Palladium-catalyzed allyl cross-coupling reactions with in situ generated organoindium reagents

Article abstract of DOI:10.1002/asia.201000890

Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions, using allylindium generated in situ from allyl halides and indium, is demonstrated. Allylindium compounds may be effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions. A variety of allyl halides, such as allyl iodide, allyl bromide, crotyl bromide, prenyl bromide, geranyl bromide, and 3-bromocyclohexene afforded the allylic cross-coupling products in good to excellent yields. Stereochemistry of the double bond is retained in the allylic cross-coupling reactions. Electrophilic cross-coupling partners, such as aryl and vinyl halides, dibromoolefin, alkynyl iodide, and aryl and vinyl triflates participate in these reactions. The presence of various substituents, such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phenylamido, nitro, and chloride groups on the aromatic ring of electrophilic coupling partners showed little effect on the efficiency of the reactions. The present conditions work equally well for not only intermolecular but also intramolecular palladium-catalyzed cross-coupling reactions. These methods provide an efficient synthetic method for the introduction of an allyl group, which can be easily further functionalized to afford an sp²- and sp-hybridized carbon. The present method complements existing synthetic methods as a result of advantageous features such as easy preparation and handling, thermal stability, high reactivity and selectivity, operational simplicity, and low toxicity of allylindium reagents.

Full text of DOI:10.1002/asia.201000890

DOI: 10.1002/asia.201000890
Palladium-Catalyzed Allyl Cross-Coupling Reactions with In Situ Generated
Organoindium Reagents
Kooyeon Lee, Hyunseok Kim, Juntae Mo, and Phil Ho Lee*[a]
Dedicated to Professor Eun Lee on the occasion of his retirement and 65th birthday
Abstract: Inter- and intramolecular
palladium-catalyzed allyl cross-cou-
pling reactions, using allylindium gen-
erated in situ from allyl halides and
indium, is demonstrated. Allylindium
compounds may be effective nucleo-
philic coupling partners in palladium-
catalyzed cross-coupling reactions. A
variety of allyl halides, such as allyl
iodide, allyl bromide, crotyl bromide,
prenyl bromide, geranyl bromide, and
3-bromocyclohexene afforded the allyl-
ic cross-coupling products in good to
excellent yields. Stereochemistry of the
double bond is retained in the allylic
cross-coupling reactions. Electrophilic
cross-coupling partners, such as aryl
and vinyl halides, dibromoolefin, alkyn-
yl iodide, and aryl and vinyl triflates
participate in these reactions. The pres-
ence of various substituents, such as n-
butyl, ketal, acetyl, ethoxycarbonyl, ni-
trile, N-phenylamido, nitro, and chlo-
ride groups on the aromatic ring of
electrophilic coupling partners showed
little effect on the efficiency of the re-
actions. The present conditions work
equally well for not only intermolecu-
lar but also intramolecular palladium-
catalyzed cross-coupling reactions.
These methods provide an efficient
synthetic method for the introduction
of an allyl group, which can be easily
further functionalized to afford an sp2-
and sp-hybridized carbon. The present
method complements existing synthetic
methods as a result of advantageous
features such as easy preparation and
handling, thermal stability, high reactiv-
ity and selectivity, operational simplici-
ty, and low toxicity of allylindium re-
agents.
Keywords: allylation · allylindium ·
cross-coupling · indium · palladium
Introduction
ners, and nucleophilic coupling partners. Among these, reac-
tions using organoindium reagents have become a favorite
owing to their reactivity and selectivity, thermal stability,
ease of preparation and handling, operational simplicity, and
low toxicity.[2] On the basis of these properties, palladium-
À
The development of efficient synthetic methods for C C
bond formation is an important continuing research subject
in organic synthesis. Transition-metal-catalyzed cross-cou-
pling reactions of organometallic reagents with a wide range
catalyzed cross-coupling reactions using triACTHUNRTGNEUNG(organo)indiums
of electrophilic coupling partners represent one of the most
have been reported.[3] Also, a wide range of indium-mediat-
ed cross-coupling reactions have been investigated.[4] Re-
cently, we reported palladium-catalyzed cross-coupling reac-
tions of allylindiums,[5] allenylindiums,[6] 1,3-butadien-2-ylin-
[1]
À
useful methods to form C C bonds. Especially, Palladium-
catalyzed cross-coupling reactions have been the central
focus of transition-metal chemistry during the past three
decades.[1g] Recently, the synthetic scope of cross-coupling
reactions has been continuously expanded by development
and application of new catalysts, electrophilic coupling part-
diums,[7] vinyl indium,[8] tetra
organothiolates),[10] and tri
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
of electrophiles. Moreover, we have described palladium-
catalyzed carbonylative cross-coupling reactions of tri-
ACHUTNGRENNUG CAHTUNGTREN(NNGU organo)indates with electro-
(organo)indiums[12] and tetra
philes.[13] It was found that palladium-catalyzed inter- and in-
tramolecular cross-coupling reactions of aryl and vinyl hal-
ides were mediated by indium.[14]
[a] Dr. K. Lee, Dr. H. Kim, J. Mo, Prof. Dr. P. H. Lee
Department of Chemistry
Institute for Molecular Science and Fusion Technology
Kangwon National University
Chuncheon 200-701 (Republic of Korea)
Fax : (+82)33-253-7582
Further functionalization of the allyl group allows its in-
troduction into organic compounds.[15] Therefore, many ally-
lation methods, such as Friedel–Crafts reaction,[16] Claisen
E-mail: phlee@kangwon.ac.kr
Chem. Asian J. 2011, 6, 2147 – 2157
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2147

FULL PAPERS
rearrangement,[17] and substitution reactions of allyl halides
with organometallic reagents,[18] have been investigated.
Moreover, palladium-catalyzed cross-coupling reactions
have attracted much attention in allylation methods.[19] One
of the most frequently used methods for allyl cross-coupling
reactions is the Stille cross-coupling reaction, in which allyl-
stannanes have been used as nucleophilic coupling partners.
These reagents have attracted much attention owing to their
availability, air- and moisture-stability, and their compatibili-
ty with a variety of functional groups.[20] However, the Stille
cross-coupling reaction has some limitations, such as difficul-
ties associated with preparation of regiochemically defined
allylstannanes, their tendency to undergo allylic isomeriza-
tion, tin removal from the product, tin toxicity, and excess
use of organostannanes arising from dummy ligands. Al-
though allylstannanes are generally accessible from organo-
metallic reagents, such procedures are sometimes inade-
quate and the requisite allylmetals are difficult to obtain.
Allylmetals must ideally be prepared in situ from the reac-
tion of metals with allyl halides. The advantage of allylmag-
nesium halide and allyllithium as a nucleophilic coupling
partner is their availability.[21] However, these reagents show
low functional group tolerance. In this sense, development
of new allylmetals as coupling partners is necessary to over-
come these difficulties. Our interest, both in overcoming the
limitations of allyl cross-coupling reactions using allylmetals
and applying indium metal to organic synthesis,[22,2b] have
led us to investigate the participation of organoindium re-
agents in metal-catalyzed reactions.[23] Moreover, tri-
Results and Discussion
Optimization of Cross-Coupling Reactions of In Situ
Generated Allylindium Reagent with 1-Iodonaphthalene
Our initial study focused on palladium-catalyzed cross-cou-
pling reactions of 1-iodonaphthalene with allylindium re-
agent generated in situ from a reaction of allyl iodide and
indium.[26] The catalytic activity of several palladium com-
plexes was examined and the results are summarized in
Table 1. Among the catalysts screened, [Pd
(2 mol%) and [Pd(PPh3)4] (4 mol%) showed high catalytic
activity (Table 1, entries 4 and 21). Other palladium com-
plexes, such as PdCl2, Pd(OAc)2, [Pd(CH3CN)2Cl2], and [Pd-
(PhCN)2Cl2], produced 1-allylnaphthalene in good yields
2ACHTUNGERTN(NUNG dba)3]CHCl3
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
(Table 1, entries 14–17). Among the ligands tested, triphe-
nylphosphine gave the best results (Table 1, entry 4). The
use of lithium halide as an additive is critically important for
Table 1. Reaction optimization of 1-iodonaphthalene with allylindium.[a]
Entry Catalyst
Solvent
Additive
t
Yield
[h] [%][b]
1
2
3
4
5
6
7
8
G
2A
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/Ph3P
2A(dba)3]CHCl3/
(MeO)2C6H3]3P
3 A(o-
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
–
1
0
R
LiCl
LiCl
LiCl
LiCl
LiCl
LiBr
LiI
16 46[c]
E
16 50[d]
T
1
1
1
1
1
93
R
64[e]
27[f]
90
ACHTUNGTRENNUNG
N
AHCTUNGTRENNUNG
G
indium(I) iodide.[3c,24] Lloyd-Jones and co-workers reported
that reaction of iodobenzene or benzenediazonium tetra-
fluoroborate with allylindium in the presence of various pal-
ladium and nickel complexes did not proceed.[25] Herein, we
report in full the novel intermolecular and intramolecular
palladium-catalyzed cross-coupling reactions of a wide range
of allylindium reagents generated in situ from allyl halides
and indium with organic electrophiles, such as aryl and vinyl
halides and aryl and vinyl triflates (Scheme 1). Also, stereo-
selectivity, chemoselectivity, and relative reactivity of allylin-
dium reagents in cross-coupling reactions will be discussed.
T
91
9
10
N
nBu4NCl 16 67 (5)[g]
LiCl
N
21 10
21 11
20 11
R
ACHTUNGTRENNUNG
11
E
DMF
LiCl
12
13
T
DMF
DMF
LiCl
LiCl
E
C
3
75
Furyl)3P
PdCl2/Ph3P
PdACHTUGNTRENNNUG
[Pd
[Pd
[Pd
[Pd
[Pd
[Pd
[Pd
14
15
16
17
18
19
20
21
22
DMF
DMF
DMF
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
1
1
3
1
4
4
86
86
70
87
0
N
E
DMF
N
Benzene
Toluene
THF
R
0
N
18 58
G
DMF
1
20
91
0
N
DMF/
H2O[i]
THF/
23
24
[Pd
A
LiCl
LiCl
20
20
0
0
H2O[j]
DMF/
H2O[i]
N
ACHTUNGERTN(NUNG 2-
[a] Reactions performed with [Pd
2ACHTUGNTREN(UNGN dba)3]CHCl3 (2 mol%)/ligand
(16 mol%) or [Pd(PPh3)4] (4 mol%) in the presence of additive
AHCTUNGTRENNUNG
(3.0 equivalents) in DMF at 1008C unless otherwise noted. Allylindium
was obtained from the reaction of indium (1 equiv) with allyl iodide
(1.5 equiv). [b] Yield of isolated product. [c] In/allyl iodide=0.66:1.
[d] In/allyl iodide=1:1. [e] LiCl (2 equiv) was used. [f] LiCl (1 equivalent)
was used. [g] 1-Iodonaphthalene. [h] PPh3 (2 mol%) was added. [i] DMF/
H2O=6:1. [j] THF/H2O=6:1.
Scheme 1. Palladium-catalyzed allyl cross-coupling reactions. DMF=
N,N-dimethylformamide.
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Chem. Asian J. 2011, 6, 2147 – 2157

Palladium-Catalyzed Allyl Cross-Coupling Reactions
a successful reaction (Table 1, entries 1 and 4). The cross-
coupling reactions did not proceed without lithium chloride
(Table 1, entry 1). Use of 3 equivalents of lithium chloride
gave the best results (Table 1, entries 4–6). Although lithium
bromide and lithium iodide gave similar results as lithium
chloride (Table 1, entries 7 and 8), lithium chloride was used
owing to molecular weight and price. In the case of tetra-n-
butylammonium chloride, 1-allylnaphthalene was obtained
in 67% yield (Table 1, entry 9). N,N-Dimethylformamide
was the best solvent among several reaction media (ben-
zene, toluene, THF, DMF, DMF–H2O, and THF–H2O) that
were examined (Table 1, entries 18–24). Allylindium reagent
generated in situ from the reaction of indium (1 equiv) with
allyl iodide (1.5 equiv) gave the best result as a nucleophilic
coupling partner. Use of indium in less than 1 equivalent
and allyl iodide in less than 1.5 equivalents resulted in a
sluggish reaction and gave lower yields as well as longer re-
action times (Table 1, entries 2 and 3). Of the catalytic sys-
tems examined, the best results were obtained with [Pd2
Cross-Coupling Reactions of In Situ Generated Allylindium
Reagents with Halonaphthalenes
To demonstrate the efficiency and scope of the present
method, we applied a variety of in situ generated allylindi-
um reagents in cross-coupling reactions. The results are sum-
marized in Table 2. Aryl iodide was more reactive than aryl
bromide toward allylindium. Thus, a slightly higher yield of
cross-coupling product from 1-iodonaphthalene was ob-
tained (Table 2, entries 1 and 2). The reaction of allylindium
obtained from allyl iodide with 1- or 2-bromonaphthalene
gave the desired products in 88% and 80% yields, respec-
tively (Table 2, entries 2 and 4). Under the optimum reac-
tion conditions, treatment of 1-iodonaphthalene with allylin-
dium derived from allyl bromide gave 1-allylnaphthalene in
87% yield (Table 2, entry 5). The presence of various alkyl
substituents at the a- and g-position exhibited little effect on
both the reaction rates and product yields. The reaction of
2a with crotyl bromide (1c, cis/trans=1:5) in the presence
of indium provided a 1:3.2 mixture of a-attack (cis/trans=
1.5:1, 3c) and g-attack products (3d), but the product result-
ing from g-attack predominates (Table 2, entry 6). Benzalde-
hyde reacted with prenyl bromide and indium, producing
2,2-dimethyl-1-phenyl-3-buten-1-ol in 90% yield, which was
the g-attacked product, in water (Scheme 2).[26c] However, 1-
iodonaphthalene was treated with prenylindium to afford
exclusively 1-prenylnaphthalene (3g), which was the a-at-
ACHTUNGTRENNUNG(dba)3CHCl3] (2 mol%)/Ph3P (16 mol%) or [PdCAHTUNGTREN(NGUN PPh3)4]
(4 mol%) in the presence of LiCl (3 equiv) in N,N-dimethyl-
formamide at 1008C for 1 hour under nitrogen atmosphere
(Table 1, entries 4 and 21).
Table 2. Palladium-catalyzed allyl cross-coupling reactions of allylindiums with halonaphthalenes.[a]
Entry
Allyl Halide
Naph-X
t [h]
Product
Yield [%][b]
93
1
1a
1-I (2a)
1
3a
2
3
4
1-Br (2b)
1-Cl (2c)
2-Br (2d)
3
3
3
3a
3a
3b
88
0
80
5
1b
1-I (2a)
11
3a
87
6
7
1c[c]
1-I (2a)
24
27
3c 3e
3d 3 f
86 (1[f]:3.2)[g]
61 (1[h]:4)[g]
1-Br (2b)
8
2-Br (2d)
7
61 (1[h]:4.1)[i]
9
1d
1-I (2a)
25
3g[d]
88
10
11
1-Br (2b)
2-Br (2d)
20
6
3g[d]
3h[e]
72
84
12
1e
1 f
1-I (2a)
24
3i
71 (1:2)[j]
13
1-I (2a)
3
3j[d]
66
14
15
1-Br (2b)
2-Br (2d)
22
4
3j[d]
80
50
3k[e]
16
1g
1-I (2a)
22
0
[a] Reactions performed with [Pd2ACHTNUTRGNEUNG(dba)3]CHCl3 (2 mol%)/ligand (16 mol%) and LiCl (3 equiv) in DMF at 1008C. Allylindium was obtained from the re-
action of indium (1 equiv) with allyl iodide (1.5 equiv). Naph=naphthalene. [b] Yield of isolated product. [c] cis/trans=1:5. [d] 1-Allyl substituted naph-
thalenes. [e] 2-Allyl substituted naphthalenes. [f] cis/trans=1.5:1. [g] 3c/3d ratio. [h] cis/trans=1:1. [i] 3e/3 f ratio. [j] cis/trans ratio.
Chem. Asian J. 2011, 6, 2147 – 2157
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P. H. Lee et al.
FULL PAPERS
Table 3. Palladium-catalyzed allyl cross-coupling reactions of allylindi-
ums with aryl halides.[a]
Entry Allyl
Halide
FG
t
Product Yield [%][b]
[h]
1
2
3
1a
1b
1c
4-nBu (4a)
1
5a
75
60
22 5a
21 5b[c]
5c[d]
71 (4.8[e]:1)[f]
4
5
6
1d
1 f
1a
15 5d
50
70
93
Scheme 2. g-Attack in addition to carbonyl compound and a-attack in
palladium-catalyzed cross-coupling reaction of prenylindium. THF=tet-
rahydrofuran, dppf=1,1’-bis(diphenylphosphino)ferrocene.
3
3
5e
5 f
4-CCH3
AHCTUNTGREN(NGNU OCH2CH2O) (4b)
7
8
9
10
1 f
1a
1b
1c
3
1
9
4
5g
5h
89
88
70
4-Ac (4c)
tacked product, in 88% yield under the present conditions
(Table 2, entry 9). Reaction of benzaldehyde with organoin-
dium reagent obtained from prenyl bromide and indium in
water proceeded through cyclic transition states, all with the
carbonyl oxygen coordinated with indium, producing the g-
attack product selectively. Regioselectivity appears to be
governed by the steric size of the g-substituent, but not by
the degree of substitution. Therefore, the palladium-cata-
lyzed cross-coupling reaction of prenylindium with 1-iodo-
naphthalene might be governed by the steric size owing to
the absence of a carbonyl oxygen, selectively producing the
a-attack product. In the case of crotyl bromide, the results
are complicated owing to the isomer mixture (cis/trans=1:5)
of crotyl bromide and an ambiguous steric effect.
The reaction of 2a with in situ generated geranylindium
from indium and geranyl bromide gave cross-coupling prod-
uct 3i in 71% yield (cis/trans=1:2) (Table 2, entry 12). In
the case of 3-bromocyclohexene, the desired products were
obtained in moderate to good yields (Table 2, entries 13–
15). However, use of allylindium reagents derived from
ethyl 4-bromocrotonate and indium did not afford the de-
sired product (Table 2, entry 16).
5h
5i[c]
60 (1[g]:1)[f]
5j[d]
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
1d
1 f
1a
1d
1a
1a
1 f
1a
1a
1d
1d
1a
1a
1a
1c
15 5k
72
66
96
3
1
1
2
2
2
7
7
8
8
6
6
3
9
5l
2-EtO2C (4d)
5m
5n
5o
5p
5q
5r
5r
5s
5s
5t
76
3-EtO2C (4e)
4-EtO2C (4 f)
84 (7)[h]
84
75
73
4-NC (4g)
71[i] (4:1)[j]
86
81[i]
4-BnNHCO (4h)
3-O2N (4i)
76
5t
71[i]
5u
5v[c]
5w[d]
5x
5y
5z
94
89 (1[k]:1.2)[f]
26
27
28
29
1d
1e
1 f
1e
9
9
9
6
88
88 (1:2)[l]
81
4-Cl (4j)
5a’
65 (1:3)[l] (21)[m]
[a] Reactions performed in the presence of [Pd2ACHTNUTRGNE(UGN dba)3]CHCl3 (2 mol%)/
PPh3 (16 mol%) and LiCl (3.0 equiv) in DMF at 1008C. Allylindium was
obtained from the reaction of indium (1 equivalent) with allyl iodide
(1.5 equiv). Aryl iodides were used unless otherwise noted. [b] Yield of
isolated product. [c] a-Attack product. [d] g-Attack product. [e] cis/
trans=1:1.5. [f] Ratio of a-attack and g-attack product. [g] cis/trans=1:1.
[h] Ethyl benzoate. [i] Aryl bromide was used. [j] Ratio of 4-allylbenzoni-
Intermolecular Cross-Coupling Reactions of In Situ
Generated Allylindium Reagents with Electrophilic
Coupling Partners
trile and 4-trans-(1-propenyl)-benzonitrile. [PdACTHUNTRGNE(UNG PPh3)4] (4 mol%) was
used. [k] cis/trans=1:1.5. [l] cis/trans ratio. [m] 4,4’-Dichlorobiphenyl.
Next, we applied this catalytic system to a variety of aryl
and vinyl halides and aryl and vinyl triflates. For a vast
number of aryl iodides, the presence of various substituents,
such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phe-
nylamido, nitro, and chloride groups on the aromatic ring,
showed little effect on the efficiency of the reactions. The
results are summarized in Table 3.
Palladium-catalyzed cross-coupling reactions of 4-n-butyl-
iodobenzene with a variety of allyl halide (1a–1d and 1 f)
and indium gave the desired products in good yields
(Table 3, entries 1–5). It should be mentioned that 4-iodoa-
cetophenone, having a labile keto group toward allylindium,
provided allylic cross-coupling products in good yields
(Table 3, entries 8–12). In the case of ethyl iodobenzoate,
yield and selectivity of cross-coupling reactions are inde-
pendent on electronic and steric effect (Table 3, entries 13–
17). 4-Iodobenzonitrile was treated with prenylindium to
give 4-prenylbenzonitrile in 86% yield (Table 3, entry 20).
Subjecting 4-bromobenzonitrile and N-benzyl-4-bromoben-
zamide to prenylindium and allylindium afforded the de-
sired products in 81% and 71% yields, respectively
(Table 3, entries 21 and 23). In the case of 1-iodo-3-nitro-
benzene, the desired products were obtained in good to ex-
cellent yields from a wide range of allylindium reagents
(Table 3, entries 24–28). In general, yields of the cross-cou-
pling products were increased for aryl iodides possessing an
electron withdrawing group. These results can be under-
stood on the basis of the fact that an electron withdrawing
group on aryl halides generally enhances the rate of oxida-
tive addition of the palladium center to this substrate.[27] Re-
action of 4-iodoanisole with allylindium did not proceed.
Although 1-iodonaphthalene reacted with allylmagnesium
bromide in the presence of [Pd
2ACHTUNGTREN(UNGN dba)3]CHCl3 (2 mol%)/
dppf (8 mol%, THF, 258C, 7 h) to afford 1-allylnaphthalene
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Palladium-Catalyzed Allyl Cross-Coupling Reactions
in 88% yield, reaction of 4-iodoacetophenone with allylmag-
nesium bromide gave rise to 1-(4-iodophenyl)-1-methyl-3-
buten-1-ol (91%) obtained from the addition of allylmagne-
sium bromide to the ketone group (THF, 258C, 15 min).
This result indicates that the allylindium reagent shows
better chemoselectivity than allylmagnesium bromide in the
cross-coupling reactions and also has more covalent charac-
ter than allylmagnesium bromide (Scheme 3). Treatment of
methyl-3-buten-1-ol in 50% yield as a major compound, in-
dicating that selectivity of these functional groups for ally-
lindium is benzaldehyde>iodobenzene>acetophenone>
bromobenzene.
We then applied the present method to 1,3,5-tribromo-
benzene to obtain 1,3,5-triACHTNUTRGNE(NUG allyl)benzene, which can be used
effectively in material and polymer sciences. Reaction of
1,3,5-tribromobenzene with 6 equivalents of allyl iodide and
4 equivalents of indium in the presence of [Pd
(3 mol%) and (tBu)3P (3 mol%) produced 1,3,5-tri-
(allyl)benzene in 81% yield (DMF, 1008C, 24 h, Scheme 5).
2ACHTUNGERTN(NUNG dba)3]CHCl3
AHCTUNGTRENNUNG
Scheme 5. Palladium-catalyzed allyl cross-coupling reaction of allylindi-
um with 1,3,5-tribromobenzene.
Heteroatoms turned out to be compatible with the em-
ployed reaction conditions. Treatment of allylindium with 5-
iodo-1,3-dimethyl-1H-pyrimidine-2,4-dione under the opti-
mum conditions gave the desired compound in 73% yield
(Scheme 6). The reaction worked equally well with 3-
bromo-2-methylpropene and trans-cinnamy bromide. More-
over, reaction of 3-bromoquinoline and 4-bromoisoquinoline
with allylindium afforded the corresponding allylic cross-
coupling products in 70% and 65% yields, respectively.
Encouraged by these results, palladium-catalyzed cross-
coupling reactions of allylindium with vinyl halides, dibro-
moolefin, and alkynyl iodide were examined. The results are
summarized in Table 4. a-Bromostyrene was treated with al-
lylindium to give 2-phenyl-1,4-pentadiene (7a) and trans-1-
Scheme 3. Reactivity comparison between allylmagnesium bromide, allyl-
zinc bromide, and allylindium reagent.
1-iodonaphthalene with allylzinc bromide[28] obtained from
allyl bromide and zinc afforded 1-allylnaphthalene and 1,1’-
bi
ACHTUNGTRENNUNG
presence of [PdACHTUNGTRENNUNG
258C, 20 h). 1-(4-Iodophenyl)-
1-methyl-3-buten-1-ol was ob-
tained in 87% yield from reac-
tion of 4-iodoacetophenone
with allylzinc bromide in the
presence
of
[PdACTHUNGTRENNU(G PPh3)4]
(4 mol%) (THF, 258C, 15 min).
Selectivity in the allyl cross-
coupling reaction between aryl
halide, aldehyde, and ketone
groups
was
examined
(Scheme 4). Although 4-iodo-
benzaldehyde reacted with ally-
lindium to give 1-(4-iodo-
phenyl)-3-buten-1-ol and 1-(4-
allylphenyl)-3-buten-1-ol
in
63% yield and 15% yields, re-
spectively, 4-iodoacetophenone
selectively produced 4-allylace-
tophenone in 88% yield. More-
over, treatment of 4-bromoace-
tophenone with allylindium af-
forded 1-(4-bromo-phenyl)-1- Scheme 4. Selectivity between aryl halide, aldehyde, and ketone groups.
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P. H. Lee et al.
FULL PAPERS
7h) in 96% yield (Table 4, entry 6). Under the optimum re-
action conditions, reaction of cis- and trans-b-bromostyrene
with allylindium afforded selectively cis- and trans-1-phenyl-
1,4-pentadiene in 84% and 89% yields, respectively, indicat-
ing that stereochemistry of the double bond is retained in
the allylic cross-coupling reaction.
It should be noted that 3- or 2-iodo-2-cyclohexen-1-one
having labile ketone group toward allylindium provided the
desired products 7j, 7k, 7l, and 7m in good yields (Table 4,
entries 8–11), respectively. 1,2-Addition product (1-allyl-3-
iodo-2-cyclohexen-1-ol) from reaction of 6e with allylindium
was obtained in 77% yield in the absence of palladium cata-
lyst. Although reaction of 6e with allylindium reagent was
carried out in N,N-dimethylformamide at 1008C for 4 hours,
the 1,2-addition product was only obtained in 75% yield.
Therefore, formation of 7j through 1,2-addition followed by
oxy-Cope rearrangement was excluded. With these results in
hand, the present reaction proceeded definitely through a
palladium-catalyzed cross-coupling reaction (Scheme 8).
Scheme 6. Palladium-catalyzed allyl cross-coupling reaction of allylindi-
um with haloheterocycles.
phenyl-1,4-pentadiene (7b) in 65% and 32% yields, respec-
tively (Table 4, entry 1). Although the mechanism of forma-
tion of 7b is not clear, we believe that 1,4-diene 7b might
be produced by oxidative addition of palladium to a-bro-
mostyrene, dehydropalladation owing to a steric effect to
produce phenylacetylene, and then hydropalladation to phe-
nylacetylene followed by an allyl cross-coupling reaction.[29]
In the case of 2-bromo-5-phenyl-1-pentene (6b), 4-(3-phe-
nylpropyl)-1,4-pentadiene (7g) was produced in 86% yield
(Table 4, entry 5). This result supports the mechanism of for-
mation of 7b mentioned above. The reaction of a-bromos-
tyrene with crotyl bromide (cis/trans=1:5) in the presence
of indium produced a 1.9:1 mixture of a-attack (cis/trans=
1:1, 7c) and g-attack products (7d) (Table 4, entry 2). Treat-
ment of 6a with geranylindium produced the desired prod-
uct 7e in 97% yield (Table 4, entry 3). In case of b,b-dibro-
mostyrene (6d),[30] the twofold cross-coupling product 7i
was obtained in 92% yield with 2 equivalents of allylindium
(Table 4, entry 7). Treatment of iodophenylacetylene[31] with
prenylindium regioselectively produced 5-methyl-1-phenyl-
4-hexen-1-yne (7n) in 82% yield (Table 4, entry 12).
Stereochemistry in cross-coupling reactions using an ally-
lindium reagent was examined (Scheme 7). The reaction of
b-bromostyrene (cis/trans=1:4) with allylindium gave cross-
coupling product 1-phenyl-1,4-pentadiene (cis/trans=1:4,
Scheme 8. Reaction mechanism of allylindium with 3-iodo-2-cyclohex-
ene-1-one.
As an extension of this work, we applied this catalytic
system in a variety of aryl and vinyl triflates. The results are
summarized in Table 5. Reactivity of naphthyl triflates de-
rived from 1- and 2-naphthtol is similar to that of 1-halo-
naphthalene. Under the optimized conditions, 8a reacted
with allyl iodide and indium to produce 3a in 92% yield
(Table 5, entry 1). Whereas addition reaction of prenylindi-
um to benzaldehyde usually gave the product resulting from
g-attack (Scheme 2),[26] reaction of 8a with prenylindium re-
Scheme 7. Stereochemistry in reaction of cis- and trans-b-bromostyrene
with allylindium.
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Palladium-Catalyzed Allyl Cross-Coupling Reactions
Table 4. Palladium-catalyzed allyl cross-coupling reactions of allylindiums with vinyl halides and alkynyl iodide.[a]
Entry
Allyl
Halide
Vinyl Halide
t [h]
Product
Yield [%][b]
97 (2:1)[c]
7a
7b
7c
1
1a
6a
6a
3.5
2
1c[d]
5
89 (1.9[e]:1)[f]
7d
7e
3
4
1e
1 f
6a
6a
6.5
3
97 (1:1)[g]
91
7 f
5
6
1a
1a
6b
5
7g
7h
86[h]
6c[i]
2.5
96 (1:4)[g]
7
1a
6d
3
7i
92[j,k]
8
1a
6e
3
7j
88
9
1b
1d
6e
6 f
3
1
7k
7l
96
84
10
11
12
1 f
6 f
6g
1
1
7m
7n
89
1d
82[j]
[a] Reactions performed in the presence of [Pd
ACHTUNGTRENNUNG
7b. [d] cis/trans=1:5. [e] Isomeric ratio of 7c: cis/trans=1:1. [f] 7c(a)/7d(g) ratio. [g] cis/trans ratio. [h] [Pd CTHUNGTRENNUNG
used as catalyst. [i] cis/trans=1:4. [j] [Pd2ACHTUNGTRENNUNG
used.
gioselectively produced 3g in 87% yield resulting from a-
attack (Table 5, entry 2). Reaction of 8b with 3-bromocyclo-
hexene in the presence of indium afforded 2-(cyclohex-2-
enyl)naphthalene in 86% yield (Table 5, entry 6). In the
case of triflate (8c) of 4-hydroxyacetophenone, the cross-
coupling product (5h) and homoallyl alcohol were produced
in 30% and 55% yields, respectively (Table 5, entry 7). Sub-
jecting vinyl triflates (8d, 8e, 8 f, and 8g) to in situ generat-
ed allylindium produced the corresponding allylic com-
pounds in good to excellent yields (Table 5, entries 8–12).
selected for initial examination as it was expected that cycli-
zation of this substrate would be facilitated by a Thorpe–
Ingold effect.[32] Subjecting 10c to the optimum conditions
gave the desired compound 11c in 78% yield (Table 6,
entry 3). Compound 10b, having one ethoxycarbonyl group
on the backbone chain, was cyclized to produce 11b in 75%
yield (Table 6, entry 2). Also, iodobenzene having allyl bro-
mide 10a was smoothly cyclized to give 1-vinylindane in
69% yield under the optimum reaction conditions (Table 6,
entry 1), indicating that presence of a geminal Thorpe–
Ingold buttressing is helpful but not a prerequisite for suc-
cessful cyclization, as 10a partakes in the reaction. Exposure
of 10d, containing a moiety of vinyl bromide and allyl bro-
mide, to indium (1 equivalent) and lithium iodide (3 equiv)
Intramolecular Cross-Coupling Reactions Using In Situ
Generated Allylindium Reagents
On the basis of above results, intramolecular cross-coupling
reactions were investigated. The results are summarized in
Table 6. Intramolecular cross-coupling reaction of 10c was
(DMF, 1008C, 1 h) in the presence of [PdACHTGNUETRN(NUG PPh3)4] (4 mol%)
provided the desired product (11d) in 82% yield (Table 6,
entry 4). Iodobenzene derivative (10e), having a nitrogen
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P. H. Lee et al.
FULL PAPERS
Table 5. Palladium-catalyzed allyl cross-coupling reactions of allylindi-
ums with aryl and vinyl triflates.[a]
Table 6. Intramolecular palladium-catalyzed allyl cross-coupling reac-
tions.[a]
Entry Allyl
Halide
Triflate
t
Product
Yield
[%][b]
Entry
Reactant
t
Product
Yield
[%][b]
[h]
[h]
1
10a
10b
1
1
11a
11b
69
1
1a
2
3a
92[c]
8a
8a
8a
2
3
1d
1 f
15
7
3g
3j
87[c]
85[c]
2
75
4
1a
20
3b
92
8b
8b
8b
5
6
1d
1 f
21
3
3h
3k
83
86
3
4
5
10c
10d
10e
1
1
1
11c
11d
11e
78
82
71
7
8
9
1a
1a
1a
3
2
5h
7a
30 (55)[d]
8c
8d
8e
62
21
93[c]
9a
9b
10
1a
16
84
8 f
8 f
6
7
10 f
10g
1
1
11 f
11g
83
73
11
12
1 f
1a
8
2
73
82
9c
9d
8g
8
10h
1
11h
84
[a] Reactions performed in the presence of [Pd
PPh3 (4 mol%) and LiCl (3 equiv) in DMF at 1008C. [b] Yield of isolated
product. [c] [Pd(PPh3)4] (4 mol%) was used. [d] 4-(1-Hydroxy-1-methyl-
2ACHTUNGTREN(UNGN dba)3]CHCl3 (2 mol%)/
ACHTUNGTRENNUNG
but-3-enyl)phenyl trifluoromethanesulfonate.
9
10i
10j
1
1
11i
11j
84
76
linkage, produced N-tosyl-3-vinylindoline (11e) in 71%
yield (Table 6, entry 5). 10 f, possessing an allyl chloride
moiety, was smoothly cyclized to produce 11 f in 83% yield
(Table 6, entry 6). Exposure of 10g, having an ether linkage
on the backbone chain, to palladium catalyst and indium
gave the tetrahydropyran derivative 11g in 73% yield
(Table 6, entry 7). Next, we applied the present conditions
to 10i and 10j and the 7- and 8-membered ring compounds
(11i and 11j) were obtained in 84% and 76% yields, re-
spectively (Table 6, entries 9 and 10). Although a wide range
of allyl acetates was used in the intramolecular palladium-
catalyzed allylic cross-coupling reaction, a variety of allyl
halides was used in the present reaction.[5f]
Use of LiCl instead of LiI gave rise to 11 f in 10% yield
together with the reduced compound in 10% yield. In addi-
tion, reaction did not take place without LiI (Scheme 9).
The corresponding allyl iodide was quantitatively produced
from the reaction of 10 f with LiI (3 equiv) in [D7]N,N-dime-
thylformamide. As a result of allyl chlorides being poor sub-
10
[a] Reactions performed in the presence of [PdACTHUNRTGNEUNG(PPh3)4] (4 mol%) and
LiI (3 equiv) in DMF at 1008C. [b] Yield of isolated product.
strates for forming allylindium species and indium metal
reacts with aryl iodides in the presence of LiCl in DMF to
produce aryl or vinyl indium species,[4i] intramolecular cycli-
zation of vinyl bromide or aryl iodides and allyl chlorides
(Table 6, entries 6 and 10) might proceed through oxidative
addition of palladium(0) to allyl halides to form p-allyl pal-
ladium complexes and subsequent reaction of aryl/vinyl
indium species with p-allyl palladium complexes. Another
possibility is that the allylindium intermediate may be
formed from an initial palladium p-allyl complex that subse-
quently undergoes reductive transmetallation with indium
metal.[33]
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Chem. Asian J. 2011, 6, 2147 – 2157

Palladium-Catalyzed Allyl Cross-Coupling Reactions
Conclusions
In conclusion, palladium-catalyzed allyl cross-coupling reac-
tions using in situ generated allylindium from allyl halides
and indium were successfully demonstrated. In situ generat-
ed allylindiums could be effective nucleophilic coupling
partners in palladium-catalyzed cross-coupling reactions. A
wide range of allyl halides, such as allyl iodide, allyl bro-
mide, crotyl bromide, prenyl bromide, geranyl bromide, and
3-bromocyclohexene in cross-coupling reactions, afforded
the corresponding allylic compounds in good to excellent
yields. Stereochemistry of the double bond is retained in the
allylic cross-coupling reaction. Various electrophilic cross-
coupling partners, such as aryl and vinyl halides, dibromoo-
lefin, alkynyl iodide, and aryl and vinyl triflates, participated
well in these reactions. The presence of various substituents,
such as a n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-
phenylamido, nitro, and chloride group on the aromatic ring
of electrophilic coupling partners, showed little effect on the
efficiency of the reactions. The present conditions work
equally well not only intermolecular but also intramolecular
palladium-catalyzed cross-coupling reactions. This method
provides an efficient synthetic method for the introduction
of an allyl group, which can be easily further functionalized
to a sp2- and sp-hybridized carbon. The present method
complements existing synthetic methods as a result of ad-
vantageous features such as easy preparation and handling,
thermal stability, high reactivity and selectivity, operational
simplicity, and low toxicity of
Scheme 9. Effect on LiX in cross-coupling reaction.
Mechanistic Insights
It is stated that allylindium(I) is formed by reaction of allyl
iodide and indium in water, but that in N,N-dimethylforma-
mide, at least two allylindium compounds were formed, one
of which is the same as the compound formed in aqueous
media.[24] Although the mechanism of reaction of in situ
generated allylindium compounds with a variety of electro-
philic coupling partners is not clear at the present time, a
possible reaction pathway is described in Scheme 10. Oxida-
allylindium reagents. These re-
sults should immediately pro-
vide more opportunities for the
elucidation of efficient new cat-
À
alytic C C bond forming reac-
tions.
Acknowledgements
This work was supported by the CRI
Program (No. 2011-0009011) of the
National Research Foundation of
Korea and by NRF grant (2009-
0087013) funded by MEST. This work
was supported by the second phase of
the Brain Korea 21 Program in 2009.
Dr. Sung Hong Kim at the KBSI
(Daegu) is thanked for obtaining the
MS data. The NMR data were ob-
tained from the central instrumental
facility in Kangwon National Univer-
sity.
Scheme 10. Mechanism of palladium-catalyzed allyl cross-coupling reactions.
tive addition of palladium catalyst to electrophile, subse-
quent transmetallation with allylindium reagent in situ gen-
erated from allyl halide (Br and I), and indium, and reduc-
tive elimination affords the allylic cross-coupling products.
Although the role of lithium chloride in the coupling reac-
tion has not been established, we believe that lithium chlo-
ride might accelerate the transmetallation step.
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2156
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Received: December 12, 2010
Published online: May 2, 2011
Chem. Asian J. 2011, 6, 2147 – 2157
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