Direct palladium/carboxylic acid-catalyzed C-allylation of cyclic 1,3-diones with allylic alcohols in water

Article abstract of DOI:10.1016/j.tet.2007.11.082

The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of cyclic 1,3-diones using allylic alcohols directly gave the corresponding C-allylated products in good yields.

Full text of DOI:10.1016/j.tet.2007.11.082

Available online at www.sciencedirect.com
Tetrahedron 64 (2008) 1204e1212
www.elsevier.com/locate/tet
Direct palladium/carboxylic acid-catalyzed C-allylation
of cyclic 1,3-diones with allylic alcohols in water
*
Kim-Hong Gan, Ciou-Jyu Jhong, Shyh-Chyun Yang
Faculty of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung 807, Taiwan, ROC
Received 7 September 2007; received in revised form 14 November 2007; accepted 23 November 2007
Abstract
The direct activation of CeO bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by
carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of cyclic 1,3-diones using allylic alcohols
directly gave the corresponding C-allylated products in good yields.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: Palladium-catalyzed; Water; Cyclic 1,3-diones; Allylic alcohols
1. Introduction
bond in allylic alcohols on interaction with a transition metal
complex.40e43 Successful applications using allylic alcohols
directly in catalytic processes are even more limited. This
apparently stems from the poor capability of a nonactivated
hydroxyl to serve as a leaving group.37 Ozawa et al. reported
that (p-allyl)palladium complexes bearing diphosphinidene-
cyclobutene ligands effectively catalyze C- and N-allylation
using allylic alcohols without OH activators.44 However, the
addition of pyridine as a base was required for the C-allylation
of active methylene compounds to enhance their nucleophilic-
ity. Patil and Yamamoto disclosed the direct palladium-
catalyzed allylic substitution of allylic alcohols by carbon
pronucleophiles.45 We have reported our attempts and some
successful applications of a process involving the CeO bond
cleavage with direct use of allylic alcohols catalyzed by palla-
dium complexes in the presence of Ti(OiPr)4 in benzene.46e49
Organic reactions in water have recently attracted much atten-
tion, because water is a safe and economical substitute for
conventional organic solvent.50e54 Thus, development of
atom-economical reactions in water is one of the most impor-
tant goals of synthetic chemistry. Due to our continuing inter-
est in the palladium-catalyzed allylation of anilines, we have
recently disclosed a new catalytic system for palladium/
carboxylic acid-catalyzed allylation of anilines with allylic
alcohols in water as a suspension medium.55 Herein, we will
The palladium-catalyzed allylation is a powerful tool for
CeC, CeN, and CeO bond formation, which has been widely
applied to organic chemistry.1e3 The processes have been
shown to proceed by attack of nucleophiles on intermediate
h3-allylpalladium(II) complexes generated by oxidative addi-
tion of allylic compounds including halides,4e6 esters,7e15
carbonates,16e20 carbamates,21,22 phosphates,23,24 and related
derivatives25e28 to a Pd(0) complex. Because these substrates
are synthesized from the corresponding allylic alcohols, palla-
dium-catalyzed conversion of allylic alcohols directly into
allylation products is highly beneficial, especially from the
viewpoint of the atom economy.29,30 For achieving the palla-
dium-catalyzed direct cleavage of CeO bond in allylic
alcohols, various processes have been reported.31 These
processes include conversion of allylic alcohols into the
esters of inorganic acids (e.g., As2O3,32 B2O3,33 CO2 ) or em-
1
ployment of a Lewis acid (e.g., BEt3,34,35 BF3,36 BPh3,37
SnCl238,39). However, there have been only limited and spo-
radic reports dealing with the direct cleavage of the CeO
* Corresponding author. Fax: þ886 (7) 3210683.
E-mail address: scyang@kmu.edu.tw (S.-C. Yang).
0040-4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.11.082

K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
1205
Table 1
Allylation of 1,3-cyclohexadione (1a) with cinnamyl alcohol (2a): temperature
describe a novel catalysis of palladium complex, which medi-
ates C-allylation of cyclic 1,3-diones with allylic alcohols
using water as solvent.
and acid effectsa
Entry
Additive
Yield (%)b
Yield (%)b
of 3a
Yield (%)b
of 4a
(3aþ4a)
3
99
6
1c
2
3d
4e
5f
6g
7i
8j
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
d
PhOCH2CO2H
CH3(CH2)10CO2H
Ph2CHCO2H
4-OctC6H4CO2H
PhCO2H
3
21
6
2. Results and discussion
78
The palladium-catalyzed allylation of cyclic 1,3-diones
with cinnamyl alcohol was investigated under various condi-
tions (Scheme 1). When a mixture of 1,3-cyclohexadione
(1a, 1 mmol) and cinnamyl alcohol (2a, 0.8 mmol) was heated
in the presence of catalytic amounts of Pd(OAc)2 (0.05 mmol),
PPh3 (0.2 mmol), and 1-adamantanecarboxylic acid
(1-AdCO2H) (0.5 mmol) in water at 50 ꢀC for 15 min, 2-cin-
namyl-1,3-cyclohexadione (3a) was formed in only 3% yield
(entry 1 in Table 1). The reaction, under reflux, increased
the yields of products 3a and 2,2-dicinnamyl-1,3-cyclohexa-
dione (4a) to 21 and 78%, respectively (entry 2). It was con-
firmed that the yield was decreased in the absence of PPh3
(entry 3). The reaction did not occur in the absence of the pal-
ladium species as a catalyst (entry 4). As expected, increasing
the relative amount of 1,3-cyclohexadione favored the forma-
tion of the desired diallylated product 4a (entries 5 and 6). The
reaction gave only 40% yield without water as solvent (entry
7). The absence of a carboxylic acid gave moderate yields
of products (entry 8). The effect of water may activate allyl
alcohol via hydration of the hydroxyl group for the smooth
generation of the p-allylpalladium intermediate.56 Other carb-
oxylic acids such as PhOCH2CO2H (entry 9), lauric acid
(entry 10), and 4-octylbenzoic acid (entry 12) were also effec-
tive for the allylation. PhCO2H (entry 13), CH3CO2H (entry
15), and dodecylbenzenesulfonic acid (DBSA) (entry 16)
gave moderate yields of products. Ph2CHCO2H (entry 11)
and 4-aminobenzoic acid (entry 14) retarded the allylation.
Strong acids such as C6F5OH (entry 17) also enhanced the
substitution reaction.
0
99
99h
40
62
91
89
33
88
58
28
73
49
99
17
1
82
98
24
36
71
84
25
73
26
16
55
38
95
16
26
20
5
9
10
11
12
13
14
15
16
17
a
8
15
32
12
18
11
4
H2NC6H4CO2H
CH3CO2H
DBSA
C6F5OH
Reaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd(OAc)2 (0.05 mmol),
PPh3 (0.2 mmol), and additive (0.5 mmol) in water (5 mL) were refluxed for
15 min.
b
Isolated yield was based on 2a.
Stirred at 50 ꢀC for 15 min.
Without PPh3.
c
d
e
Without Pd(OAc)2.
Compound 2a (1.2 mmol) was used.
f
g
Compound 2a (4 mmol) was used.
Isolated yield was based on 1a.
h
i
Without water.
Without additive.
j
of various monodentate ligands including PPh3, Bu3P,
(2-MeC6H4)3P, (2-furyl)3P, (2-pyridyl)Ph2P, (3-MeC6H4)3P,
(4-MeC6H4)3P, (4-MeOC6H4)3P, (4-FC6H4)3P, (4-ClC6H4)3P,
[2,6-(MeO)2C6H3]3P, and [2,4,6-(MeO)3C6H2]3P (entries 1
and 13e23) showed that PPh3 (entry 1), (2-furyl)3P (entry
15), (2-pyridyl)Ph2P (entry 16), (3-MeC6H4)3P (entry 17),
(4-MeC6H4)3P (entry 18), and (4-FC6H4)3P (entry 20) were
the most effective ligands. The bidentate ligands such as
dppp, dppb, and dpph could give good results (entries 24e
26). (ꢁ)-BINAP afforded low yields of products (entry 27).
Results for C-allylation of a number of cyclic 1,3-diones
(1bei) with cinnamyl alcohol (2a) using Pd(OAc)2, PPh3,
and 1-AdCO2H in water are summarized in Table 3. Dimedone
(1b) underwent mono- and diallylation, while the addition of
1-AdCO2H provided mono- and diallylated products in quan-
titatively yields (entry 1). 2,4-Quinolinediol (1c) also reacted
to give the C-allylated products in good yields (entry 2).
With 3-hydroxy-1H-phenalen-1-one (1d), only the diallylated
product 2,2-dicinnamyl-2H-phenalen-1,3-dione (4d) was ob-
tained, however, in a very low yield (entry 3). The reaction
gave 36% yield under reflux for 30 min (entry 4). Cyclic
1,3-diones 1e and 1f also afforded only diallylated product
in high yields (entries 5 and 6). Using Pd(OAc)2 as catalyst
was more effective than PdCl2 (entry 7). 4-Hydroxycoumarin
(1g) gave monoallylated products 3g and 5 in 68 and 6%,
respectively (entry 8). Compound 5 may be produced via
Ph
Ph
O
Ph
O
HO
Ph
HO
O
O
O
2a
+
Pd catalyst, ligand
additive, H2O
1a
3a
4a
Scheme 1. Allylation of 1,3-cyclohexadione (1a) with cinnamyl alcohol (2a).
A comparative study of different palladium catalysts and
phosphine ligands in water was undertaken (Table 2). Among
the palladium catalysts including Pd(OAc)2 (entry 1), Pd-
(acac)2 (entry 2), PdCl2(1,10-phen) (entry 3), Pd(OCOCF3)2
(entry 4), PdCl2(MeCN)2 (entry 5), PdCl2(PhCN)2 (entry 6),
PdCl2 (entry 7), Pd(propionate)2 (entry 8), Pd(hfacac)2 (entry
9), Pd2(dba)3 (entries 10 and 11), and Pd(PPh3)4 (entry 12)
were used. Pd(OAc)2, PdCl2, Pd(hfacac)2, and Pd(PPh3)4
were found to be the superior. However, using Pd2(dba)3
with extra PPh3 as catalyst increased the yield of products
(entry 11). The catalytic reactivity of the phosphine ligands
is likely due to improved catalyst stability. In the presence

1206
K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
Table 2
Allylation of 1,3-cyclohexadione (1a) with cinnamyl alcohol (2a): palladium and phosphine ligand effectsa
Entry
Palladium
Ligand
Yield (%)b
Yield (%)b
of 3a
Yield (%)b
of 4a
(3aþ4a)
1
Pd(OAc)2
Pd(acac)2
PPh3
PPh3
99
70
77
59
52
74
95
81
99
2
21
3
78
67
66
51
44
71
87
75
69
2
3
PdCl2(1,10-phen)
Pd(OCOCF3)2
PdCl2(MeCN)2
PdCl2(PhCN)2
PdCl2
PPh3
PPh3
11
8
4
5
PPh3
PPh3
8
6
3
7
PPh3
PPh3
8
8
Pd(propionate)2
c
Pd(hfacac)2
6
9
PPh3
d
30
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
a
Pd2(dba)3
Pd2(dba)3
Pd(PPh3)4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PPh3
d
87
99
5
2
85
86
13
5
Bu3P
(2-MeC6H4)3P
(2-Furyl)3P
(2-Pyridyl)Ph2P
(3-MeC6H4)3P
(4-MeC6H4)3P
(4-MeOC6H4)3P
(4-FC6H4)3P
(4-ClC6H4)3P
[2,6-(MeO)2C6H3]3P
[2,4,6-(MeO)3C6H2]3P
dpppd
44
99
99
99
99
87
99
96
3
5
39
96
97
83
90
81
92
93
3
2
16
9
6
7
3
3
4
4
80
80
81
6
11
33
47
6
69
47
34
dppbe
dpphf
(ꢁ)-BINAPg
Reaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd catalyst (0.05 mmol), ligand (0.2 mmol), and 1-AdCO2H (0.5 mmol) in water (5 mL) were refluxed for
15 min.
b
c
d
e
f
Isolated yield was based on 2a.
Palladium hexafluoroacetylacetonate.
1,3-Bis(diphenylphosphino)propane.
1,4-Bis(diphenylphosphino)butane.
1,6-Bis(diphenylphosphino)hexane.
(ꢁ)-2,20-Bis(diphenylphosphino)-1,10-binaphthyl.
g
Table 3
Allylation of cyclic 1,3-diones (1bei) with cinnamyl alcohol (2a)a
Entry
1
Yieldsb (%)
O
Ph
Ph
OH
O
O
Ph
1
O
O
1b
3b (73)
4b (26)
Ph
OH
O
OH
Ph
Ph
2
N
H
O
N
H
O
N
H
O
4c (29)
1c
3c (59)
O
Ph
Ph
HO
O
O
3
4d (9)
1d

K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
1207
Table 3 (continued)
Entry
4c
1
Yieldsb (%)
1d
4d (36)
O
Ph
Ph
O
O
O
O
O
O
5
O
O
1e
4e (99)
O
Ph
OH
O
6
Ph
O
O
1f
1f
4f (98)
7d
4f (62)
O
OH
Ph
Ph
OH
O
O
Ph
3g (68)
5 (6)
OH
Ph
O
O
8
O
1g
O
Ph
O
4g
O
OH
Cl
Cl
Ph
Ph
OH
O
O
3h (31)
Ph
6 (9)
OH
Ph
Cl
O
O
9
Cl
O
O
Ph
1h
O
4h
O
O
Ph
Ph
O
Ph
Ph
HN
HN
HN
O
O
N
O
4i (10)
Ph
7 (40)
O
HN
O
Ph
Ph
NH
O
Ph
10
N
O
1i
O
N
O
Ph
8 (47)
a
Reaction conditions: 1 (1 mmol), 2a (0.8 mmol), Pd(OAc)2 (0.05 mmol), PPh3 (0.2 mmol), and 1-AdCO2H (0.5 mmol) in water (5 mL) were refluxed for
15 min.
b
c
d
Isolated yield was based on 2a.
Refluxed for 30 min.
PdCl2 was used.

1208
K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
Table 4
Reaction of 1,3-cyclohexadione (1a) with allylic alcohols 2a
diallyated product 4g, which was hydrolyzed and then decarb-
oxylated to compound 5. 6-Chloro-4-hydroxycoumarin (1h)
reacted as 1g, affording the corresponding products 3h and 6
in 31 and 9%, respectively (entry 9). Allylation of 1i gave mix-
tures of di-, tri-, and tetraallylated pyrimidine 4i, 7, and 8 in
yields of 10, 40, and 47%, respectively (entry 10).
Entry
2
Yieldsb (%)
OH
O
OH
1
Results for allylation of 1,3-cyclohexadione with both aro-
matic and aliphatic allylic alcohols 2bej using Pd(OAc)2,
PPh3, and 1-AdCO2H are summarized in Table 4. In addition
to the parent cinnamyl alcohol (2a), trans-1,3-diphenyl-
2-propen-1-ol (2b) reacted to give the allylating product 9 in
moderate yields (entry 1). Steric factors affected the yield.
In contrast to the previous systems for allylic substitution, re-
actions of aliphatic allylic alcohols occurred with only low
yields (entries 2e9). Treatment of 1,3-cyclohexadione (1a)
with crotyl alcohol (2c) gave only stereoisomeric product 10
in the yield of 33% (entry 2). The formation of regioisomeric
product was not observed. The 80:20 E/Z ratio of 10 was de-
2b
9 (52)
OH
O
OH
2
3
2c
c
10 (33) (E/Z = 80/20)
10 (43) (E/Z¼82:18)c
OH
2d
1
termined by H NMR. Product E alkene arose from the more
thermodynamically stable syn p-allyl complex. Both regioiso-
meric alcohols 2c and 2d gave identical product 10 in similar
E/Z ratios (entry 3). The loss of the stereochemistry of the
starting alcohol 2c is due to a rapid s$h3$s interconver-
sion of the p-allyl intermediate compared to the rate of alkyl-
ation of this intermediate. With the unsymmetrical allylic
alcohols 2, the major products were obtained from approach
of 1 at the less sterically hindered primary site. Both regioiso-
meric alcohols 2e and 2f reacted with 1,3-cyclohexadione to
give only more highly substituted alkene 11 (entries 4 and
5). Similarly, 3-methyl-2-buten-1-ol (2g) and its regioisomer
2h, 2-methyl-3-buten-2-ol yielded only monoallylated product
12 (entries 6 and 7). Using geraniol (2i) as allylating reagent
gave only monoallylated product 13 in 24% yield (entry 8).
The secondary alcohol 2j gave 66% yields (entry 9).
OH
O
OH
4
2e
11 (57)
11 (38)
5
6
7
8
OH
2f
Although a detailed mechanistic study for the allylation of
cyclic 1,3-diones 1 with allylic alcohols 2 has not been under-
taken, the reaction most likely proceeds via the pathway out-
lined in Scheme 2, in which the substituent on allylic alcohol
O
OH
OH
2g
12 (13)
12 (12)
OH
2h
O
HO
O
Pd0Ln
OH
OH
2
3
OH
13 (24)
2i
O
Pd
L
Pd
OH
L
X
HO
15
O
OH
9
16
X = OH or
OCOR
2j
14 (66)
HO
O
a
H2O or
HOCOR
Reaction conditions: 1a (1.0 mmol), 2 (0.8 mmol), Pd(OAc)2 (0.05 mmol),
PPh3 (0.2 mmol), 1-adamantanecarboxylic acid (0.5 mmol), and water (5 mL)
were refluxed for 30 min.
1
b
Isolated yield was based on 2.
Determined by GC.
Scheme 2. Proposed mechanism of the allylation of cyclic 1,3-diones 1 with
allylic alcohols 2.
c

K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
1209
is omitted. Oxidative addition of alcohol 2 or protonated
alcohol, formed by the acid, to Pd(0) species affords the
p-allylpalladium intermediate (15). The formation of p-allyl-
palladium may be accelerated by the acid, possibly by proton-
ation to increase the leaving group ability of the OH group of
allyl alcohol.57 Formation of a p-allylpalladium with carb-
oxylic acid could be the key for the rate enhancement by the
acid.58 Intermolecular nucleophilic substitution of pronucleo-
philes 1 takes place at the p-allyl system to give intermediate
16, which undergoes reductive elimination to produce 2-allyl-
ated-1,3-diones. In the presence of cyclic 1,3-diones, which
may be relatively reactive toward the palladium center, 15
should be predominantly transformed to 16 to afford allylated
compound.
(ethyl acetate/n-hexane 1:4) of the residue afforded 3a and
4a in 21 and 79% yields, respectively.
4.2.2. 2-Cinnamyl-1,3-cyclohexadione (3a)
White crystals. Mp 161e162 ꢀC (methanol/hꢂex1ane) (160e
162 ꢀC59). IR (KBr) n: 3421, 2948, 1577 cm
.
1H NMR
(CD3OD) d: 1.96 (quin, J¼6.4 Hz, 2H, CH2), 2.44 (t,
J¼6.4 Hz, 4H, CH2ꢃ2), 3.13 (d, J¼6.8 Hz, 2H, CH2), 6.18
(dt, J¼6.8, 16.0 Hz, 1H, vinyl H), 6.33 (d, J¼16.0 Hz, 1H,
vinyl H), 7.10e7.14 (m, 1H, ArH), 7.20e7.29 (m, 4H,
ArH). 13C NMR (CD3OD) d: 22.0 (CH2), 26.1 (CH2), 33.8
(CH2), 114.8 (C), 126.9 (CH), 127.6 (CH), 129.3 (CH),
129.4 (CH), 130.6 (CH), 139.4 (C). EIMS m/z: 228 (Mþ),
200, 172, 157, 144, 138, 130, 115, 104, 91. HRESI-MS calcd
for C15H17O2 [Mþ1]þ 229.1228, found 229.1227.
3. Conclusions
4.2.3. 2,2-Dicinnamyl-1,3-cyclohexadione (4a)
White crystals. Mp 109e110 ꢀC (chloroform/hexane)
In summary, we have developed a catalytic system that
enables reactions of cyclic 1,3-diones with allylic alcohols
as allylating agents in water. This is a simple and efficient
route for CeC bond formation. The effect of addition of a carb-
oxylic acid to promote the palladium-catalyzed allyleOH
bond cleavage remarkably enhanced both the reaction rate
and the yield. The alkylation of aromatic allylic alcohol
worked well with cyclic 1,3-diones, giving generally good to
high yields of the corresponding allylic 1,3-diones.
(110e111 ꢀC59). IR (KBr) n: 3398, 2925, 1693 cmꢂ1 1H
.
NMR (CDCl3) d: 1.85 (quin, J¼6.8 Hz, 2H, CH2), 2.54 (t,
J¼6.8 Hz, 4H, CH2ꢃ2), 2.72 (d, J¼7.6 Hz, 2H, CH2), 5.96
(dt, J¼7.6, 15.6 Hz, 1H, vinyl H), 6.39 (d, J¼15.6 Hz, 1H,
vinyl H), 7.18e7.31 (m, 10H, ArH). 13C NMR (CDCl3) d:
16.4 (CH2), 40.2 (CH2), 40.4 (CH2), 68.6 (C), 123.6 (CH),
126.2 (CH), 127.5 (CH), 128.5 (CH), 134.3 (CH), 136.7 (C),
210.9 (C). EIMS m/z: 344 (Mþ), 326, 308, 282, 254, 243,
235, 227, 220, 205, 198, 179, 167, 156, 141, 128, 118, 115,
92, 91. HRESI-MS calcd for C24H25O2 [Mþ1]þ 345.1854,
found 345.1852.
4. Experimental section
4.1. General considerations: general method
4.2.4. 2-Cinnamyl-5,5-dimethyl-1,3-cyclohexadione (3b)
White crystals. Mp 166e167 ꢀC (methanol/hꢂex1ane) (165e
.
1H NMR
All melting points were uncorrected. IR absorption spectra
were recorded on a PerkineElmer System 2000 FT-IR spectro-
photometer. Proton and carbon-13 NMR spectra were mea-
sured with a Unity-400 or Mercury Plus-400 spectrometer.
Carbon multiplicities were obtained from DEPT experiments.
Chemical shifts (d) and coupling constants (Hz) were measured
with respect to TMS or chloroform-d1. MS and high-resolution
mass spectra (HRMS) were taken on a Thermo-Finnigan trace
GC or JEOL TMSD-100 instrument, with a direct inlet system.
Elemental analyses were carried out on a Heraeus CHN-O-
Rapid elemental analyzer.
167 ꢀC60). IR (KBr) n: 3446, 2958, 1558 cm
(CD3OD) d: 1.08 (s, 6H, CH3ꢃ2), 2.33 (s, 4H, CH2ꢃ2),
3.13 (dd, J¼1.2, 6.4 Hz, 2H, CH2), 6.18 (dt, J¼6.4, 15.6 Hz,
1H, vinyl H), 6.33 (d, J¼16.0 Hz, 1H, vinyl H), 7.10e7.15
(m, 1H, ArH), 7.21e7.28 (m, 4H, ArH). 13C NMR
(CD3OD) d: 26.3 (CH2), 28.4 (CH3), 32.0 (C), 47.4 (CH2),
112.7 (C), 126.4 (CH), 127.0 (CH), 128.9 (CH), 129.8 (CH),
130.1 (CH), 138.7 (C). EIMS m/z: 256 (Mþ), 254, 239, 221,
212, 199, 170, 155, 141, 128, 115, 102, 91, 77. HRESI-MS
calcd for C17H21O2 [Mþ1]þ 257.1541, found 257.1540.
4.2. General procedure for the palladium-catalyzed
allylation of cyclic 1,3-diones
4.2.5. 2,2-Dicinnamyl-5,5-dimethyl-1,3-cyclohexadione (4b)
Yellow crystals. Mp 148e149 ꢀC (chloroꢂfo1rm/hexane)
.
1H NMR
(149 ꢀC61). IR (KBr) n: 3447, 2954, 1693 cm
4.2.1. Reaction with 1,3-cyclohexadione (1a)
(CDCl3) d: 0.95 (s, 6H, CH3ꢃ2), 2.57 (s, 4H, CH2ꢃ2), 2.70
(dd, J¼1.2, 7.6 Hz, 4H, CH2ꢃ2), 6.01 (dt, J¼7.6, 16.0 Hz,
2H, vinyl H), 6.43 (d, J¼16.0 Hz, 2H, vinyl H), 7.18e7.31
(m, 10H, ArH). 13C NMR (CDCl3) d: 28.7 (CH3), 30.7 (C),
38.4 (CH2), 52.3 (CH2), 68.5 (C), 123.8 (CH), 126.2 (CH),
127.4 (CH), 128.5 (CH), 134.4 (CH), 136.9 (C), 209.0 (C).
EIMS m/z: 372 (Mþ), 354, 336, 321, 299, 281, 263, 255,
243, 225, 220, 207, 205, 199, 179, 167, 154, 142, 128, 117,
115, 105, 92. HRESI-MS calcd for C26H29O2 [Mþ1]þ
373.2167, found 373.2169.
Cinnamyl alcohol (2a) (107 mg, 0.8 mmol) and 1-adaman-
tanecarboxylic acid (90 mg, 0.5 mmol) were suspended in
water (5 mL) at rt, and then Pd(acac)2 (11 mg, 0.05 mmol),
PPh3 (52 mg, 0.2 mmol), and 1,3-cyclohexadione (112 mg,
1 mmol) were added. The whole mixture was heated under
reflux conditions for 15 min. After the mixture was cooled to
rt, water and brine were added. The organic materials were
extracted with dichloromethane, dried over magnesium sulfate,
and concentrated under vacuum. Column chromatography

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K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
4.2.6. 3-Cinnamyl-4-hydroxyquinoline-2(1H)-one (3c)
4.2.10. (4E)-2-Cinnamyl-1-(2-hydroxyphenyl)-5-
phenylpent-4-en-1-one (5)
Yellow crystals. Mp 221e222 ꢀC (methanol/hexane). IR
(KBr) n: 3024, 1602 cmꢂ1
.
1H NMR (CDCl3) d: 3.56 (d,
Colorless oil. IR (KBr) n: 3026, 1632 cmꢂ1 1H NMR
.
J¼5.2 Hz, 2H, CH2), 6.36 (dt, J¼5.6, 16.0 Hz, 1H, vinyl H),
6.43 (d, J¼16.0 Hz, 1H, vinyl H), 7.10e7.14 (m, 1H, ArH),
7.20e7.35 (m, 6H, ArH), 7.51 (ddd, J¼1.6, 7.2, 8.4 Hz, 1H,
ArH), 7.99 (dd, J¼1.2, 8.4 Hz, 1H, ArH). 13C NMR
(CDCl3) d: 27.3 (CH2), 110.0 (C), 116.4 (CH), 117.3 (C),
123.2 (CH), 123.9 (CH), 127.0 (CH), 127.9 (CH), 128.1
(CH), 129.4 (CH), 131.2 (CH), 131.6 (CH), 138.6 (C), 139.2
(C), 160.9 (C), 166.4 (C). EIMS m/z: 277 (Mþ), 246, 230,
187, 186, 168, 146, 130, 115, 91. HRESI-MS calcd for
C18H16NO2 [Mþ1]þ 278.1181, found 278.1182.
(CDCl3) d: 2.49e2.56 (m, 2H, CHꢃ2), 2.69e2.77 (m, 2H,
CHꢃ2), 3.75 (quin, J¼6.8 Hz, 1H, CH), 6.14 (dt, J¼7.2,
15.6 Hz, 2H, vinyl H), 6.43 (d, J¼15.6 Hz, 2H, vinyl H),
6.90 (ddd, J¼1.2, 7.2, 8.0 Hz, 1H, ArH), 7.00 (dd, J¼1.2,
8.4 Hz, 1H, ArH), 7.17e7.30 (m, 10H, ArH), 7.47 (ddd,
J¼1.6, 7.2, 8.4 Hz, 1H, ArH), 7.82 (dd, J¼1.6, 8.0 Hz, 1H,
ArH), 12.55 (s, 1H, OH). 13C NMR (CDCl3) d: 35.3 (CH2),
45.9 (CH), 118.8 (CH), 118.9 (CH), 119.0 (C), 126.1 (CH),
126.6 (CH), 127.3 (CH), 128.5 (CH), 129.8 (CH), 132.6
(CH), 136.5 (CH), 137.1 (C), 163.1 (C), 208.6 (C). EIMS
m/z: 368 (Mþ), 350, 277, 251, 233, 218, 205, 183, 149, 131,
121, 115, 93, 91. Anal. Calcd for C26H24O2$H2O: C, 84.75;
H, 6.57. Found: C, 84.38; H, 7.00.
4.2.7. 3,3-Dicinnamylquinoline-2,4(1H,3H)-dione (4c)
Colorless oil. IR (KBr) n: 3059, 1659 cmꢂ1 1H NMR
.
(CDCl3) d: 2.86e2.98 (m, 4H, CH2ꢃ2), 5.99 (dt, J¼7.6,
15.6 Hz, 2H, vinyl H), 6.43 (d, J¼16.0 Hz, 2H, vinyl H),
6.88 (d, J¼8.0 Hz, 1H, ArH), 7.08e7.29 (m, 11H, ArH),
7.42e7.47 (m, 1H, ArH), 7.94 (d, J¼8.0 Hz, 1H, ArH), 9.31
(s, 1H, NH). 13C NMR (CDCl3) d: 41.3 (CH2), 62.3 (C),
116.2 (CH), 119.5 (C), 123.2 (CH), 123.6 (CH), 126.2 (CH),
127.3 (CH), 127.4 (CH), 128.3 (CH), 134.3 (CH), 136.2
(CH), 136.8 (C), 140.7(C), 173.7 (C), 196.5 (C). EIMS m/z:
393 (Mþ), 378, 364, 316, 302, 277, 276, 258, 248, 230,
219, 203, 186, 176, 175, 157, 146, 129, 117, 115, 91, 77.
HRESI-MS calcd for C27H24NO2 [Mþ1]þ 394.1807, found
394.1809.
4.2.11. 6-Chloro-3-cinnamyl-4-hydroxy-2H-chromen-2-one
(3h)
Brown crystals. Mp 200e201 ꢀC (methanol/hexane). IR
1
(KBr) n: 3287, 1670 cmꢂ1. H NMR (CD3OD) d: 3.47 (dd,
J¼1.6, 6.0 Hz, 2H, CH2), 6.30 (dt, J¼6.0, 16.0 Hz, 1H, vinyl
H), 6.46 (d, J¼15.6 Hz, 1H, vinyl H), 7.13e7.17 (m, 1H,
ArH), 7.22e7.26 (m, 2H, ArH), 7.30e7.35 (m, 3H, ArH),
7.57 (dd, J¼2.4, 8.8 Hz, 1H, ArH), 7.92 (d, J¼2.4 Hz, 1H,
ArH). 13C NMR (CD3OD) d: 28.5 (CH2), 104.1 (C), 118.2
(CH), 119.8 (C), 123.8 (CH), 126.5 (CH), 127.4 (CH), 127.4
(CH), 128.7 (C), 128.9 (CH), 130.8 (CH), 131.2 (CH), 138.0
(C), 151.7 (C), 161.5 (C), 163.5 (C). EIMS m/z: 314
(Mþþ2), 312 (Mþ), 297, 277, 265, 223, 221, 209, 202, 157,
155, 130, 128, 115, 91. HRESI-MS calcd C18H14O3Cl
[Mþ1]þ 313.0631, found 313.0630.
4.2.8. 2,2-Dicinnamyl-2H-phenalene-1,3-dione (4d)
1
Deep yellow oil. IR (KBr) n: 2921, 1668 cmꢂ1. H NMR
(CDCl3) d: 2.97 (d, J¼7.6 Hz, 4H, CH2ꢃ2), 6.00 (dt, J¼7.6,
15.6 Hz, 2H, vinyl H), 6.40 (d, J¼16.0 Hz, 2H, vinyl H),
7.09e7.19 (m, 10H, ArH), 7.72 (t, J¼8.0 Hz, 2H, ArH), 8.18
(d, J¼8.4 Hz, 2H, ArH), 8.47 (d, J¼7.2 Hz, 2H, ArH). 13C
NMR (CDCl3) d: 40.1 (CH2), 67.2 (C), 124.0 (CH), 126.1
(CH), 126.6 (CH), 127.2 (CH), 127.5 (C), 128.3 (CH), 128.9
(CH), 131.4 (C), 132.9 (C), 134.1 (CH), 134.4 (CH), 137.0
(C), 197.7 (C). EIMS m/z: 428 (Mþ), 410, 392, 352, 337,
312, 311, 293, 283, 265, 252, 221, 211, 210, 205, 183, 165,
155, 127, 117, 115, 91, 77. HRESI-MS calcd for C31H25O2
[Mþ1]þ 429.1854, found 429.1851.
4.2.12. (4E)-1-(5-Chloro-2-hydroxyphenyl)-2-cinnamyl-5-
phenylpent-4-en-1-one (6)
Colorless oil. IR (KBr) n: 3026, 1638 cmꢂ1 1H NMR
.
(CDCl3) d: 2.47e2.54 (m, 2H, CHꢃ2), 2.66e2.73 (m, 2H,
CHꢃ2), 3.64 (quin, J¼6.8 Hz, 1H, CH), 6.11 (dt, J¼7.6,
15.6 Hz, 2H, vinyl H), 6.42 (d, J¼15.6 Hz, 2H, vinyl H),
6.93 (d, J¼8.0 Hz, 1H, ArH), 7.16e7.30 (m, 10H, ArH),
7.37 (dd, J¼2.8, 8.8 Hz, 1H, ArH), 7.75 (d, J¼2.8 Hz, 1H,
ArH), 12.43 (s, 1H, OH). 13C NMR (CDCl3) d: 35.1 (CH2),
46.1 (CH), 119.5 (C), 120.4 (CH), 123.6 (C), 126.1 (CH),
126.1 (CH), 127.3 (CH), 128.5 (CH), 129.0 (CH), 132.9
(CH), 136.3 (CH), 136.9 (C), 161.5 (C), 207.8 (C). EIMS
m/z: 402 (Mþ), 386, 384, 311, 287, 285, 267, 243, 232, 217,
204, 180, 157, 155, 143, 129, 117, 115, 99, 91. Anal. Calcd
for C26H23ClO2: C, 77.51; H, 5.75. Found: C, 77.57; H, 5.79.
4.2.9. 3-Cinnamyl-4-hydroxy-2H-chromen-2-one (3g)
Yellow crystals. Mp 285e286 ꢀC (methanol/hexane). IR
1
(KBr) n: 3220, 1668 cmꢂ1. H NMR (CD3OD) d: 3.48 (dd,
J¼1.6, 6.0 Hz, 2H, CH2), 6.31 (dt, J¼6.0, 16.0 Hz, 1H, vinyl
H), 6.45 (d, J¼16.0 Hz, 1H, vinyl H), 7.10e7.36 (m, 7H,
ArH), 7.57e7.61 (m, 1H, ArH), 7.93e7.96 (m, 1H, ArH).
13C NMR (CD3OD) d: 27.8 (CH2), 104.1 (C), 117.4 (CH),
117.8 (C), 124.4 (CH), 125.2 (CH), 127.1 (CH), 128.0
(CH), 129.3 (CH), 129.5 (CH), 131.8 (CH), 133.0 (CH),
138.9 (C), 153.8 (C), 162.8 (C), 166.1 (C). EIMS m/z: 278
(Mþ), 249, 231, 213, 202, 188, 187, 157, 128, 121, 115, 91,
77. HRESI-MS calcd for C18H15O3 [Mþ1]þ 279.1021, found
279.1021.
4.2.13. 5,5-Dicinnamylpyrimidine-2,4,6(1H,3H,5H)-trione
(4i)
White crystals. Mp 220e221 ꢀC (metꢂha1nol/hexane)
(226e228 ꢀC59). IR (KBr) n: 3447, 1638 cm
.
1H NMR
(CDCl3) d: 2.88 (dd, J¼0.8, 7.6 Hz, 4H, CH2ꢃ2), 6.14 (dt,
J¼7.6, 15.6 Hz, 2H, vinyl H), 6.53 (d, J¼15.6 Hz, 2H, vinyl
H), 7.20e7.38 (m, 10H, ArH), 10.42 (br s, 2H, NHꢃ2). 13C
NMR (CDCl3) d: 42.7 (CH2), 58.0 (C), 123.8 (CH), 127.8

K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
1211
(CH), 129.2 (CH), 130.1 (CH), 136.5 (CH), 138.3 (C), 150.5
(C), 173.2 (C). EIMS m/z: 360 (Mþ), 342, 324, 282, 269,
243, 232, 220, 219, 205, 183, 180, 179, 170, 155, 143, 142,
129, 117, 115, 91, 77. HRESI-MS calcd for C22H21N2O3
[Mþ1]þ 361.1552, found 361.1554.
(CDCl3) d: 2.66e2.75 (m, 4H, CH2ꢃ2), 4.34 (s, 2H, CH2),
6.02 (dt, J¼7.6, 15.6 Hz, 2H, vinyl H), 6.49 (d, J¼15.6 Hz,
2H, vinyl H), 7.20e7.32 (m, 10H, ArH). 13C NMR (CDCl3)
d: 38.3 (CH2), 54.5 (C), 73.2 (CH2), 120.7 (CH), 126.3
(CH), 128.0 (CH), 128.6 (CH), 136.0 (CH), 136.1 (C), 175.9
(C), 210.2 (C). EIMS m/z: 332 (Mþ), 304, 286, 241, 223,
219, 205, 192, 181, 167, 155, 141, 129, 118, 115, 91, 77.
HRESI-MS calcd for C22H21O3 [Mþ1]þ 333.1491, found
333.1494.
4.2.14. 1,5,5-Tricinnamylpyrimidine-2,4,6(1H,3H,5H)-
trione (7)
White crystals. Mp 154e155 ꢀC (chloroform/hexane)
(157e158 ꢀC59). IR (KBr) n: 3422, 1681 cmꢂ1 1H NMR
.
(CDCl3) d: 2.92 (d, J¼7.6 Hz, 4H, CH2ꢃ2), 4.56 (d,
J¼6.8 Hz, 2H, CH2), 5.94 (dt, J¼7.6, 15.6 Hz, 2H, vinyl H),
6.06 (dt, J¼6.8, 15.6 Hz, 1H, vinyl H), 6.47 (d, J¼15.6 Hz,
2H, vinyl H), 6.65 (d, J¼16.0 Hz, 1H, vinyl H), 7.10e7.23
(m, 15H, ArH), 8.82 (s, 1H, NH). 13C NMR (CDCl3) d: 42.0
(CH2), 42.9 (CH2), 57.7 (C), 121.1 (CH), 121.7 (CH), 126.3
(CH), 126.5 (CH), 127.8 (CH), 127.9 (CH), 128.5 (CH),
128.5 (CH), 135.2 (CH), 135.8 (CH), 135.9 (C), 136.1 (C),
149.2 (C), 170.8 (C), 171.1 (C). EIMS m/z: 476 (Mþ), 461,
398, 385, 359, 299, 271, 258, 243, 232, 219, 218, 205, 180,
167, 155, 141, 129, 118, 115, 91. HRESI-MS calcd for
C31H29N2O3 [Mþ1]þ 477.2178, found 477.2180.
4.2.18. 2-(But-2-enyl)cyclohexane-1,3-dione (10)
White crystals. Mp 112e113 ꢀC (chloroform/hexane). IR
1
(KBr) n: 3403, 2942, 1602 cmꢂ1. H NMR (CDCl3) d: 1.67
(dq, J¼1.6, 6.4 Hz, 3H, CH3), 1.96 (quin, J¼6.4 Hz, 2H,
CH2), 2.42 (t, J¼6.0 Hz, 4H, CH2ꢃ2), 3.07 (d, J¼6.4 Hz,
2H, CH2), 5.48 (dtq, J¼1.6, 6.4, 15.2 Hz, 1H, vinyl H), 5.65
(dtq, J¼1.6, 6.4, 15.2 Hz, 1H, vinyl H). 13C NMR (CDCl3)
d: 17.8 (CH3), 20.6 (CH2), 25.1 (CH2), 26.3 (CH2), 113.3
(C), 127.4 (CH), 129.1 (CH), 175.3 (C), 204.6 (C). EIMS
m/z: 166 (Mþ), 151, 149, 137, 123, 110, 96, 91, 79, 77.
HRESI-MS calcd for C10H15O2 [Mþ1]þ 167.1072, found
167.1072.
4.2.15. 1,3,5,5-Tetracinnamylpyrimidine-2,4,6(1H,3H,5H)-
trione (8)
4.2.19. 2-(2-Cyclohexen-1-yl)cyclohexane-1,3-dione (14)
White crystals. Mp 124e126 ꢀC (chloroform/hexane)
White crystals. Mp 119e120 ꢀC (chloroform/hexane). IR
(138e139 ꢀC59). IR (KBr) n: 3385, 2931, 1602 cmꢂ1 1H
.
1
(KBr) n: 3428, 1680 cmꢂ1. H NMR (CDCl3) d: 2.95 (dd,
NMR (CDCl3) d: 1.33e1.42 (m, 1H), 1.59e2.05 (m, 5H),
2.08e2.14 (m, 2H, CH2), 2.34e2.45 (m, 4H, CH2ꢃ2),
3.68e3.73 (m, 1H, CH), 3.82 (ddt, J¼2.4, 2.8, 10.0 Hz, 1H,
vinyl H), 6.11 (ddt, J¼2.4, 3.6, 10.0 Hz, 1H, vinyl H), 7.28
(br s, 1H, OH). 13C NMR (CDCl3) d: 20.6 (CH2), 21.5
(CH2), 25.0 (CH2), 28.2 (CH2), 29.2 (CH2), 30.4 (CH), 36.5
(CH2), 118.2 (C), 130.6 (CH), 132.7 (CH), 172.7 (C), 197.7
(C). EIMS m/z: 192 (Mþ), 177, 164, 136, 121, 109, 91, 79,
77. HRESI-MS calcd for C12H17O2 [Mþ1]þ 193.1228, found
193.1227.
J¼0.8, 7.6 Hz, 4H, CH2ꢃ2), 4.61 (dd, J¼1.2, 6.8 Hz, 4H,
NCH2ꢃ2), 5.90 (dt, J¼7.6, 15.6 Hz, 2H, vinyl H), 6.09 (dt,
J¼6.8, 16.0 Hz, 2H, vinyl H), 6.43 (d, J¼16.0 Hz, 2H, vinyl
H), 6.66 (d, J¼16.0 Hz, 2H, vinyl H), 7.06e7.24 (m, 20H,
ArH). 13C NMR (CDCl3) d: 42.6 (CH2), 43.6 (CH2), 57.7
(C), 121.4 (CH), 122.1 (CH), 126.2 (CH), 126.6 (CH), 127.7
(CH), 127.8 (CH), 128.5 (CH), 128.5 (CH), 135.0 (CH),
135.6 (CH), 136.1 (C), 136.1 (C), 150.0 (C), 170.6 (C).
EIMS m/z: 592 (Mþ), 574, 488, 475, 432, 404, 371, 314,
271, 257, 243, 229, 218, 212, 181, 158, 142, 130, 119, 118,
115, 91. HRESI-MS calcd for C40H37N2O3 [Mþ1]þ
593.2804, found: 593.2801.
4.2.20. 2-(Hex-2-enyl)cyclohexane-1,3-dione (11)
1
Light brown oil. IR (KBr) n: 3447, 2956, 1617 cmꢂ1. H
NMR (CDCl3) d: 0.89 (t, J¼7.2 Hz, 3H, CH3), 1.38 (sextet,
J¼7.2 Hz, 2H, CH2), 1.90e2.03 (m, 4H, CH2ꢃ2), 2.43 (t,
J¼6.4 Hz, 4H, CH2ꢃ2), 3.10 (d, J¼6.8 Hz, 2H, CH2), 5.46
(dtt, J¼1.6, 6.8, 15.2 Hz, 1H, vinyl H), 5.67 (dtt, J¼1.6, 6.8,
15.2 Hz, 1H, vinyl H). 13C NMR (CDCl3) d: 13.6 (CH3),
20.6 (CH2), 22.4 (CH2), 25.2 (CH2), 26.4 (CH2), 34.4 (CH2),
113.1 (C), 128.1 (CH), 133.1 (CH), 179.8 (C), 204.6 (C).
EIMS m/z: 194 (Mþ), 179, 165, 152, 137, 123, 113, 109, 95,
91, 79, 77. HRESI-MS calcd for C12H19O2 [Mþ1]þ
195.1385, found 195.1385.
4.2.16. 5,5-Dicinnamyl-2,2-dimethyl-1,3-dioxane-4,6-dione
(4e)
White crystals. Mp 121e122 ꢀC (chloroform/hexane)
(131 ꢀC59). IR (KBr) n: 2913, 1742, 1695 cmꢂ1 1H NMR
.
(CDCl3) d: 1.51 (s, 6H, CH3ꢃ2), 2.95 (d, J¼8.0 Hz, 4H,
CH2ꢃ2), 6.08 (dt, J¼8.0, 15.6 Hz, 2H, vinyl H), 6.53 (d,
J¼15.6 Hz, 2H, vinyl H), 7.19e7.32 (m, 10H, ArH). 13C
NMR (CDCl3) d: 29.6 (CH3), 41.9 (CH2), 56.1 (C), 105.8
(C), 121.6 (CH), 126.2 (CH), 127.8 (CH), 128.5 (CH), 137.8
(CH), 136.0 (C), 168.5 (C). EIMS m/z: 376 (Mþ), 359, 341,
319, 301, 290, 273, 255, 244, 217, 206, 205, 199, 181, 167,
155, 141, 129, 117, 115, 104, 91, 77. HRESI-MS calcd for
C24H24O4Na [MþNa]þ 399.1572, found 399.1573.
4.2.21. 2-(3-Methylbut-2-enyl)cyclohexane-1,3-dione (12)
White crystals. Mp 125e127 ꢀC (chloroform/hexane). IR
1
(KBr) n: 3421, 2939, 1610 cmꢂ1. H NMR (CDCl3) d: 1.71
(s, 3H, CH3), 1.74 (s, 3H, CH3), 1.95 (quin, J¼6.8 Hz, 2H,
CH2), 2.44 (t, J¼6.8 Hz, 4H, CH2ꢃ2), 3.04 (d, J¼7.2 Hz,
2H, CH2), 5.13e5.17 (m, 1H, vinyl H), 6.10 (br s, 1H, OH).
13C NMR (CDCl3) d: 17.4 (CH3), 20.7 (CH2), 21.1 (CH2),
4.2.17. 3,3-Dicinnamyl-3H,5H-furan-2,4-dione (4f)
White crystals. Mp 99e100 ꢀC (chloroform/hexane)
(99e100 ꢀC59). IR (KBr) n: 2911, 1693 cmꢂ1 1H NMR
.

1212
K.-H. Gan et al. / Tetrahedron 64 (2008) 1204e1212
10. Trost, B. M. Pure Appl. Chem. 1992, 64, 315.
22.1 (CH2), 25.7 (CH3), 114.7 (C), 122.2 (CH), 133.9 (C),
186.5 (C), 204.9 (C). EIMS m/z: 180 (Mþ), 165, 162, 151,
147, 137, 125, 118, 110, 95, 92, 81, 79, 77. HRESI-MS calcd
for C11H17O2 [Mþ1]þ 181.1228, found 181.1227.
11. Backvall, J. E. Pure Appl. Chem. 1992, 64, 429.
12. Giambastiani, G.; Poli, G. J. Org. Chem. 1998, 63, 9608.
13. Uozumi, Y.; Danjo, H.; Hayashi, T. J. Org. Chem. 1999, 64, 3384.
14. Rajesh, S.; Banerji, B.; Iqbal, J. J. Org. Chem. 2002, 67, 7852.
15. Wallner, O. A.; Szabo, K. J. J. Org. Chem. 2003, 68, 2934.
16. Stary, I.; Zajicek, J.; Kocovsky, P. Tetrahedron 1992, 48, 7229.
17. Goux, C.; Massacret, M.; Lhoste, P.; Sinou, D. Organometallics 1995, 14,
4585.
4.2.22. 2-((2E,6E)-3,7-Dimethylocta-2,6-dienyl)cyclo-
hexane-1,3-dione (13)
White crystals. Mp 94e96 ꢀC (chloroform/hexane). IR
18. Deardorff, D. R.; Savin, K. A.; Justman, C. J.; Karanjawala, Z. E.;
Sheppeck, J. E., II; Hager, D. C.; Aydin, N. J. Org. Chem. 1996, 61, 3616.
19. Kadota, J.; Katsuragi, H.; Fukumoto, Y.; Murai, S. Organometallics 2000,
19, 979.
1
(KBr) n: 3430, 2921, 1565 cmꢂ1. H NMR (CDCl3) d: 1.59
(s, 3H, CH3), 1.67 (s, 3H, CH3), 1.74 (s, 3H, CH3), 1.95
(quin, J¼6.4 Hz, 2H, CH2), 2.01e2.13 (m, 4H, CH2ꢃ2),
2.37e2.46 (m, 4H, CH2ꢃ2), 3.07 (d, J¼7.6 Hz, 2H, CH2),
5.02e5.08 (m, 1H, vinyl H), 5.19 (tq, J¼1.2, 7.2 Hz, 1H, vinyl
H). 13C NMR (CDCl3) d: 16.1 (CH3), 17.7 (CH3), 20.6 (CH2),
21.1 (CH2), 25.6 (CH3), 26.3 (CH2), 39.6 (CH2), 39.8 (CH2),
114.1 (C), 122.0 (CH), 123.7 (CH), 132.0 (C), 137.3 (C),
138.8 (C), 205.0 (C). EIMS m/z: 248 (Mþ), 233, 215, 205,
187, 178, 163, 149, 137, 121, 107, 91, 81, 79, 77. HRESI-
MS calcd for C16H25O2 [Mþ1]þ 249.1854, found 249.1853.
20. Kamijo, S.; Jin, T.; Yamamoto, Y. J. Am. Chem. Soc. 2001, 123, 9453.
21. Minami, I.; Yuhara, M.; Tsuji, J. Tetrahedron Lett. 1987, 28, 2737.
22. Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1987, 28, 4837.
23. Ziegler, F. E.; Wester, R. T. Tetrahedron Lett. 1986, 27, 1225.
24. Ziegler, F. E.; Cain, W. T.; Kneisley, A.; Stirchak, E. P.; Wester, R. T.
J. Am. Chem. Soc. 1988, 110, 5442.
25. Imidoesters: Schenck, T. G.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2058.
26. Xanthates: Auburn, P. R.; Wheland, J.; Bosnich, B. J. Chem. Soc., Chem.
Commun. 1986, 146.
27. Nitrogroups: Tamura, R.; Kamimura, A.; Ono, N. Synthesis 1991, 423.
28. Sulfones: Trost, B. M.; Schmuff, N. R.; Miller, M. J. J. Am. Chem. Soc.
1980, 102, 5979.
4.2.23. 3-Hydroxy-2-((E)-1,3-diphenylallyl)cyclohex-2-
enone (9)
29. Trost, B. M. Science 1991, 254, 1471.
30. Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259.
31. Yamamoto, A. Adv. Organomet. Chem. 1992, 34, 111.
32. Lu, X.; Lu, L.; Sun, J. J. Mol. Catal. 1987, 41, 245.
33. Lu, X.; Jiang, X.; Tao, X. J. Organomet. Chem. 1988, 344, 109.
34. Kimura, M.; Horino, Y.; Mukai, R.; Tanaka, S.; Tamaru, Y. J. Am. Chem.
Soc. 2001, 123, 10401.
1
Light yellow oil. IR (KBr) n: 3447, 1581 cmꢂ1. H NMR
(CDCl3) d: 1.81 (quin, J¼6.4 Hz, 2H, CH2), 2.32 (t, J¼
6.4 Hz, 4H, CH2ꢃ2), 5.15 (d, J¼8.4 Hz, 1H, CH), 6.43 (d, J¼
15.6 Hz, 1H, vinyl H), 6.87 (dd, J¼8.4, 15.6 Hz, 1H, vinyl H),
7.11e7.15 (m, 2H, ArH), 7.23 (t, J¼7.6 Hz, 2H, ArH), 7.25 (t,
J¼7.6 Hz, 2H, ArH), 7.28 (d, J¼7.6 Hz, 2H, ArH), 7.36 (d,
J¼7.6 Hz, 2H, ArH). 13C NMR (CDCl3) d: 20.5 (CH2), 33.0
(CH2), 42.2 (CH), 117.5 (C), 125.7 (CH), 126.1 (CH), 127.0
(CH), 127.5 (CH), 127.9 (CH), 128.3 (CH), 130.8 (CH),
130.9 (CH), 137.5 (C), 143.1 (C), 171.3 (C), 187.2 (C).
EIMS m/z: 304 (Mþ), 281, 267, 213, 186, 167, 157, 141,
129, 115, 105, 91, 77. HRESI-MS calcd for C21H21O2
[Mþ1]þ 305.1541, found 305.1539.
35. Horino, Y.; Naito, M.; Kimura, M.; Tanaka, S.; Tamaru, Y. Tetrahedron
Lett. 2001, 42, 3113.
36. Tsay, S.; Lin, L. C.; Furth, P. A.; Shum, C. C.; King, D. B.; Yu, S. F.;
Chen, B.; Hwu, J. R. Synthesis 1993, 329.
37. Stary, I.; Stara, I. G.; Kocovsky, P. Tetrahedron 1994, 50, 529.
38. Takahara, J. P.; Masuyama, Y.; Kurusu, Y. J. Am. Chem. Soc. 1992, 114,
2577.
39. Masuyama, Y.; Kagawa, M.; Kurusu, Y. Chem. Lett. 1995, 1121.
40. Lumin, S.; Falck, J. R.; Capdevila, J.; Karara, A. Tetrahedron Lett. 1992,
33, 2091.
41. Hirai, Y.; Shibuya, K.; Fukuda, Y.; Yokoyama, H.; Yamaguchi, S. Chem.
Lett. 1997, 221.
Acknowledgements
42. Ozawa, F.; Ishiyama, T.; Yamamoto, S.; Kawagishi, S.; Murakami, H.;
Yoshifuji, M. Organometallics 2004, 23, 1698.
43. Muzart, J. Tetrahedron 2005, 61, 4179.
We gratefully acknowledge the National Science Council of
the Republic of China for financial support.
44. Ozawa, F.; Okamoto, H.; Kawagishi, S.; Yamamoto, S.; Minami, T.;
Yoshifuji, M. J. Am. Chem. Soc. 2002, 124, 10968.
45. Patil, N. T.; Yamamoto, Y. Tetrahedron Lett. 2004, 45, 3101.
46. Yang, S.-C.; Tsai, Y.-C. Organometallics 2001, 20, 763.
47. Shue, Y.-J.; Yang, S.-C.; Lai, H.-C. Tetrahedron Lett. 2003, 44, 1481.
48. Yang, S.-C.; Lai, H.-C.; Tsai, Y.-C. Tetrahedron Lett. 2004, 45, 2693.
49. Hsu, Y.-C.; Gan, K.-H.; Yang, S.-C. Chem. Pharm. Bull. 2005, 53, 1266.
50. Organic Synthesis in Water; Grieco, P. A., Ed.; Blackie Academic and
Professional: London, 1998.
References and notes
1. Sakamoto, M.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1996,69, 1065.
2. Tsuji, J. Transition Metal Reagents and Catalysts; Wiley: New York, NY,
2000.
3. Tsutsumi, K.; Yabukami, T.; Fujimoto, K.; Kawase, T.; Morimoto, T.;
Kakiuchi, K. Organometallics 2003, 22, 2996.
51. Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous Media; John Wiley
and Sons: New York, NY, 1997.
4. Goldeski, S. A. Nucleophiles with AllyleMetal Complexes. Comprehen-
sive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon:
New York, NY, 1991; Vol. 4, Chapter 3.3.
52. Lindstrom, U. M. Chem. Rev. 2002, 102, 2751.
¨
53. Manabe, K.; Kobayashi, S. Chem.dEur. J. 2002, 8, 4095.
54. Huang, J.; Zhou, L.; Jiang, H. Angew. Chem., Int. Ed. 2006, 45, 1945.
55. Yang, S.-C.; Hsu, Y.-C.; Gan, K.-H. Tetrahedron 2006, 62, 3949.
56. Kinoshita, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2004, 6, 4085.
57. Xiao, W.-J.; Alper, H. J. Org. Chem. 1998, 63, 7939.
5. Harrington, P. J. Transition Metal Allyl Complexes: Pd, W, Mo-assisted
Nucleophilic Attack. Comprehensive Organometallic Chemistry II; Abel,
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, NY,
1995; Vol. 12, Chapter 8.2.
6. Tsuji, J. Palladium Reagents and Catalysts; Wiley: New York, NY, 1995.
7. Trost, B. M. Angew. Chem., Int. Ed. Engl. 1989, 28, 1173.
8. Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38.
9. Tsuji, J. Synthesis 1990, 739.
58. Amatore, C.;Jutand, A.;Meyer, G.; Mottier, L. Chem.dEur. J. 1999, 5, 466.
59. Prat, M.; Moreno-Manas, M.; Ribas, J. Tetrahedron 1988, 44, 7205.
60. Suzuki, K.; Sekiya, M. Chem. Pharm. Bull. 1971, 19, 1540.
61. Sigismondi, S.; Sinou, D. J. Mol. Catal. A 1997, 116, 289.