Triethylborane as an efficient promoter for palladium-catalyzed allylation of active methylene compounds with allyl alcohols

Article abstract of DOI:10.1016/S0040-4020(03)01234-1

Without prior activation of allyl alcohols, allylation of a variety of active methylene compounds with allyl alcohols proceeds smoothly at rt-50°C in the presence of catalytic amounts of Pd(OAc)₂ (1-10mol%), Et ₃B (30-240mol%), a phosphine ligand (1-20mol%), and a base (0 to 50-60mol%).

Full text of DOI:10.1016/S0040-4020(03)01234-1

Tetrahedron 59 (2003) 7767–7777
Triethylborane as an efficient promoter for palladium-catalyzed
allylation of active methylene compounds with allyl alcohols
*
Masanari Kimura, Ryutaro Mukai, Naoko Tanigawa, Shuji Tanaka and Yoshinao Tamaru
Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, 1-14 Bunkyo, Nagasaki 852-8521, Japan
Received 9 July 2003; accepted 28 July 2003
Abstract—Without prior activation of allyl alcohols, allylation of a variety of active methylene compounds with allyl alcohols proceeds
smoothly at rt–508C in the presence of catalytic amounts of Pd(OAc) (1–10 mol%), Et B (30–240 mol%), a phosphine ligand
1–20 mol%), and a base (0 to 50–60 mol%).
q 2003 Elsevier Ltd. All rights reserved.
2
3
(
1
. Introduction
Recently we have demonstrated that a sub-catalytic amount
of triethylborane (Et B) nicely promotes the palladium-
3
1
3a
Palladium-catalyzed allylation of active methylene com-
pounds is a well-established, efficient method for C–C bond
formation. In most cases, carboxylic acid esters, carbon-
ates, phosphates, and related compounds of allyl alcohols
have been utilized as substrates. Apparently the direct use of
allyl alcohols as substrates is more desirable; however, the
poor capability of the hydroxyl group as a leaving group has
catalyzed allylations of amines, active methylene com-
1
3b
pounds (pK ¼5–13),
o-hydroxypropiophenones (a-car-
13c
and even aliphatic aldehydes
a
1
2
bon of the ketones),
3
1
14
(pK ¼ca. 16) under mild reaction conditions (room
a
temperature–508C). In the presence of a stoichiometric
amount of Et B, on the other hand, allyl alcohols
3
dramatically change the reactivity and undergo nucleophilic
15
allylation of aromatic aldehydes (umpolung).
4
limited their use.
5
In 1970, Atkins et al. reported that allyl alcohols
themselves reacted with acetylacetone (pK ¼9) to give 3-
Allylation of malonates with allyl alcohols using a stoichio-
1
6
metric amount of triphenylborane (Ph B) has been reported.
3
a
allylpentane-2,4-dione in good yield when heated at 858C in
the presence of catalytic amounts of Pd(acac)2 [acac¼
This method seems to be similar to ours regarding the reagents
used. However, these two are essentially different from a
mechanistic point of view. Furthermore, in a practical sense,
the method using Ph B seems not to be very attractive, since it
3
requires Ph B (110 mol%) and n-butyllithium (250 mol%)
3
6
acetylacetonato] and PPh . Later, Bergbreiter et al. and
3
7
Chauvin et al. revealed that even less acidic b-ketoesters
(
pK ¼ca. 11) and malonates (pK ¼ca. 13) also underwent
a
a
palladium-catalyzed allylation with allyl alcohols, though
under rather harsh conditions (heating at around 1008C).
Meanwhile, there have been developed several methods that
enable the allylation to proceed under milder conditions
and heating at 658C in THF. Detrimentally, the yields in
general are modest.
This paper is a full account of our preliminary commu-
1
3b
(room temperature-refluxing THF), where allyl alcohols are
in situ activated through transformation into the esters of
inorganic acids, such as As O , B O , and CO . The
2
effect of Ti(O–i-Pr) as an additive was also noted.
4
break through has been brought about by Ozawa et al.,
who have succeeded in allylation of amines, malonates, and
b-ketoesters at 508C with allyl alcohols using a sp -
hybridized bidentate phosphine–palladium complex in the
presence of pyridine.
nication and discloses results of a full range of combination
of reaction partners: active methylene compounds and allyl
alcohols. Only relevant portions are cited from the communi-
8
9
10
3
2
3
2
1
1
A
cation. The catalytic cycles and the catalytic roles that Et B
3
1
2
0
and an Pd species play are also discussed in detail.
2
2. Results and discussion
1
3b
In a previous communication, wehavedisclosedthathighly
acidiccarbo-nucleophiles, suchasMeldrum’sacid(pK ¼5.2),
a
Keywords: active methylene compounds; allyl alcohols; allylation;
catalytic reaction; palladium; triethylborane.
react with a variety of allyl alcohols to provide diallylation
products in 70–90% isolated yields, where Et B greatly
accelerate the reaction. Less acidic carbo-nucleophiles, such
*
Corresponding author. Tel./fax: þ81-95-847-9008;
3
e-mail: tamaru@net.nagaski-u.ac.jp
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)01234-1

7768
M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
Scheme 1. Pd-catalyzed allylation of diethyl malonate with 2-cyclohexenol.
as malonates (pK ¼ca. 13), required both Et B and a base
Table 1 reveals that the catalytic system shows quite
satisfactory results, giving rise to expected monoallylation
products (2) for active methine compounds and diallylation
products (1) for active methylene compounds in good to
excellent yields. The following points may be worth
mentioning. First, the least acidic ethyl benzenesulfonyl-
acetate exclusively provided a monoallylation product 2a,
even in the presence of an excess amount of allyl alcohol
a
3
(
NaH) for the allylation to proceed at a reasonable rate at
room temperature (run 1, Scheme 1). In the absence of the
base (run 3), no reaction took place even under energetic
conditions: an elevated temperature and a long period of the
reaction time. In the absence of Et B (run 2), on the other
3
hand, the allylation proceeded slowly at 508C, yielding an
expected product, albeit in low yield.
(run 1). No diallylation product was produced in any trace
We examined a scope of the catalytic system, Et B/a
3
amount. Retardation of the second allylation may be
attributed to the low acidity and/or steric hindrance
associated with the primary product 2a. Second, as was
noted, highly acidic nucleophiles, such as 2-formylcyclo-
hexanone (run 14) and Meldrum’s acid (run 16), do not
necessitate any base and the reactions are completed within
a few hours at room temperature. Finally, and most
remarkably, acetylacetone (AA) and 2-acetylcyclohexanone
(AC) are exceptionally unreactive, yielding expected
products, albeit in poor yields (runs 9–12). Despite close
structural similarity, AC and 2-acetylcyclopentanone (run
13) show a distinctive difference in reactivity.
base/Pd(OAc) /PPh , for a wide range of active methylene
2
3
and methine compounds (pK ¼5–14) using two typical
a
allyl alcohols: 2-propen-1-ol (allyl alcohol) and trans-3-
phenyl-2-propen-1-ol (trans-cinnamyl alcohol). The results
are summarized in Table 1. Table 2 also lists the results of
allylation of a-acetyl-g-butyrolactone examined for the
purpose of demonstrating applicability to a wide structural
variety of primary and secondary allyl alcohols. In Tables 1
and 2, the relative amounts of each component of the
catalytic system were fixed as shown in equation (1), where
as a precaution for carbo-nucleophiles and allyl alcohols of
1
3b
low reactivity, the amount of Et B was doubled as compared
3
2
3
with that in Scheme 1. For active methylene compounds (di-
allylation), 240 mol% of an allylic alcohol and 110 mol% of
a base were applied (conditions A–C, footnote a, Table 1).
For active methine compounds, 110 mol% of an allylic
alcohol and 60 mol% of a base were used (conditions D–F).
Et B is stable toward hydrolysis by water and alcohols,
3
while it undergoes hydrolysis when exposed to some weakly
acidic compounds of chelation ability (e.g. 2-hydroxypyr-
idine, AA, AC) and forms cyclic diethylboric acid esters
2
4
24
(e.g. 5a and 5b in Scheme 2). According to the literature,
Scheme 2. Pd-Catalyzed allylation of isolated diethylborates 5 with allyl alcohol.

M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
7769
Table 1. Palladium-catalyzed allylation of active methylene and methine compounds using allyl alcohol and cinnamyl alcohol in the presence of triethylborane
Run
Active methylene compounds
pK
a
R¼H
R¼Ph
a
a
Temp (8C), time (h)
% yield isolated
Temp (8C), time (h)
% yield isolated
1
1
1
7
1
2
3
PhSO
CH (CO
MeCOCH
2
CH
Et)
CO
2
CO
2
Et
14
13
11
A: rt, 5
A: rt, 2
A: 50, 1
2a: 74
1a: 70
1b: 98
–
–
8
8
b
2
2
2
–
B: 50, 1
–
1c: 73
2
2
Me
4
5
6
7
–
D: rt, 2
2b: 93
2b: 95
2d: 88
2f: 92
D: rt, 1.5
E: rt, 1
2c: 93
2c: 95
2e:89
E: rt, 1
19
12.0
D: rt, 1
D: rt, 1.5
D: rt, 1.5
D: rt, 3
–
2g: 85
1
8
8
9
CH
CH
CH
2
2
2
(CN)
(COMe)
(COMe)
2
11
9
A: rt, 2
–
–
1d: 87
–
–
–
–
1
8
2
(AA)
(AA)
A: 50, 24
B: 50, 48
1e: 7
1e: , 5
10
2
2
0
1
1
9.9
E: rt, 2
2h: 24
D: rt, 2
E: rt, 3
E: rt, 2
2i: 32
2i: 16
2k: 84
1
2
3
–
–
21
8.1
1
E: rt, 1
2j: 85
19
19
22
14
15
16
7.1
5.8
5.2
–
–
F: rt, 1
–
2l: 85
–
O
2
NCH
2
CO
2
Et
A: rt, 2
C: rt, 2.5
1f: 64
1g: 78
C: rt, 2
1h: 85
a
Conditions A: an active methylene compound (1.0 mmol), an allylic alcohol (2.4 mmol), and KHMDS (potassium bis(trimethylsilyl)amide, 1.1 mmol);
Conditions B: under the conditions A using Et N (1.1 mmol) in place of KHMDS; Conditions C: under the conditions A without the base, Conditions D: an
3
active methine compound (1.0 mmol), an allylic alcohol (1.1 mmol), and KHMDS (0.6 mmol); Conditions E: under the conditions D using Et
in place of KHMDS; Conditions F: under the conditions D without the base.
NaH in place of KHMDS.
3
N (0.6 mmol)
b
acetylacetone (AA), for example, reacts with Et B in
3
sis may be accelerated by a base, being present in the
reaction mixture. The progress of reaction could be
monitored conveniently by means of TLC (hexane/
refluxing THF (3 h) and provides air- and moisture-stable
diethylboronium acetylacetonate in 84% isolated yield after
distillation. Under our allylation conditions, AA, AC, 2-
acetylcyclopentanone, and 2-formylcyclohexanone, all
readily reacted with Et B at room temperature and provided
3
corresponding cyclic diethylboric acid esters. The hydroly-
EtOAc¼4:1 v/v, R
5 ¼ca. 0.7; R
¼
f(diethylborates
)
f(b-dicarbonyls)
ca. 0.6, R
the latter two were so reactive that they faded away
completely at room temperature within 1–2 h (runs 13 and
¼ca. 0.4). Among these diethylborates,
f(allylation products)

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M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
Table 2. Et
3
B-Promoted, Pd-catalyzed allylation of a-acetyl-g-butyrolactone with a variety of allyl alcohols
Run
Allyl alcohol
Temp (8C), time (h)
% isolated of products
1
rt, 3
b
7
7
2 (2.5:1)
3 (2.5:1)
2
3
rt, 2
rt, 1
b
4
5
6
rt, 1
rt, 1
rt, 2
7
rt, 12 then 50, 10
a
8
9
rt, 40
rt, 5
3 2 3
Reaction conditions: a-acetyl-g-butyrolactone (1.0 mmol), an allylic alcohol (1.1 mmol), Et B (2.4 mmol), Pd(OAc) (10 mol%), PPh (20 mol%), KHMDS
(
2
0.6 mmol) in THF (5 mL) under N .
a
Dppf (20 mol%) in place of PPh
Diastereomeric mixture (1.4:1).
Diastereomeric mixture (1.7:1).
3
.
b
c
1
4). The former two, on the other hand, were very reluctant
From a mechanistic point of view, the results associated
with equation (b) seem to be particularly important, which
indicate that 5b is capable of activating an allylic alcohol as
a precursor of a p-allylpalladium species, and also 5b is
reactive enough toward the thus-formed p-allylpalladium
species (vide infra).
and either remained at a final stage of reactions (runs 11 and
2) or faded away very slowly (runs 9 and 10), probably
owing to decomposition.
1
These results suggest that the formation of boric acid
esters might not be a main cause of reluctant reactivity
associated with AA and AC. In fact, the reactions of allyl
alcohol with boric acid esters of AC (5a) and 2-
acetylcyclopentanone (5b), prepared independently,
showed an apparent difference in reactivity (Eq. (a) and
Table 2 summarizes the results for the reactions of a-acetyl-
g-butyrolactone with a wide structural variety of primary
and secondary allyl alcohols. The yield and regioselectivity
1
3b
are similar to those reported for diethyl benzylmalonate;
(
b), Scheme 2). Even under forcing conditions, 5a did not
a- and g-methylallyl alcohols showed the identical product
distribution, giving rise to a mixture of straight and
branched chain isomers in a ratio of 2.5:1 (runs 1 and 2).
a-Phenylallyl alcohol (run 3) and a-vinylallyl alcohol (run
6), on the other hand, provided straight chain products
react with allyl alcohol, while 5b did react with the same
alcohol under usual conditions, though in a somewhat lower
yield and at a lower reaction rate compared with the in situ
reaction (run 13, Table 1).

M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
7771
1
3b
exclusively. This is presumably due to conjugation
stabilization of the double bonds that the straight chain
isomers are engaged in.
sub-catalytic level, i.e. a smaller amount than that of
active methylene compounds. It should be noted that under
such conditions, Et B is subject to hydrolysis (vide infra)
3
and is completely converted to a boric acid ester 5. This
apparently indicates that under such conditions, allyl
alcohol is activated not by Et B, but some other species
3
Under usual conditions, g,g-dimethylallyl alcohol was
exceptionally unreactive (run 7). Even under energetic
conditions, the expected product were obtained in a low
yield and with a low regioselectivity. Interestingly, the yield
and the regioselectivity were remarkably improved by the
like 5 (cf. Eq. (c), Scheme 2. See also Section 3).
In order to estimate minimum loadings of Pd(OAc)2,
phosphine ligands, and Et B, the allylation of a-acetyl-g-
0
use of dppf [1,1 -bis(diphenylphosphino)ferrocene] in place
of PPh (run 8).
3
butyrolactone and AC was examined (Scheme 3). Runs 1–3
indicate that the amount of Et B can be reduced to 30 mol%
3
3
Encouraged with this, we re-examined the hitherto unsuc-
cessful allylation, the allylation of AA and AC (runs 9–12,
Table 1) with bidentate phosphine ligands varying the
degrees of bite angle. The results in runs 1–5 (Table 3)
clearly indicate that the allylation of AA sharply depends on
the kind of phosphine ligands and that the bidentate ligands
with bite angle larger than 1008, e.g. dppb and dppf,
remarkably increase the yield. Furthermore, dppf greatly
accelerates the reaction (run 5, Table 3).
in a combination of Pd(OAc) and PPh , 10 and 20 mol%
2
3
each. Comparison of runs 4 and 5 reveals that the catalyst
composition of Et B (30 mol%)/Pd(OAc) (5 mol%)/PPh
3
3
2
(10 mol%) almost reaches the lowest limit of loading. Runs
6–8 indicate that a combination of Pd(OAc) and dppf, in
2
5 mol% each, is almost the lowest limit for successful
reaction. Loading the lower amounts of these reagents, e.g.
3 mol% each (run 8), apparently causes a significant
decrease in the yield.
2
5
The product 4 was not detected by careful TLC monitoring
during a whole course of reaction (runs 2–5, Table 3).
Accordingly, 4 is regarded to be formed during a work-up
under alkaline conditions (NaOH, H O ), presumably via
Almost at a final stage of the present study, we found by
chance that a particular combination Pd(OAc) and BINAP
2
0
0
[2,2 -bis(diphenylphosphino)-1,1 -binaphthyl] in 1:1 ratio
was marvelous; to our pleasant surprise, the combination of
these, 3 mol% each, showed the best record and gave rise to
2h in 94% isolated yield (run 10, Scheme 3). This
observation indicates that allylation of AC sharply depends
on not only a bite angle, but also a basicity of bidentate
2
2
de-acylation through the retro-Claisen condensation of 1e:
2
addition of OH to one of the acetyl groups of 1e followed
by a bond cleavage giving rise to a mixture of acetic acid
and an enolate of 4.
2
5
ligands. The bite angle of BINAP is 878. Relied on a
guide-line deduced from Table 3 (vide supra), regrettably,
we have ignored this ligand through this study.
A remarkable improvement in yields with dppf was also
confirmed for the allylation of AC (runs 6–8, Table 3). In
accord with this, dppf turned out to promote the allylation of
5
a with allyl alcohol (Eq. (c), Scheme 2). The causes of
In order to assess the efficiency of BINAP as a ligand for the
0
dramatic differences observed for the two pairs of reactions,
equations (a) and (c), i.e. a ligand effect, and equations (a)
and (b), i.e. a ring size effect, are not clear at present.
present Et B- and Pd -catalyzed allylation, we re-examined
3
the reaction of AC with cinnamyl alcohol (runs 11 and 12 in
Table 1) as well as the reaction of a-acetyl-g-butyrolactone
with a-vinylallyl alcohol (run 6 in Table 2), specific
combinations of reactants having been so far unsatisfactory.
InScheme4aresummarizedtheresults.Inthesameschemeare
Run 8 in Table 3 indicates that, although we have so far used
an excess amount of Et B, the amount can be reduced to a
3
Table 3. Effects of ligands and bases on allylation of acetylacetone (AA) and 2-acetylcyclohexanone (AC)
Run
Nu
Ligand (mol%)
Bite angle (8)
Base
Et
3
B (equiv.)
Temp (8C), Time (h)
% isolated yield
1
2
3
4
5
6
7
8
AA
AA
AA
AA
AA
AC
AC
AC
PPh
dppe (20)
dppp (20)
dppb (20)
dppf (20)
3
(20)
Et
Et
Et
Et
Et
3
3
3
3
3
N
N
N
N
N
2.4
2.4
2.4
2.4
2.4
2.4
2.4
0.6
50/48
50/24
50/24
50/20
50/2
rt/2
50/1
50/1
1e: trace
1e: 36
1e: 32
1e: 65
1e: 78
2h: 32
2h: 80
2h: 83
a
85
95
99
106
4: 13
4: 14
4: 22
4: 9
b
c
PPh (20)
dppf (20)
dppf (20)
3
KHMDS
KHMDS
KHMDS
2
.4 mmol of an allylic alcohol for AA and 1.1 mmol for AC.
a
1
1
1
,2-Bis(diphenylphosphino)ethane.
,3-Bis(diphenylphosphino)propane.
,4-Bis(diphenylphosphino)butane.
b
c

7772
M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
2 3
Scheme 3. Reactions using reduced amounts of Pd(OAc) , phosphines, and Et B.
also listed the results examined with dppf as a reference ligand
under the identical reaction conditions. From these results, it
maybe concludedthat BINAP is much superior to dppf and any
other phosphine ligands examined so far in this study.
3. Mechanistic consideration
Scheme 5 illustrates the most probable catalytic cycles with
0
respect to an Pd species and Et B. Catalytic cycle A might
3
Scheme 4. Remarkable improvement in yields by the use of BINAP as a ligand.

M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
7773
0
Scheme 5. Plausible catalytic cycles with respect to Pd and Et
3
B and boric acid derivatives.
be applied to reactions that do not involve hydrolysis of
Et B, where an essential role of Et B is to activate an allyl
alcohol by coordination to the hydroxy group, through
which oxidative addition of Pd into the C–O bond might
proceed with ease. Use of a base is essential to activate
weakly acidic nucleophiles as their conjugate bases.
alcohol through an equilibrium shown in equation (d)
(Scheme 5). As was demonstrated by equations (b) and (c)
in Scheme 2, cyclic diethylborates 5 might serve as potent
nucleophiles toward a p-allylpalladium species (II or III)
under certain conditions.
3
3
0
In Schemes B and C, the participation of a base is not
referred to explicitly. Indeed, allylation of some highly
acidic nucleophiles, e.g. 2-formylcyclohexanone (run 14,
Table 1) and Meldrum’s acid (run 16, Table 1) proceed
smoothly even in the absence of a base. For less acidic
nucleophiles, however, a base might help them react with
Et B and/or Et BOH to form reactive cyclic diethyl borates
According to this scheme, one molecule of water is
generated for every one catalytic cycle, and in principle,
Et B and a base (NaOH from NaH, KOH from KHMDS) as
well as an Pd species remain intact and the reaction should
be catalytic with respect to all these reagents. In practice,
3
0
however, Et B may be damaged partially by air and some
3
3
2
other side reactions and the base may be neutralized by the
thus-formed boric acids.
5 (vide supra).
In all catalytic cycles A–C, one molecule of water is
generated for every catalytic cycle, i.e. the present Et B–Pd
Catalytic cycles B and C might be applied to reactions that
involve hydrolysis of Et B to 5. The cycles B and C differ in
that in cycle B, diethylhydroxyborane (Et BOH) serves as
2
3
catalyzed allylation may be regarded as the condensation
þ
3
reaction between active methylene compounds (H donors)
and allyl alcohols (OH2 donors).
either a Lewis acid or a Brønsted acid to activate an allylic
alcohol, while in cycle C, it serves as an acid portion of an
9
allyl ester IV. Catalytic cycle B illustrates only the case
that Et BOH plays as a Lewis acid; the case that Et BOH as
2
2
4. Conclusion
a Brønsted acid might be accounted for in a similar way. In
catalytic cycles B and C, not only Et BOH, but also an
intermediate 5a might also contribute to activate an allylic
2
In this paper, we have disclosed that without prior activation
of allyl alcohols, allylation of a variety of combination of

7774
M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
3
4
active methylene compounds (pK 5–14) and allyl alcohols
a
ethyl 1-allyl-2-oxocyclohexanecarboxylate (2b), ethyl 1-
5
3
proceeds smoothly at rt–508C in the presence of Pd(OAc)2
(
allyl-2-oxocyclopentanecarboxylate (2d), ethyl 1-trans-
3
6
1–10 mol%), Et B (30–240 mol%), a phosphine ligand
3
cinnamyl-2-oxocyclopentanecarboxylate (2e), a-acetyl-
3
7
(
as a unique co-catalyst and plays many roles to promote the
1–20 mol%), and a base (0 to 50–60 mol%). Et B serves
a-allyl-g-butyrolactone (2f), a-acetyl-a-trans-cinnamyl-
3
3
7
g-butyrolactone (2g), 2-acetyl-2-allylcyclohexanone
3
(2h), 5-phenyl-3-trans-cinnamylhex-5-en-2-one (4).
8
39
reaction depending on the kind of b-dicarbonyl compounds.
(1) The primary role is to activate an allylic alcohol by
coordinating to the hydroxy group, through which oxidative
5.2. General procedure for palladium-catalyzed
allylation of active methylene compounds
0
addition of an Pd species to the C–O bond takes place
easily at room temperature–508C. (2) Neither being
verified, nor pursued in detail, Et B might be responsible
3
for reduction of Pd(OAc) to an Pd species, which is
2
(1) Allylation of 2-acetylcyclohexanone (run 10, Scheme 3):
Into a two-necked flask equipped with a reflux condenser at
the top of which was attached a N balloon were placed
0
maintained active as long as organoborane species that
possess B–Et bonds of reducing ability persist. (3) Et B
2
Pd(OAc) (6.75 mg, 0.03 mmol) and rac-BINAP (18.6 mg,
2
3
activates some b-dicarbonyl compounds, such as acetyl-
acetone and 2-acetylcyclohexanone, by forming cyclic
diethylborates 5, which in the presence of an appropriate
bidentate ligand, such as dppf and BINAP, not only
serves as a nucleophile, but also as a promoter of oxidative
0.03 mmol). The flask was purged with N and then THF
2
(5 mL), 2-acetylcyclohexanone (140.1 mg, 1.0 mmol), allyl
alcohol (61.8 mg, 1.1 mmol), KHMDS (1.2 mL, 0.5 M in
toluene), and Et B (0.60 mL, 1.0 M in hexane) were added
3
successively at room temperature via syringe. The mixture
was stirred and heated at 508C for 2 h, during which the
mixture was colored red. The mixture was diluted with
EtOAc (20 mL) and washed with 2N HCl, sat. NaHCO3,
0
addition of an Pd species to the C–O bond of an allylic
alcohol.
and then brine. The extract was dried (MgSO ) and
4
5
. Experimental
concentrated in vacuo and the residual oil was subjected
to column chromatography over silica gel (gradient: hexane
to hexane/EtOAc¼16/1, v/v) to give 2-acetyl-2-allylcyclo-
Reactions employed oven-dried glassware unless otherwise
noted. Thin layer chromatography (TLC) employed glass
.25 mm silica gel plates with UV indicator (Merck, Silica
hexanone (2g, 169.5 mg, R
¼0.5, hexane/EtOAc¼4/1) in
f
0
94% yield.
gel 60F254). Flash chromatography columns were packed
with 230–400 mesh silica gel as a slurry in hexane. Gradient
flash chromatography was conducted eluting with a
continuous gradient from hexane to the indicated solvent.
Proton and carbon NMR data were obtained with a JEOL-
GX400 with tetramethylsilane as an internal standard.
Chemical shift values were given in ppm downfield from
the internal standard. Infrared spectra were recorded with a
JASCO A-100 FT-IR spectrophotometer. High resolution
mass spectra (HRMS) were measured with a JEOL JMS-
DX303. Combustion analyses were performed by the
Instrumental Analysis Center of Nagasaki University.
Analysis agreed with the calculated values within ^0.4 %.
(2) Cinnamylation of acetylacetone (run 5, Table 3): Into
a solution of Pd(OAc) (12.0 mg, 0.1 mmol) and dppf
(110.8 mg, 0.2 mmol) in THF (5 mL) were successively
introduced cinnamyl alcohol (322.0 mg, 2.4 mmol),
2
acetylacetone (100.1 mg, 1.0 mmol), Et
0.6 mmol), and Et B (2.4 mL, 1 M in hexane). The
mixture was heated at 508C for 2 h under N . Into the
mixture were added 6N NaOH (1 mL) and 30% H
N (60 mg,
3
3
2
O
2 2
(2 mL) and the mixture was heated at 508C for 2 h. After
dilution with EtOAc (20 mL), the mixture was worked up
in an usual way similar to the procedure (1). 3,3-Bis-
(trans-cinnamyl)pentane-2,4-dione (1e, 259.5 mg, 78%
isolated yield; R ¼0.40, hexane/EtOAc¼4/1, v/v) and 5-
f
5
.1. Solvents and reagents
phenyl-3-(trans-cinnamyl)hex-5-en-2-one (4, 26.3 mg,
% isolated yield, R ¼0.55) were isolated as spectro-
9
scopically homogeneous materials.
f
THF (tetrahydrofuran) was distilled from sodium/benzo-
phenone ketyl under N prior to use. Triethylamine was
2
distilled from CaH2 under N . KHMDS (potassium
2
bis(trimethylsilyl)amide, 0.5 M in toluene, Aldrich), Et B
3
5.3. New compounds appeared in Table 1
5.3.1. Methyl 2,2-di(trans-cinnamyl)acetoacetate (1c). IR
(
1.0 M in hexane, Kanto Kagaku), allyl alcohols, active
2
1
methylene compounds, phosphine ligands, and Pd(OAc)2
were used as received from commercial sources. 2-
Formylcyclohexanone was prepared according to the
(neat) 1745 (s), 1712 (s), 1198 (m), 1107 (s), 968 (s) cm
;
1
H NMR (400 MHz, CDCl3) d 2.19 (s, 3H), 2.78 (br dd,
J¼7.5, 14.5 Hz, 2H), 2.84 (br dd, J¼7.5, 14.5 Hz, 2H), 3.75
(s, 3H), 6.00 (dt, J¼15.6, 7.5 Hz, 2H), 6.45 (br d, J¼
2
6
literature procedure.
15.6 Hz, 2H), 7.19 – 7.33 (m, 10H). Anal. Calcd for
The structures of trivial allylation products were determined
by spectral means (IR, HRMS) especially by comparison of
C H O : C, 79.28; H, 6.94. Found: C, 78.91; H, 7.00.
23 24 3
1
the H NMR data with those of authentic samples: diethyl
2
5.3.2. 2-trans-Cinnamyl-2-ethoxycarbonylcyclohexanone
(2c). IR (neat) 1741 (s), 1714 (s), 1647 (s), 1616 (s), 1450
(s), 1404 (s), 1369 (s), 1298 (s), 1259 (s), 1218 (s), 1193 (s),
7
28
diallylmalonate (1a), methyl diallylacetoacetate (1b),
2
diallylmalononitrile (1d), 3,3-bis-(trans-cinnamyl)pen-
9
3
0
21
1
tane-2,4-dione (1e),
ethyl 2,2-diallyl-2-nitroacetate
5,5-diallyl-2,2-dimethyl-1,3-dioxane-4,6-dione
1g), 5,5-bis-cinnamyl-2,2-dimethyl-1,3-dioxane-4,6-
1176 (s), 1130 (s), 1082 (s), 1060 (s) cm ; H NMR
(400 MHz, CDCl
3
1
(
(
1f),
3
) d 1.21 (t, J¼7.6 Hz, 3H), 1.48–1.79 (m,
3
2
4H), 2.02 (m, 1H), 2.46–2.55 (m, 3H), 2.49 (dd, J¼13.7,
7.0 Hz, 1H), 2.74 (br dd, J¼13.7, 7.0 Hz, 1H), 4.17 (q,
3
2
33
dione (1h), ethyl 2-benzenesulfonyl-4-pentenoate (2a),

M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
7775
J¼7.6 Hz, 2H), 6.17 (ddd, J¼15.5, 7.7, 7.0 Hz, 1H), 6.37 (d,
J¼15.5 Hz, 1H), 7.17–7.33 (m, 5H); HRMS, calcd for
C H O : 286.1569. Found m/z (relative intensity):
J¼7.0 Hz, 1H), 4.06 – 4.25 (m, 2H), 5.20 (dm, J¼10.6 Hz,
1H), 5.22 (d, J¼16.9 Hz, 1H), 5.76 (ddm, J¼10.6, 16.9 Hz,
1
1H). H NMR (400 MHz, CDCl , minor isomer) d 1.11 (d,
3
1
8
22
3
þ
2
86.1571 (M , 100).
J¼7.0 Hz, 3H), 2.16 (m, 1H), 2.40 (s, 3H), 2.85 (m, 1H),
3
.26 (qm, J¼7.0 Hz, 1H), 4.06 – 4.25 (m, 2H), 5.07 (br d,
5
.3.3. 2-trans-Cinnamyl-2-acetylcyclohexanone (2i). IR
J¼10.6 Hz, 1H), 5.13 (br d, J¼16.9 Hz, 1H), 5.47 (ddm,
J¼10.6, 16.9 Hz, 1H).
(
neat) 1697 (s), 1598 (m), 1433 (s), 1359 (s), 970 (s) cm21
;
H NMR (400 MHz, CDCl ) d 1.62 (m, 4H), 2.13 (s, 3H),
1
3
2
.26–2.34 (m, 2H), 2.50 (br dd, J¼14.3, 7.7 Hz, 2H), 2.60
5.4.3. a-Acetyl-a-(b-methylallyl)-g-butyrolactone (3b).
IR (neat) 1768 (s), 1712 (s), 1375 (s), 1359 (s), 1159 (s),
(
(
J¼14.3, 7.5 Hz, 1H), 2.72 (dd, J¼14.3, 7.5 Hz, 1H), 6.02
1029 (s) cm2 ; H NMR (400 MHz, CDCl ) d?1.70 (s, 3H),
1 1
dt, J¼15.8, 7.5 Hz, 1H), 6.39 (d, J¼15.8 Hz, 1H), 7.18–
3
7
m/z (relative intensity): 256.1466 (M , 100).
.33 (m, 5H); HRMS, calcd for C H O : 256.1463. Found
2.14 (dt, J¼13.2, 9.0 Hz, 1H), 2.34 (s, 3H), 2.60 (d,
J¼15.6 Hz, 1H), 2.91 (d, J¼15.6 Hz, 1H), 3.00 (ddd,
J¼13.2, 7.1, 2.9 Hz, 1H), 4.19 (dt, J¼7.1, 9.0 Hz, 1H), 4.31
(dt, J¼2.9, 9.0 Hz, 1H), 4.69 (s, 1H), 4.89 (s, 1H); HRMS,
calcd for C H O : 182.0943. Found m/z (relative inten-
1
7
20 2
þ
5
.3.4. 2-Acetyl-2-allylcyclopentanone (2j). IR (neat) 1737
2
1 1
(
s), 1703 (s), 1355 (s), 1130 (s), 921 (s) cm ; H NMR
1
0
14
3
þ
(
1
1
400 MHz, CDCl ) d 1.76 (dt, J¼12.8, 7.8 Hz, 1H), 1.82–
sity): 182.0957 (M , 3.9), 140.0825 (100).
3
.92 (m, 3H), 2.21 (s, 3H), 2.31 (ddd, J¼8.4, 5.8, 1.3 Hz,
H), 2.42 (ddt, J¼14.4, 7.4, 1.3 Hz, 1H), 2.64 (br dt,
5.4.4. a-Acetyl-a-(b-phenylallyl)-g-butyrolactone (3c).
IR (neat) 3057 (s), 1766 (s), 1712 (m), 1629 (s), 1494 (s),
1444 (s), 1357 (s), 1218 (s), 1159 (s), 1028 (s), 958 (s), 912
J¼12.8, 5.8 Hz, 1H), 2.69 (ddt, J¼14.4, 7.4, 1.3 Hz, 1H),
5
.10 (tq, J¼10.3, 1.3 Hz, 1H), 5.11 (br d, J¼16.9 Hz, 1H),
.57 (ddt, J¼16.9, 10.3, 7.4 Hz, 1H). Anal. Calcd for
(s) cm2 ; H NMR (400 MHz, CDCl ) d 1.19 (dt, J¼13.2,
1 1
5
C H O : C, 72.26; H, 8.49. Found: C, 72.34; H, 8.44.
3
8.8 Hz, 1H), 2.28 (s, 3H), 2.76 (ddd, J¼13.2, 7.3, 3.1 Hz,
1
0 14 2
1
H), 3.05 (dd, J¼15.4, 1.1 Hz, 1H), 3.39 (dd, J¼15.4,
5
.3.5. 2-Acetyl-2-trans-cinnamylcyclopentanone (2k). IR
neat) 3026 (s), 1732 (s), 1703 (s), 1577 (s), 1450 (s),
1.1 Hz, 1H), 4.07 (dt, J¼7.3, 8.8 Hz, 1H), 4.16 (td, J¼8.8,
3.1 Hz, 1H), 5.10 (d, J¼1.1 Hz, 1H), 5.33 (s, 1H), 7.29–
7.33 (m, 5H). Anal. Calcd for C H O : C, 73.75; H, 6.60.
(
357 (s), 1141 (s), 970 (s) cm2 ; H NMR (400 MHz,
CDCl ) d 1.81–1.93 (m, 3H), 2.25 (s, 3H), 2.28–2.40 (m,
1
1
1
1
5 16 3
Found: C, 73.78; H, 6.82.
3
2
1
7
H), 2.60 (ddd, J¼14.4, 7.0, 1.5 Hz, 1H), 2.46–2.70 (m,
H), 2.82 (ddd, J¼14.4, 7.7, 1.5 Hz, 1H), 5.94 (dt, J¼15.8,
.7 Hz, 1H), 6.44 (d, J¼15.8 Hz, 1H), 7.21–7.31 (m, 5H).
5.4.5. a-Acetyl-a-(trans-2,4-pentadienyl)-g-butyrolac-
1
tone (3d). H NMR (400 MHz, CDCl ) d 2.10 (dt,
3
Anal. Calcd for C H O :C, 79.31; H, 7.49. Found: C,
J¼13.2, 8.8 Hz, 1H), 2.35 (s, 3H), 2.69 (dd, J¼14.7,
6.8 Hz, 1H), 2.78 (dd, J¼14.7, 6.8 Hz, 1H), 2.87 (ddd,
J¼13.2, 7.3, 3.7 Hz, 1H), 4.18 (dt, J¼8.8, 8.2 Hz, 1H), 4.28
(ddd, J¼9.0, 8.8, 3.3 Hz, 1H), 5.09 (d, J¼9.5 Hz, 1H), 5.19
(d, J¼16.1 Hz, 1H), 5.45 (dt, J¼15.0, 7.5 Hz, 1H), 6.16 (dd,
J¼15.0, 10.4 Hz, 1H), 6.27 (dt, J¼16.8, 10.4 Hz, 1H). Anal.
Calcd for C H O : C, 68.02; H, 7.27. Found: C, 68.23; H,
1
6 18 2
7
9.34; H, 7.55.
5
.3.6. 2-trans-Cinnamyl-2-formylcyclohexanone (2l). IR
neat) 1728 (s), 1699 (s), 1598 (w), 1132 (m), 970 (m), 748
(
(
2
1 1
m), 694 (m) cm ; H NMR (400 MHz, CDCl3) d 1.67 –
.97 (m, 5H), 2.23 – 2.53 (m, 3H), 2.66 (br dd, J¼7.6,
1
1
1
1 14 3
4.3 Hz, 1H), 2.70 (br dd, J¼7.6, 14.3 Hz, 1H), 6.06 (dt,
7.39.
J¼15.8, 7.6 Hz, 1H), 6.43 (br d, J¼15.8 Hz, 1H), 7.18 –
1
3
7
2
1
2
2
.32 (m, 5H), 9.57 (s, 1H); C NMR (100 MHz, CDCl3) d
1.5, 26.3, 31.8, 35.8, 41.1, 65.0, 123.5, 126.2, 127.5, 128.5,
34.2, 136.8, 200.9, 208.8; HRMS, calcd for C H O :
42.1307. Found m/z (relative intensity): 242.1292 (M ,
8), 213 (100).
5.4.6. a-Acetyl-a-(g,g-dimethylallyl)-g-butyrolactone
(3e). IR (neat) a mixture with 3e 1770 (s), 1674 (m),
0
1440 (s), 1377 (s), 1359 (s), 1163 (s), 1029 (s), 954
1
6
18
2
þ
21 1
(s) cm ; H NMR (400 MHz, CDCl ) d 1.65 (s, 3H), 1.71
3
(s, 3H), 2.04 (dt, J¼12.8, 8.8 Hz, 1H), 2.33 (s, 3H), 2.57 (dd,
J¼14.8, 6.6 Hz, 1H), 2.77 (dd, J¼14.8, 8.1 Hz, 1H), 2.87
(ddd, J¼12.8, 7.3, 3.7 Hz, 1H), 4.17 (dt, J¼7.3, 8.8 Hz, 1H),
5
5
.4. New compounds appeared in Table 2
4
.27 (td, J¼8.8, 3.7 Hz, 1H), 4.29 (br dd, J¼8.8, 6.6 Hz,
.4.1. a-Acetyl-a-(trans-crotyl)-g-butyrolactone (3a). IR
1H); HRMS, calcd for C H O : 196.1099. Found m/z
11 16 3
(relative intensity): 196.1087 (M , 65.5), 178.1020 (100).
0
s), 1359 (s), 1166 (s), 1028 (s), 972 (s) cm ; H NMR
þ
(
(
(
(
neat) a mixture with 3a 1766 (s), 1712 (s), 1436 (s), 1375
21 1
400 MHz, CDCl ) d 1.66 (dd, J¼6.2, 1.1 Hz, 3H), 2.09
5.4.7. a-Acetyl-a-(a,a-dimethylallyl)-g-butyrolactone
1
3
0
ddt, J¼13.2, 8.8, 6.6 Hz, 1H), 2.34 (s, 3H), 2.56 (ddt,
(3e ). H NMR (400 MHz, CDCl ) d 1.16 (s, 3H), 1.22 (s,
3
J¼14.3, 6.6, 1.5 Hz, 1H), 2.70 (dd, J¼14.3, 7.3 Hz, 1H),
3H), 2.35 (s, 3H), 5.05 (d, J¼17.4 Hz, 1H), 5.12 (d,
2
1
1
.85 (ddd, J¼13.2, 7.3, 3.7 Hz, 1H), 4.17 (dt, J¼8.8, 7.3 Hz,
H), 4.26 (td, J¼8.8, 3.7 Hz, 1H), 5.20 (br dq, J¼15.2,
.1 Hz, 1H), 5.61 (br dq, J¼15.2, 6.2 Hz, 1H). Anal. Calcd
J¼10.8 Hz, 1H), 7.25 (dd, J¼17.4, 10.8 Hz, 1H).
5.4.8. a-Acetyl-a-(2-cyclohexenyl)-g-butyrolactone (3f).
A mixture of diastereomers in a ratio of 1.7:1; IR (neat)
for C H O : C, 65.91; H, 7.74. Found: C, 66.08; H, 7.75.
1
0 14 3
1
1
1
761 (s), 1711 (s), 1165 (s), 1026 (s), 951 (m) cm2 ; H
NMR (400 MHz, CDCl , major isomer) d 1.03 (dtm,
0
a mixture of diastereomers in a ratio of 1.4:1; H NMR
5
.4.2. a-Acetyl-a-(a-methylallyl)-g-butyrolactone (3a ).
1
3
J¼10.3, 13.2 Hz, 1H), 1.48 – 2.08 (m, 6H), 2.36 (s, 3H),
2.82 (dm, J¼7.2 Hz, 1H), 3.26 (dm, J¼13.2 Hz, 1H), 4.08
(ddd, J¼7.2, 9.2, 10.3 Hz, 1H), 4.26 (dm, J¼9.2 Hz, 1H),
(
2
400 MHz, CDCl , major isomer) d 0.91 (d, J¼7.0 Hz, 3H),
3
.16 (m, 1H), 2.36 (s, 3H), 2.85 (m, 1H), 3.26 (qm,

7776
M. Kimura et al. / Tetrahedron 59 (2003) 7767–7777
1
5
NMR (400 MHz, CDCl , minor isomer) 1.22 (m, 1H), 1.48
.34 (dm, J¼10.3 Hz, 1H), 5.93 (dm, J¼10.3 Hz, 1H). H
8. Lu, X.; Lu, L.; Sun, J. J. Mol. Catal. 1987, 41, 245.
9. Lu, X.; Jiang, X.; Tao, X. J. Organomet. Chem. 1988, 344,
109.
3
–
2.08 (m, 6H), 2.41 (s, 3H), 2.88 (dm, J¼8.5 Hz, 1H), 3.19
m, 1H), 4.16 (q, J¼8.5 Hz, 1H), 4.25 (dm, J¼8.5 Hz, 1H),
.14 (dm, J¼10.3 Hz, 1H), 5.85 (dm, J¼10.3 Hz, 1H). Anal.
Calcd for C H O : C, 69.21; H, 7.74. Found: C, 69.50; H,
(
5
10. Sakamoto, M.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc.
Jpn 1996, 69, 1065.
11. Itoh, K.; Hamaguchi, N.; Miura, M.; Nomura, M. J. Chem.
Soc. Perkin Trans. 1 1992, 2833.
1
2 16 3
7
.71.
1
2. Ozawa, F.; Okamoto, H.; Kawagishi, S.; Yamamoto, S.;
Minami, T.; Yoshifuji, M. J. Am. Chem. Soc. 2002, 124,
10968.
5
1
.4.9. Diethylboron acetylacetonate. IR (neat) 1589 (s),
1
539 (s), 1386 (s), 1365 (s), 1064 (m) cm2 ; H NMR
1
(
400 MHz, CDCl ) d 0.41 (q, J¼7.8 Hz, 4H), 0.76 (s,
13. (a) Kimura, M.; Futamata, M.; Shibata, K.; Tamaru, Y.
J. Chem. Soc. Chem. Commun. 2003, 124. (b) Tamaru, Y.;
Horino, Y.; Araki, M.; Tanaka, S.; Kimura, M. Tetrahedron
Lett. 2000, 41, 5705. (c) Horino, Y.; Naito, M.; Kimura, M.;
Tanaka, S.; Tamaru, Y. Tetrahedron Lett. 2001, 42, 3113.
3
1
1
J¼7.8 Hz, 6H), 5.41 (s, 1H); B NMR (125 MHz, CDCl ,
3
relative to H BO ) d 25.16; HRMS, calcd for C H BO :
3
3
9
17
þ
2
1
1
68.1322. Found m/z (relative intensity): 168.1324 (M , 1),
67 (1), 139 (100).
1
4. Kimura, M.; Horino, Y.; Mukai, R.; Tanaka, S.; Tamaru, Y.
J. Am. Chem. Soc. 2001, 123, 10401.
5
(
1
.4.10. Diethylboron 2-acetyl-1-cyclohexenolate (5a). IR
neat) 1595 (s), 1492 (m), 1460 (m), 1379 (m), 1363 (s),
15. (a) Kimura, M.; Tomizawa, T.; Horino, Y.; Tanaka, S.;
Tamaru, Y. Tetrahedron Lett. 2000, 41, 3627. Nucleophilic
allylation of carbonyls with allyl alcohols promoted by
058 (m) cm2 ; H NMR (400 MHz, CDCl ) d 0.37 (q,
1
1
3
J¼7.8 Hz, 4H), 0.76 (t, J¼7.8 Hz, 6H), 1.68–1.71 (m, 4H),
1
1
0
2
.06 (s, 3H), 2.26–2.34 (m, 4H); B NMR (125 MHz,
CDCl3, relative to H BO ) d 26.45; HRMS, calcd for
diethylzinc in the presence of an Pd species; in press.
Kimura, M.; Shimizu, M.; Shibata, K.; Tazoe, M.; Tamaru, Y.
Angew. Chem. Int. Ed. 2003, 42, 3392.
16. Stary, I.; Stara, I. G.; Kocovsky, P. Tetrahedron Lett. 1993, 34,
3
3
C H BO : 208.1635. Found m/z (relative intensity):
2
1
2
21
þ
2
07.1496 (M , 4), 179 (100).
1
79.
7. Bordwell, F. G.; Bares, J. E.; Bartmess, J. E.; McCollum, G. J.;
1
van der Puy, M.; Vanier, N. R.; Matthews, W. S. J. Org. Chem.
1
Acknowledgements
977, 42, 326.
8. Smith, M. B.; March, J. Advanced Organic Chemistry; Wiley:
New York, 2001; pp. 330–331.
1
Financial support from the Ministry of Education, Science,
Sports and Culture, Japanese Government, Grant-in-Aid for
Scientific Research B, is acknowledged.
1
9. Values estimated by using Advanced Chemistry Development
Software V4.67.
2
0. Iglesias, E. J. Org. Chem. 2003, 68, 2680.
1. Emilia, I. New J. Chem. 2002, 26, 1352.
2
22. Pihlaja, K.; Seilo, M. Acta Chem. Scand. 1969, 23, 3003.
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4
2, 2043. (d) Buckwalter, B. L.; Burfitt, I. R.; Felkin, H.; Joly-
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