5). 2-Fluoro-1-(1-naphthyl)-
were prepared from the corresponding β-substituted fluorovinyl
sulfones, the attempt of the preparation of 2 was unsuccessful. J.
R. McCarthy, E. W. Huber, T. Le, F. M. Laskovics, and D. P.
Matthews, Tetrahedron, 52, 45 (1996).
10 L. Xue, L. Lu, S. D. Pedersen, Q. Liu, R. M. Narske, and
D. J. Burton, J. Org. Chem., 62, 1064 (1997).
11 P. J. Stang, M. Hanack, and L. R. Subramanian, Synthesis,
1982, 85.
12 a) H. B. Kwon, B. H. McKee, and J. K. Stille, J. Org.
Chem., 55, 3114 (1990). b) A. M. Echavarren and J. K. Stille, J.
Am. Chem. Soc., 110, 1557 (1988). c) E. A. Echavarren and J. K.
2-propen-1-one (3m) (Table 5, Entry 3).
To a solution of 2
(92.7 mg, 0.28 mmol) in DMF (3.5 mL) were added 1-naphthyl
triflate (56.6 mg, 0.21 mmol), Bu4NI (189.0 mg, 0.51 mmol), and
a catalytic amount of Pd[PPh3]4 (4.9 mg, 2.5 mol%). After argon
was replaced with carbon monoxide (balloon), the mixture was
heated at 80 °C for 4 h. After the usual workup, column chroma-
tography (silica gel, hexane–ether = 20:1) of the residue afforded
35.9 mg of 2-fluoro-1-(1-naphthyl)-2-propen-1-one (3m) as a col-
orless oil (88% yield).

2502 Bull. Chem. Soc. Jpn., 75, No. 11 (2002)
Tributyl(1-fluorovinyl)stannane with Aryl
Stille, J. Am. Chem. Soc., 109, 5478 (1987). d) W. J. Scott and J.
K. Stille, J. Am. Chem. Soc., 108, 3033 (1986).
13 V. Farina and B. Krishnan, J. Am. Chem. Soc., 113, 9585
(1991).
14 T. Hanamoto, S. Harada, K. Shindo, and M. Kondo, Chem.
Commun., 1999, 2397.