Palladium-catalyzed allylation of carbonyl compounds with various allylic compounds using In-InCl3 in aqueous media

Article abstract of DOI:10.1055/s-2003-38059

Various allylic compounds can be effectively applied to palladium-catalyzed allylation of carbonyl compounds via the formation of π-allylpalladium(II) intermediates and their transmetalation with indium in the presence of indium trichloride in aqueous media.

Full text of DOI:10.1055/s-2003-38059

SPECIAL TOPIC
775
Palladium-Catalyzed Allylation of Carbonyl Compounds with Various Allylic
Compounds Using In–InCl3 in Aqueous Media
P
alladium-Cata
a
lyze
d
A
llyl
e
a
tion of Ca
g
-
ounds Su Jang,a Gyochang Keum,a Soon Bang Kang,a Bong Young Chung,b Youseung Kim*a
a
Biochemicals Research Center, Korea Institute of Science and Technology, Cheongryang P. O. Box 131, Seoul 130-650, Korea
Fax +82(2)9585189; E-mail: yosekim@kist.re.kr
b
Department of Chemistry, Korea University, Seoul 136-701, Korea
Received 15 February 2003
effective with various carbonyl compounds, gave a good
diastereoselectivity, and had economical benefit than the
use of indium(I) halide alone. Also the combination of in-
dium with several other metal salts was possible.
Abstract: Various allylic compounds can be effectively applied to
palladium-catalyzed allylation of carbonyl compounds via the for-
mation of -allylpalladium(II) intermediates and their transmetala-
tion with indium in the presence of indium trichloride in aqueous
media.
R1 OH
R2
O
In, InCl3, Pd(PPh3)4
r.t., THF/H2O (1:1)
Key words: allylation, palladium, indium, indium trichloride,
aqueous
X
+
R1
R2
2
1
3
X = Cl, OH, OAc, OC(O)OCH3
The chemistry of metallic indium is of current interest in
organic synthesis due to its ability to mediate many organ-
ic transformations and its exceptional stability to air and
water.1 Among many indium mediated reactions, the Bar-
bier-type allylation reaction is most widely applied in or-
ganic synthesis.2 However, the allylating reagent has been
limited to allylic halides, particularly allyl bromide and
iodide. Allyl chloride also has been used with iodide salt
via in situ generation of allyl iodide, and reported as an ef-
ficient allylating reagent in pure water under sonication or
in a 1:1 mixture of water and t-butanol.3 Our continuous
efforts 4 in the area of indium chemistry led us to find out
that various allylic compounds can be effectively applied
to the indium-mediated allylation reaction of carbonyl
compounds via the formation of -allylpalladium(II)
complexes, their transmetalation with indium in the pres-
ence of a catalytic amount of Pd(PPh3)4 and InCl3 in aque-
ous media (Scheme 1). Thus allyl alcohol reacted with 2
equivalents of indium metal and benzaldehyde using 2
mol% of Pd(PPh3)4 and 0.5 equivalents of indium trichlo-
ride at room temperature in a 1:1 mixture of water and
THF to afford the corresponding homoallylic alcohol in
high yield.
Scheme 1
The results under various reaction conditions are summa-
rized in Table 1. In the case of palladium-catalyzed reac-
tion of benzaldehyde with indium and allyl alcohol, the
optimized ratio of benzaldehyde, allyl alcohol and indium
was 1:3:2. The addition of half equivalent of indium chlo-
ride as an additive in aqueous THF solution gave the best
result (entry 6). The reaction hardly proceeds, if any, in
THF or DMF (entry 2 and 3) and gave a lower yield in
pure water (entry 4) under these Pd(0)–In–InCl3 condi-
tions. Without indium trichloride the reaction did not pro-
ceed even at 50 °C for 24 hours (entry 1), and when 0.1
equivalents of indium trichloride was used, the reaction of
allyl alcohol gave the allylation product in lower yield
(entry 5). When other Lewis acids, such as SnCl4, FeCl3,
and CuCl (entry 8–10) instead of InCl3, were used, the re-
actions of allyl alcohol provided the corresponding prod-
ucts in satisfactory yields respectively. But the reactions
with other additives such as SnCl2 (entry 7), FeCl2 and
ZnCl2 gave a trace amount of the desired products. It
should be noted that the reaction of allyl alcohol with 2
equivalents of InCl (entry 11) or InI (entry 12) instead of
using In–InCl3 afforded the allylation products in 50%
and 55% yields respectively. The occurrence of these pal-
ladium catalyzed reactions with InCl instead of combin-
ing indium and InCl3 suggests that active species might be
InCl, which could be formed by the reaction of indium
with metal chloride salts having higher reduction poten-
tials than In(I).7 The similar result was reported by us in
the In–InCl3 mediated cross-coupling reaction of methyl
vinyl ketone and benzaldehyde.8 The reaction in organic
solvents with this combined use of indium and indium(III)
chloride was unsuccessful probably due to slow genera-
tion of the InCl species through the reaction of In and
InCl3 in organic solvents.
Organopalladium compounds are known to undergo
transmetalation with a number of metal salts, active met-
als, or organometallic compounds, such as Zn, SnCl2,
SmI2, Et3B, Et2Zn and Me6Sn2.5 The reaction transforms
electrophilic palladium intermediates into nucleophilic
organometallic compounds or umpolung type of com-
pounds. Recently, allylic and allenic indium reagents have
been prepared via transient organopalladium intermedi-
ates with indium or indium(I) iodide.6 Our combined use
of indium and indium(III) chloride in aqueous media was
Synthesis 2003, No. 5, Print: 01 05 2003.
Art Id.1437-210X,E;2003,0,05,0775,0779,ftx,en;C00403SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

776
T.-S. Jang et al.
SPECIAL TOPIC
Table 1 Palladium-catalyzed Allylation of Benzaldehyde with Indi-
Table 2 Palladium-catalyzed Allylation of Various Carbonyl Com-
um and Allyl Alcohol under Various Conditionsa
pounds with In–InCl3 and Allyl Alcohola
Entry Additive
(equiv)
Solvent
Time Temp Yield
Entry Substrate
Time (h) Product
Yield (%)b
94
(h)
24
24
20
44
72
20
20
20
20
20
22
4
(°C)
(%)b of 3a
1
2
PhCHO
20
20
20
20
20
26
72
72
20
48
20
48
20
20
20
20
96
2
3a
3b
3c
3d
3e
3f
1
THF–H2O
DMF
50
NRc
trace
12
62
60
94
5
o-FPhCHO
100
98
2
3
InCl3 (0.5)
InCl3 (0.5)
InCl3 (0.5)
InCl3 (0.1)
InCl3 (0.5)
SnCl2 (1)
SnCl4 (1)
FeCl3 (1)
CuCl (1)
InCl (2)d
InI (2)d
r.t.
r.t.
50
3
m-FPhCHO
THF
4
p-FPhCHO
100
98
4
H2O
5
o-BrPhCHO
5
THF–H2O
THF–H2O
THF–H2O
THF–H2O
THF–H2O
THF–H2O
THF–H2O
THF–H2O
50
6
p-MePhCHO
p-t-BuPhCHO
p-MeOPhCHO
p-NCPhCHO
p-MeO2CPhCHO
p-HO2CPhCHO
CH3(CH2)8CHO
Cinnamaldehyde
3-Furaldehyde
Nicotinaldehyde
Cyclohexanone
Acetophenone
Ethylacetoacetate
99
6
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
7
3g
3h
3i
80
7
8
96
8
76
87
86
50
55
9
76
9
10
11
12
13
14
15
16
17
18
3j
46
10
11
12
3k
3l
74
79
3m
3n
3o
3p
3q
3r
63
a Reactions were carried out with 1 equiv of PhCHO, 3 equiv of allyl
alcohol, 2 equiv of In, and 2 mol% of Pd(PPh3)4.
89
b Isolated yield.
c No reaction.
75
d Without indium.
75
90
As shown in Table 2, the In–InCl3 system was also effec-
tive for the allylation of various carbonyl compounds such
as aromatic aldehydes, heteroaromatic aldehydes, aliphat-
ic aldehydes, and ketones with allyl alcohol in aqueous
media.
68c
a Reactions were carried out with 1 equiv of substrate, 3 equiv of allyl
alcohol, 2 equiv of In, 0.5 equiv of InCl3 and 2 mol% of Pd(PPh3)4 in
THF–H2O, 1:1 at r.t.
b Isolated yield.
Also, this reaction was effectively applicable to other al-
lylic compounds with various leaving groups such as allyl
trifluoroacetate, chloride, carbonate, acetate, and phenyl
sulfone. The results are shown in Table 3. The reaction of
allyl trifluoroacetate and chloride with benzaldehyde in
the absence of InCl3 under aqueous THF solution afforded
the homoallyl alcohol in 80% and 91% yields respectively
c The bath temperature is 50 °C.
Table 3 Palladium-catalyzed Allyation of Benzaldehyde with In–
InCl3 and Various Allylic Compoundsa
requiring longer reaction time (entry 1 and 2). However, Entry
the reaction of allyl carbonate and acetate in the absence
X
InCl3
(equiv)
Time
(h)
Yield
(%)b of 3a
of InCl3 was very slow under the same conditions (entry 4
and 6).
1
OC(O)CF3
Cl
–
24
27
4
80
2
–
91
As shown in Table 4, the palladium-catalyzed allylation
reaction using the In–InCl3 system was also effective for
the allylation of various carbonyl compounds with allyl
acetate in aqueous media.
3
4
5
6
7
8
Cl
0.5
–
94
OC(O)OCH3
OC(O)OCH3
OAc
24
5
trace
96
0.5
–
The palladium-catalyzed allylation of benzaldehyde using
the In–InCl3 system with substituted allylic chlorides,
acetates and alcohols afforded the corresponding
branched homoallylic alcohols exclusively with the anti-
selectivity in aqueous media (Table 5). In the case of cin-
namyl alcohol and acetate, the reaction gave only anti-
products (entry 7 and 8). The reaction of substituted allyl
alcohols usually needed a higher reaction temperature.
24
4
trace
94
OAc
0.5
0.5
SO2Ph
40
54
a Reactions were carried out with 1 equiv of PhCHO, 3 equiv of allyl
alcohol, 2 equiv of In and 2 mol% of Pd(PPh3)4 in THF–H2O, 1:1 at r.t.
b Isolated yield.
Synthesis 2003, No. 5, 775–779 ISSN 0039-7881 © Thieme Stuttgart · New York

SPECIAL TOPIC
Palladium-Catalyzed Allylation of Carbonyl Compounds
777
Table 4 Palladium-Catalyzed Allylation of Various Carbonyl Com-
reactions, the direct formation of -allylpalladium com-
plexes from allylic alcohols usually requires severe reac-
tion conditions9 or a reagent such as SnCl2,10 Ph3P,11
Ph3B,12 and Ti(i-PrO)413 to activate hydroxyl to serve as a
leaving group. So the progress of the reaction of allyl al-
cohol is likely to be determined by the formation of -al-
lylpalladium complexes. In our results, the generation of
-allylpalladium complex from allyl chloride was acceler-
ated in the presence of indium(III) chloride. And the gen-
eration of -allylpalladium complexes from other allylic
compounds, such as allyl alcohol, acetate, and carbonate,
were practical when In–InCl3, In–FeCl3, In–CuCl, In–
SnCl4 or InCl were used. Subsequently, the complex re-
acted with indium in the presence of InCl3 through the re-
ductive transmetalation to allylindium species, which
underwent the usual indium-mediated Barbier-type allyla-
tion of carbonyl compounds. In this reaction, indium(III)
chloride have played a role in the formation of -allylpal-
ladium complexes from allylic compounds and/or in the in
situ generation of the reactive In(I) chloride by reaction
with indium(0) metal. Here, the structure of allylindium
intermediates was not found in aqueous THF whereas al-
lylindium(I) in pure water and allylindium(III) sesquiha-
lides in organic solvents were reported.14 The allylindium
intermediates from allyl chloride in the presence of
Pd(PPh3)4 (10%) was detected by 1H NMR spectroscopy.
The 1H NMR spectra of the allylindium intermediates pre-
pared from In–InCl3 and InCl(I) in D2O [allylic proton
1.57 ppm (d, J = 8.73 Hz)] and in CDCl3 extracted from
D2O [allyl signals 6.11 (m, 1 H), 4.92 (dd, J = 1.76, 16.75
Hz, 1 H), 4.70 (dd, J = 1.98, 9.95 Hz, 1 H), and 2.07 ppm
(d, J = 8.54 Hz, 2 H)] showed the same results respective-
ly. But allylindium compounds from allyl chloride and in-
dium(0) metal in the presence of Pd(PPh3)4 (10%) could
not be detected in 1H NMR spectrum because of its slow
generation and decomposition.
pounds with In–InCl3 and Allyl Acetatea
Entry Substrate
Time (h) Product
Yield (%)b
1
2
3
4
5
6
PhCHO
4
4
3a
3d
3l
94
94
61
89
76
49
p-FPhCHO
CH3(CH2)8CHO
3-Furaldehyde
Cyclohexanone
Acetophenone
12
5
3n
3p
3q
4
96
a Reactions were carried out with 1 equiv of substrate, 3 equiv of allyl
acetate, 2 equiv of In, 0.5 equiv of InCl3 and 2 mol% of Pd(PPh3)4 in
THF–H2O, 1:1 at r.t.
b Isolated yield.
Table 5 Palladium-catalyzed Allylation of Benzaldehyde with In–
InCl3 and Substituted Allylic Compoundsa
Entry Allylic
comounds
Temp. Time Product
(°C) (h)
Yield (%)b
(syn:anti)c
1
r.t.
20
93 (50:50)
93 (63:37)d
Cl
Ph
OH
2
r.t.
3
3s
Cl
3
4
50
20
20
3s
3s
91 (22:78)
95 (36:64)d
OH
r.t.
OH
OAc
5
6
50
15
5
3s
3s
90 (28:72)
90 (26:74)d
r.t.
OAc
7
50
20
78 (anti only)
Ph
Ph
Ph
OH
Ph
In, InCl3
OH
OH
OH
OH
Pd2+
Pd(0)
8
9
50
50
20
20
3t
86 (anti only)
OAc
OH
70
Ph
1) RCHO
InXn
OH
2) H+
R
3u
Scheme 2
10
50
20
45
Ph
OH
We were able to demonstrate that various allylic com-
pounds had been successfully employed in indium-medi-
ated Barbier-type allylation reactions with various
carbonyl compounds using palladium catalyst and metal
salts in aqueous media. We also managed to extend the
scope of indium utility in organic synthesis. Further stud-
ies on the exact mechanism and use of this reaction condi-
tions with various allylic compounds in aqueous media
are in progress.
3v
a Reactions were carried out with 1 equiv of substrate, 3 equiv of allyl
alcohol, 2 equiv of In, 0.5 equiv of InCl3 and 2 mol% of Pd(PPh3)4 in
THF–H2O, 1:1.
b Isolated yield.
c 1H NMR ratio.
d
-Adduct only.
The probable mechanism for the palladium-catalyzed al-
lylation of carbonyl compounds with the In–InCl3 system
All compounds and solvents were obtained commercially and used
is illustrated in Scheme 2. First of all, the reaction might in reactions without any further purification. 1H and 13C NMR spec-
tra were recorded on Bruker Avance 300 spectrometer and Varian
proceed through the generation of -allylpalladium(II)
Unity 300 spectrometer using TMS as internal standard. Electron-
complexes. Unlike other palladium catalyzed allylation
Synthesis 2003, No. 5, 775–779 ISSN 0039-7881 © Thieme Stuttgart · New York

778
T.-S. Jang et al.
SPECIAL TOPIC
impact mass spectra (EIMS) were recorded in the form of m/z on an
Agilent GC-MSD (6850-5973) system. Flash column chromatogra-
phy was performed on silica gel 60 (E. Merck).
1-(4-tert-Butylphenyl)-3-buten-1-ol (3g)
1H NMR (CDCl3): = 7.26–7.38 (4 H, m), 5.75–5.88 (1 H, m),
5.11–5.19 (2 H, m), 4.69 (1 H, t, J = 6.5 Hz), 2.48–2.52 (2 H, m),
2.06 (1 H, br), 1.31 (9 H, s).
Alcohols; General Procedure
13C NMR (CDCl3): = 150.43, 140.86, 134.69, 125.52, 125.27,
118.12, 73.11, 43.58, 34.46, 31.32.
MS (EI, 70 eV): m/z (%) = 186 [M+ – 18], 163 (100), 148, 133, 91,
A mixture of aldehyde (0.5 mmol), allyl alcohol (1.5 mmol), indium
(1.0 mmol), indium(III) chloride (0.25 mmol) and Pd(PPh3)4 (2
mol%) in THF–H2O, 1:1, 1 ml was stirred for 20 h at r.t. The reac-
tion was quenched with 1N HCl (1 mL), EtOAc (1 mL), and the
whole mixture was filtered through celite. After general work-up,
purification by flash column chromatography on silica gel (hexane–
EtOAc, 10:1) afforded the product.
77, 57.
1-(4-Methoxyphenyl)-3-buten-1-ol (3h)
1H NMR (CDCl3): = 7.23–7.27 (2 H, m), 6.84–6.88 (2 H, m),
5.70–5.84 (1 H, m), 5.08–5.16 (2 H, m), 4.64 (1 H, t, J = 6.5 Hz),
3.78 (3 H, s), 2.47 (2 H, m), 2.23 (1 H, br).
1-Phenyl-3-buten-1-ol (3a)
1H NMR (CDCl3): = 7.21–7.35 (5 H, m), 5.69–5.83 (1 H, m),
5.08–5.15 (2 H, m), 4.66 (1 H, t, J = 6.6 Hz), 2.44–2.49 (2 H, m),
2.35 (1 H, br).
13C NMR (CDCl3): = 158.66, 135.80, 133.80, 134.34, 126.77,
117.76, 113.44, 72.68, 54.93, 43.38.
MS (EI, 70 eV): m/z (%) = 160 (100) [M+ – 18], 144, 129, 115, 91,
13C NMR (CDCl3): = 143.81, 134.46, 128.26, 127.39, 125.74,
118.11, 73.23, 43.62.
77, 63.
MS (EI, 70 eV): m/z (%) = 148 [M+], 107 (100), 97, 77.
4-(1-Hydroxy-but-3-enyl)-benzonitrile (3i)
1H NMR (CDCl3): = 7.61–7.63 (2 H, m), 7.45–7.48 (2 H, m),
5.70–5.84 (1 H, m), 5.11–5.18 (2 H, m), 4.80 (1 H, dd, J = 7.7, 5.0
Hz), 2.41–2.57 (3 H, m).
1-(2-Fluorophenyl)-3-buten-1-ol (3b)
1H NMR (CDCl3): = 7.43–7.48 (1 H, m), 7.19–7.27 (1 H, m),
7.10–7.16 (1 H, m), 6.97–7.04 (1 H, m), 5.74–5.87 (1 H, m), 5.11–
5.18 (2 H, m), 5.04 (1 H, dd, J = 7.8, 5.1), 2.42–2.61 (2 H, m).
13C NMR (CDCl3): = 149.19, 133.29, 132.09, 119.19, 118.75,
110.91, 72.29, 43.66.
13C NMR (CDCl3): = 159.62, 134.07, 128.80, 128.69, 127.16,
124.13, 118.52, 115.22, 67.17, 42.48.
MS (EI, 70 eV) m/z (%) = 173 [M+], 132 (100), 104, 77.
MS (EI, 70 eV): m/z (%) = 166 [M+], 125(100), 97, 77.
Methyl 4-(1-Hydroxy-but-3-enyl)-benzoate (3j)
1H NMR (CDCl3): = 8.01 (2 H, m), 7.42 (2 H, d, J = 8.4 Hz),
5.72–5.83 (1 H, m), 5.13–5.19 (2 H, m), 4.80 (1 H, dd, J = 7.7, 5.1
Hz), 3.91 (3 H, s), 2.44–2.54 (2 H, m), 2.29 (1 H, br).
1-(3-Fluorophenyl)-3-buten-1-ol (3c)
1H NMR (CDCl3): = 7.26–7.31 (1 H, m), 7.06–7.11 (2 H, m),
6.93–6.96 (1 H, m), 5.13–5.19 (1 H, m), 5.13–5.18 (1 H, m), 4.72 (1
H, dd, J = 7.7, 5.1 Hz), 2.40–2.54 (2 H, m), 2.16 (1 H, br).
13C NMR (CDCl3): = 166.94, 148.96, 133.79, 129.69, 129.22,
118.91, 125.70, 72.73, 52.05, 43.77.
13C NMR (CDCl3): = 162.91, 146.52, 133.90, 129.84, 121.35,
118.81, 114.26, 112.71, 72.56, 43.74.
MS (EI, 70 eV): m/z (%) = 175 [M+ – 31], 165 (100), 133, 105, 91,
77, 59.
MS (EI, 70 eV): m/z (%) = 166 [M+], 125(100), 97, 77.
4-(1-Hydroxy-but-3-enyl)-benzoic acid (3k)
1H NMR (CD3OD): = 7.94 (2 H, m), 7.69 (2 H, d, J = 8.3 Hz),
5.70–5.79 (1 H, m), 4.95–5.02 (2 H, m), 4.70 (1 H, t, J = 6.5 Hz),
2.41–2.45 (2 H, m).
13C NMR (CD3OD): = 170.01, 151.10, 135.44, 130.72, 130.39,
127.01, 117.89, 74.23, 44.42.
1-(4-Fluorophenyl)-3-buten-1-ol (3d)
1H NMR (CDCl3): = 7.25–7.33 (2 H, m), 6.97–7.05 (2 H, m),
5.69–5.83 (1 H, m), 5.10–5.17 (2 H, m), 4.68 (1 H, t, J = 6.5 Hz),
2.43–2.48 (2 H, m), 2.32(1 H, br).
13C NMR (CDCl3): = 162.08, 139.53, 134.11, 127.41, 118.52,
115.12, 72.60, 43.82.
MS (EI, 70 eV): m/z (%) = 193 [M+ + 1], 175, 151 (100), 105, 79,
MS (EI, 70 eV): m/z (%) = 166 [M+], 125 (100), 97, 77.
77.
Tridec-1-en-4-ol (3l)
1-(2-Bromophenyl)-3-buten-1-ol (3e)
1H NMR (CDCl3): = 5.76–5.90 (1 H, m), 5.09–5.17 (2 H, m),
3.60–3.68 (1 H, m), 2.16–2.34 (1 H, m), 2.09–2.19 (1 H, m), 1.71 (1
H, br), 1.27–1.46 (16 H, m), 0.88 (3 H, t, J = 6.6 Hz).
1H NMR (CDCl3): = 7.48–7.54 (2 H, m), 7.28–7.34 (1 H, m),
7.08–7.13 (1 H, m), 5.79–5.93 (1 H, m), 5.14–5.20 (1 H, m), 5.08 (1
H, dd, J = 8.3, 3.8 Hz), 2.57–2.63 (1 H, m), 2.28–2.39 (2 H, m).
13C NMR (CDCl3): = 134.92, 117.95, 70.69, 36.81, 31.87, 29.63,
29.59, 29.54, 29.29, 25.64, 22.64, 14.06.
MS (EI, 70 eV): m/z (%) = 157 [M+ – 51], 97, 83 (100), 69, 55.
13C NMR (CDCl3): = 142.65, 134.18, 132.54, 128.71, 127.56,
127.26, 121.70, 118.52, 71.75, 41.97.
MS (EI, 70 eV): m/z (%) = 228 [M+ + 2], 226 [M+], 185 (100), 157,
77.
(E)-1-Phenyl-1,5-hexadien-3-ol (3m)
1H NMR (CDCl3): = 7.23–7.39 (5 H, m), 6.60 (1 H, d, J = 15.9
Hz), 6.23 (1 H, dd, J = 15.9, 6.3 Hz), 5.78–5.92 (1 H, m), 5.14–5.20
(2 H, m), 4.35 (1 H, q, J = 5.7 Hz), 2.32–2.48 (2 H, m).
13C NMR (CDCl3): = 136.62, 133.99, 131.50, 130.35, 128.53,
127.62, 126.44, 118.40, 71.71, 41.94.
MS (EI, 70 eV): m/z (%) = 156 [M+ – 18], 133 (100), 115, 105, 91,
77, 55.
1-(4-Methylphenyl)-3-buten-1-ol (3f)
1H NMR (CDCl3): = 7.12–7.23 (4 H, m), 5.71–5.85 (1 H, m),
5.09–5.16 (2 H, m), 4.66 (1 H, t, J = 6.5 Hz), 2.47 (2 H, m), 2.33 (3
H, s), 2.14 (1 H, br).
13C NMR (CDCl3): = 140.88, 137.08, 134.56, 129.00, 125.72,
118.06, 73.14, 43.64, 21.03.
MS (EI, 70 eV): m/z (%) = 144 [M+ – 18], 121 (100), 91, 77.
Synthesis 2003, No. 5, 775–779 ISSN 0039-7881 © Thieme Stuttgart · New York

SPECIAL TOPIC
Palladium-Catalyzed Allylation of Carbonyl Compounds
779
1-(3-Furyl)-3-buten-1-ol (3n)
MS (EI, 70 eV): m/z (%) = 224 [M+], 118 (100), 107, 91, 79, 77.
1H NMR (CDCl3): = 7.38–7.39 (2 H, m), 6.39–6.40 (1 H, m),
5.74–5.88 (1 H, m), 5.11–5.20 (2 H, m), 4.70 (1 H, t, J = 6.5 Hz),
2.47–2.53 (2 H, m).
3-Methyl-1-phenyl-but-3-en-1-ol (3u)
1H NMR (CDCl3): = 7.23–7.38 (5 H, m), 4.90 (1 H, s), 4.83(1 H,
m), 4.78 (1 H, t, J = 6.9 Hz), 2.41 (2 H, d, J = 6.9 Hz).
13C NMR (CDCl3): = 143.19, 138.99, 134.04, 128.37, 66.04,
42.31.
MS (EI, 70 eV): m/z (%) = 138 [M+], 120, 97 (100), 69.
13C NMR (CDCl3): = 114.05, 142.32, 127.39, 125.70, 113.91,
71.44, 48.24, 22.28.
MS (EI, 70 eV): m/z (%) = 162 [M+], 107 (100), 79, 77.
1-(3-Pyridyl)-3-buten-1-ol (3o)
1H NMR (CDCl3): = 8.35–8.36 (1 H, m), 8.27–8.29 (1 H, m),
7.45–7.68 (1 H, m), 7.16–7.21 (1 H, m), 5.64–5.79 (1 H, m), 5.00–
5.05 (2 H, m), 4.89 (1 H, br), 4.69 (1 H, t, J = 6.6 Hz), 2.42–2.48 (2
H, m).
2,2-Dimethyl-1-phenyl-but-3-en-1-ol (3v)
1H NMR (CDCl3): = 7.28–7.31 (5 H, m), 5.92 (1 H, dd, J = 17.4,
10.8 Hz), 5.05–5.16 (2 H, m), 4.43 (1 H, s), 2.03 (1 H, br), 1.01 (3
H, s), 0.96 (3 H, s).
13C NMR (CDCl3): = 147.89, 147.25, 133.93, 133,74, 123.32,
118.20, 70.74, 43.45.
13C NMR (CDCl3): = 145.16, 140.80, 127.79, 127.48, 113.81,
80.66, 42.24, 24.44, 21.06.
MS (EI, 70 eV): m/z (%) = 149 [M+], 108 (100), 80, 53.
MS (EI, 70 eV): m/z (%) = 176 [M+], 107 (100), 79, 77, 70, 55.
1-Allyl-cyclohexanol (3p)
1H NMR (CDCl3): = 5.82–5.97 (1 H, m), 5.08–5.17 (2 H, m), 2.22
(2 H, dd, J = 7.8, 1.2 Hz), 1.26–1.66 (11 H, m).
Acknowledgments
This work was fully supported by the Korea Institute of Science &
Technology and the Ministry of Science & Technology.
13C NMR (CDCl3): = 133.71, 118.56, 46.67, 37.34, 25.72, 22.13.
MS (EI, 70 eV): m/z (%) = 122 [M+ – 18], 99 (100), 81, 55.
References
2-Phenyl-pent-4-en-2-ol (3q)
1H NMR (CDCl3): = 7.41–7.46 (2 H, m), 7.29–7.36 (2 H, m),
7.19–7.26 (1 H, m), 5.54–5.69 (1 H, m), 5.08–5.16 (2 H, m), 2.64–
2.72 (1 H, m), 2.45–2.53 (1 H, m), 2.05 (1 H, br), 1.54 (3 H, d,
J = 2.7 Hz).
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13C NMR (CDCl3): = 147.63, 133.65, 128.12, 126.57, 124.73,
119.33, 73.60, 48.44, 29.82.
EIMS (EI, 70 eV): m/z (%) = 144 [M+ – 18], 121 (100), 105, 77.
Ethyl 3-Hydroxy-hex-5-enoate (3r)
1H NMR (CDCl3): = 5.79–5.93 (1 H, m), 5.06–5.14 (2 H, m), 4.18
(2 H, q, J = 7.2 Hz), 3.63 (1 H, br), 2.47 (2 H, q, J = 15.3 Hz), 2.30
(2 H, d, J = 7.8 Hz), 1.28 (3 H, t, J = 7.2 Hz), 1.25 (3 H, s).
13C NMR (CDCl3): = 133.67, 118.49, 70.68, 46.49, 44.40, 26.80,
14.13.
MS (EI, 70 eV) m/z (%) = 157 [M+ – 15], 131, 103, 85 (100), 69.
2-Methyl-1-phenyl-but-3-en-1-ol (3s)
1H NMR (CDCl3): syn isomer, = 7.22–7.34 (5 H, m), 5.68–5.86 (1
H, m), 5.00–5.06 (2 H, m), 4.58 (1 H, d, J = 5.7 Hz), 2.41–2.60 (1
H, m), 2.10 (1 H, br), 1.00 (3 H, d, J = 6.9 Hz); anti isomer,
=
7.22–7.34 (5 H, m), 5.68–5.86 (1 H, m), 5.15–5.21 (2 H, m), 4.34 (1
H, d, J = 7.8 Hz), 2.41–2.60 (1 H, m), 2.24 (1 H, br), 0.86 (3 H, d,
J = 7.2 Hz).
13C NMR (CDCl3): syn isomer, = 142.41, 140.32, 127.97, 127.25,
126.46, 115.3877.66, 44.45, 13.92; anti isomer, = 142.56, 140.61,
128.14, 127.55, 126.76, 116.62, 77.91, 46.10, 16.42.
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MS (EI, 70 eV): m/z (%) = 144 [M+ – 18], 128, 115, 107 (100), 79,
77.
1,2-Diphenyl-but-3-en-1-ol (3t)
1H NMR (CDCl3): anti isomer, = 7.10–7.29 (10 H, m), 6.25–6.37
(1 H, m), 5.24–5.34 (2 H, m), 4.89 (1 H, d, J = 7.8 Hz), 3.61 (1 H,
t, J = 8.2 Hz), 2.57 (1 H, br).
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13C NMR (CDCl3): anti isomer, = 141.84, 140.60, 137.78, 128.26,
127.80, 127.29, 126.59, 126.47, 118.20, 77.12, 59.01.
Synthesis 2003, No. 5, 775–779 ISSN 0039-7881 © Thieme Stuttgart · New York