Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols

Article abstract of DOI:10.1002/chem.201502329

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)₂] and 1,1′-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu₄NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu₄NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η³-allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

Full text of DOI:10.1002/chem.201502329

DOI: 10.1002/chem.201502329
Full Paper
&
Amination
Pentacoordinated Carboxylate p-Allyl Nickel Complexes as Key
Intermediates for the Ni-Catalyzed Direct Amination of Allylic
Alcohols
[
a]
[b]
[b]
[a]
Yusuke Kita, Hironobu Sakaguchi, Yoichi Hoshimoto, Daisuke Nakauchi,
[a]
[c]
[b]
Yasuhito Nakahara, Jean-FranÅois Carpentier,* Sensuke Ogoshi,* and
Kazushi Mashima*
[a]
Abstract: Direct amination of allylic alcohols with primary
tuted allylic alcohols. Such remarkable additive effects of
and secondary amines catalyzed by a system made of
nBu NOAc were elucidated by isolating and characterizing
4
[
Ni(1,5-cyclooctadiene)2] and 1,1’-bis(diphenylphosphino)-
some nickel complexes, manifesting the key role of a charge
3
ferrocene was effectively enhanced by adding nBu NOAc
neutral pentacoordinated h -allyl acetate complex in the
4
and molecular sieves, affording the corresponding allyl
amines in high yield with high monoallylation selectivity for
primary amines and high regioselectivity for monosubsti-
present system, in contrast to usual cationic tetracoordinat-
ed complexes earlier reported in allylic substitution
reactions.
[
6]
Introduction
reactions with hard nucleophiles such as Grignard reagents,
[
7]
[8]
[9]
organoboron, organotin, and organozinc compounds.
Transition metal-catalyzed allylic substitution reactions are effi-
cient and widely utilized synthetic protocols for constructing
Direct catalytic transformation of unactivated allylic alcohols,
which forms water as a sole coproduct, is a highly desirable
[1]
[10]
CÀC and CÀX (X=O, N, S) bonds. For such allylic substitution
reactions, precious metal complexes of palladium, platinum,
rhodium, and iridium have been developed as effective cata-
lysts. In this context, allylic halides, carbonates, and carboxy-
lates are utilized as the most convenient substrates, and their
reaction mechanisms involve a simple nucleophilic attack to
the p-allyl metal species. We have focused on both fundamen-
tal and practical research of Ni-based catalysts because of their
anomalous activities toward a variety of transformations to
replace precious metal catalysts with cheap and abundant
and rational protocol, although the hydroxy group has poor
0
leaving ability. One of us previously reported that a Ni -di-
phosphine system acted as a catalyst for the amination of allyl
[
11]
alcohol with diethylamine to prepare allylamines, the most
versatile organic compounds among allylic-substituted
[
12]
products. Some nonprecious metal complexes also act as
catalysts for direct amination of allylic alcohols with electron-
deficient nitrogen nucleophiles through carbocationic inter-
[
13,14]
mediates.
0
Herein, as an extension of our original Ni catalyst system,
we further report on the remarkable additive effects of
[
2,3]
metals.
Ni-catalyzed allylic substitution reactions with soft
[4]
[5]
[5]
nucleophiles such as amines, alcohols, and thiols are not
so well developed; in fact, nickel is a rather hard metal and
thus its complexes favorably catalyze allylic substitution
nBu NOAc to effectively improve performance for the direct
4
amination of allylic alcohols using a Ni catalyst supported by
a diphosphine ligand: a low catalyst loading, wide substrate
scope, and high monoallylation selectivity were achieved. Such
[
11b]
remarkable additive effects of nBu NOAc
were elucidated
[
a] Dr. Y. Kita, D. Nakauchi, Dr. Y. Nakahara, Prof. Dr. K. Mashima
Department of Chemistry, Graduate School of Engineering Science
Osaka University, Toyonaka, Osaka 560-8531 (Japan)
E-mail: mashima@chem.es.osaka-u.ac.jp
4
by isolating and characterizing some intermediates, including
2
an h -allyl alcohol complex and a charge-neutral pentacoordi-
3
nated h -allyl acetate complex.
[
b] H. Sakaguchi, Dr. Y. Hoshimoto, Prof. Dr. S. Ogoshi
Department of Applied Chemistry
Faculty of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan)
E-mail: ogoshi@chem.eng.osaka-u.ac.jp
Results and Discussion
[
c] Prof. Dr. J.-F. Carpentier
Institut des Sciences Chimiques de Rennes
Organometallics: Materials and Catalysis Dept.
UMR 6226 CNRS-UniversitØ de Rennes 1, 35042 Rennes Cedex (France)
E-mail: jean-francois.carpentier@univ-rennes1.fr
The Ni-catalyzed direct amination of allyl alcohol (1a) and N,N-
dibenzylamine (2a) was initially conducted in the presence of
[
Ni(cod) ] (0.5 mol%; cod=1,5-cyclooctadiene) and 1,4-bis(di-
2
phenylphosphino)butane (dppb, 1.0 mol%) at 808C in aceto-
nitrile for 6 h, giving the corresponding allylamine 3aa in 33%
yield as determined on the basis of 1a (Table 1, entry 1). Am-
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201502329.
Chem. Eur. J. 2015, 21, 14571 – 14578
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monium salts had additive effects that significantly increased
because it facilitates the replacement of 1,5-cyclooctadiene on
[
15]
the yield of 3aa: when 2.5 mol% of NH OAc was added, com-
a nickel center. Consequently, we selected dppf as the best
ligand and acetonitrile as the best solvent. The addition of
a dehydrating agent also had beneficial effects: addition of
molecular sieves 3Š (MS3Š) produced 3aa in 94% yield
(Table 2, entry 18); presumably this is due to the shift of
equilibrium in which the retro reaction of cleaving the CÀN
4
pound 3aa was obtained in 72% yield (Table 1, entry 2). The
addition of nBu NOAc also improved the yield of 3aa (82%,
4
À
Table 1, entry 3), indicating that the OAc anion played a key
role in the present catalytic system. Other counteranions of
À
À
À
tetrabutylammonium salts such as I , PF , BF4 , and tetra-
6
FÀ
0
[16]
kis(3,5-bis(trifluoromethyl)phenyl)borate (BAr ) were less effec-
bond of allylamine was facilitated by the Ni complex.
tive, leading to 31–59% yields (Table 1, entries 4–7). Among
the salts tested, we selected nBu NOAc as the best additive
4
[a]
salt to examine the amounts of the additive. Valuable additive
Table 2. Ligand and solvent screening.
effects of nBu NOAc were observed within the range of 0.5 to
4
1
0 mol% (Table 1, entries 8–11) and the best result was ob-
served using 2.5 mol% of nBu NOAc (Table 1, entry 3). On the
4
other hand, 50 mol% of nBu NOAc had no significant effect,
4
and one equivalent of the additive inhibited the reaction to
[
b]
Entry
Ligand
Solvent
Yield [%]
decrease the yield of 3aa (Table 1, entries 12 and 13).
1
2
3
4
5
6
7
8
9
dppbz
dppe
dppp
dppb
CH
CH
CH
3
CN
3
CN
3
CN
trace
trace
trace
53
86
81
trace
77
7
trace
trace
trace
53
[
a]
Table 1. Screening of additive effects.
3
CH CN
dppf
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
DPEphos
xantphos
Floriani’s ligand
PPh
PtBu
(2-MeOC
3
10
3
[b]
Entry
Additive
none
x
Yield [%]
11
6
H
4
)PPh
)PPh
2
1
1
1
1
1
1
2
3
4
5
6
7
(2-Me
IPr
2
NC
6
H
4
2
1
2
3
4
5
6
7
8
9
–
33
72
82
31
59
57
47
77
71
75
77
36
17
[
c]
NH
4
OAc
2.5
2.5
2.5
2.5
2.5
2.5
0.5
1.0
5.0
dppf
dppf
dppf
dppf
dppf
1,4-dioxane
ClCH CH Cl
74
59
77
85
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
4
4
4
4
4
4
4
4
4
4
4
NOAc
NI
NPF
NBF
2
2
hexane
toluene
CH CN
3
6
4
[
d]
F
18
94
NBAr
NOAc
NOAc
NOAc
NOAc
NOAc
NOAc
[
(
a] Reaction conditions: allyl alcohol (2.6 mmol), N,N-dibenzylamine
3.9 mmol), [Ni(cod) ] (0.5 mol%), ligand (1 mol%), nBu NOAc (2.5 mol%),
CN (0.5 mL) at 608C for 3 h. [b] Yields determined on the basis of
allyl alcohol and determined by H NMR analysis with phenanthrene as
internal standard. [c] In situ generated by IPr*HCl (1 mol%) and KOtBu
2
4
1
0
and CH
3
1
1
10
50
100
1
1
1
2
3
(5 mol%). [d] MS3Š (100 mg) was added.
[
(
a] Reaction conditions: allyl alcohol (2.6 mmol), N,N-dibenzylamine
3.9 mmol), [Ni(cod) ] (0.5 mol%), dppb (1 mol%), additive (xmol%), and
CN (0.5 mL) at 808C for 6 h. [b] Yields determined on the basis of allyl
2
CH
3
1
alcohol and determined by H NMR with phenanthrene as internal
standard.
We next screened the ligand and solvent effects under
milder conditions (608C, 3 h). The bite angle of the diphos-
phine ligand clearly affected the yield of the product. Diphos-
phine ligands with a small bite angle gave almost no reaction
(
(
Table 2, entries 1–3). 1,1’-Bis(diphenylphosphino)ferrocene
dppf) and bis[(2-(diphenylphosphino)phenyl] ether (DPEphos)
were good ligands for the present reaction and the desired
product was obtained in 86 and 81% yield, respectively
(
Table 2, entries 5 and 6). In contrast to bidentate ligands, mon-
Under the optimized conditions, we examined a variety of
odentate phosphines and 1,3-bis(2,6-diisopropyl)imidazol-2-yli-
dene (IPr) were not effective for the present system (Table 2,
entries 9–13). We next screened solvents, that is, 1,4-dioxane,
allylic alcohols (Table 3). The reaction of both linear and
branched allylic alcohols 1b and 1c proceeded smoothly to
give only the linear product 3ba with the same E/Z selectivity
(Table 3, entries 1 and 2); this indicated that this reaction pro-
ceeded through a p-allyl-nickel intermediate (see below). The
1
1
,2-dichloroethane, hexane, and toluene (Table 2, entries 14–
7), revealing that acetonitrile gave the best result, probably
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higher reactivity of branched alcohols as compared with linear
alcohols (Table 3, entries 1 vs. 2 and 3 vs. 4) suggested that the
The reactions of benzylamine as well as para-substituted ani-
lines were efficiently promoted by the Ni catalyst to provide
the desired monoallylated products 3ab, 3ac, 3ad, 3ae, and
3af in high yield and with high monoallylation selectivity.
ortho-Substituted anilines were also good substrates. The ob-
served high monoallylation selectivity can be rationalized by
the large bite angle of the bidentate phosphine ligand, which
2
C=C double bond of allylic alcohols coordinated in h -fashion
to the nickel atom prior to oxidative addition of allylic alcohols,
as later on established by X-ray crystallography (see below).
Electronic and steric effects were evaluated by using 1-aryl-2-
propen-1-ol; no marked electronic and steric trend of substi-
tuents on the aryl group was observed in terms of the yield of
allylamines. Both methoxy- and trifluoromethyl-substituted
variants were converted to allylamines in 84 and 80% yield,
respectively (Table 3, entries 5 and 6). Even with the sterically
congested substrate 1h bearing a 2-methyl group on the
phenyl group, direct amination using the present Ni catalysis
yielded the corresponding allylamine 3ha in 71% yield
3
prevents an attack of the monoallylated product onto the h -
allyl nickel intermediate (see below), similar to our previous
[
18]
platinum system. The reaction of secondary amines also pro-
ceeded smoothly with the present catalytic systems. There was
no obvious correlation between nucleophilicity and yield. N-
Methylaniline (2i), N,N-diethylamine (2j), piperidine (2k), mor-
pholine (2l), N-methylpiperazine (2m), and pyrrolidine (2n)
were all effectively applicable. In particular, the reactions of
morpholine and N-methylpiperidine proceeded smoothly to
afford the corresponding isolated products 3dl and 3dm in
excellent isolated yields.
(
Table 3, entry 7). This protocol can also be applied to the
allylic alcohol bearing a methyl group on 2-position of allyl
group (Table 3, entry 8). 1,3- 1,1- and 3,3-Disubstituted
substrates were not suitable for the present system.
To gain insight into the reac-
tion mechanism and especially
[
a]
Table 3. Scope and limitations of allylic alcohols.
the nature of the remarkable ad-
[
11b]
ditive effects of nBu NOAc,
4
we conducted time-course ex-
periments in the presence or ab-
sence of nBu NOAc under the
4
optimized conditions (Figure 1).
The initial rate dramatically in-
creased by the addition of
[
b]
Entry
Alcohol
Yield of 3 ([%])
(E/Z=84:16)
(E/Z=83:17)
[c]
[d]
[e]
1
2
3
1b (E/Z=97:3)
3ba (84)
3ba (88)
3da (82)
nBu NOAc, suggesting that the
4
1c
acetate anion plays a key role to
form an active intermediate.
1d
Thus, we performed some sto-
ichiometric reactions to clarify
the structures and reactivity of
intermediates (Scheme 1). Treat-
ment of [Ni(cod)2] with 1a
4
5
1e
3da (82)
1 f
3 fa (84)
(
1 equiv) and dppf (1 equiv) in
6
1g
3ga (80)
C D afforded the corresponding
6
6
2
olefin complex [(h -1a)Ni(dppf)]
5) in 77% yield together with
the concomitant formation of
(
7
8
1h
1i
3ha (71)
3ia (84)
2
2
[
(
(h :h -cyclooctadiene)Ni(dppf)]
6) in 23% yield after 15 min at
room temperature (Scheme 1a).
We successfully isolated com-
plex 5 by repeated precipitation,
and its molecular structure was
unambiguously determined by
X-ray diffraction analysis (Fig-
[
(
a] Reaction conditions: alcohol (2.6 mmol), 2a (3.9 mmol), [Ni(cod)
2 4
] (0.5 mol%), dppf (1.0 mol%), nBu NOAc
2.5 mol%), MS3Š (100 mg) and CH CN (0.5 mL) at 608C for 18 h. [b] Yield of the isolated product, based on
3
allylic alcohol. [c] Run for 6 h. [d] Run for 3 h. [e] Run at 808C. The product was obtained in 51% yield when
the reaction was run at 608C.
ure 2a). To our knowledge, this
0
We next investigated the amination of 1a or 1e with a
variety of primary and secondary amines over a prolonged
reaction time (Table 4). The case of primary amines raises the
question of the selectivity between monoallylation and diallyl-
ation. Although some Pd-catalyzed reactions afford diallylated
is the first crystallographic characterization of a Ni complex
2
with an h -coordinated allyl alcohol. The treatment of complex
5 with excess (30 equiv) N,N-dibenzylamine (2a) without
nBu NOAc at 608C for 3 h afforded product 3aa in 96% yield
(GC analysis; Scheme 1b); the addition of nBu NOAc (5 equiv),
4
4
[17]
products selectively from aliphatic primary amines, the pres-
ent Ni-catalyst system showed high monoallylation selectivity.
however, resulted in the formation of 3aa in only 8% yield
along with the generation of significant amounts of nickel par-
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[
a]
Table 4. Scope and limitations of amines.
Scheme 1. a) Stoichiometric reaction giving 5; b) reaction of 5 with 2a; c) re-
activity of pentacoordinated allyl nickel complexes (7 and 8); d) reaction of
tetracoordinated nickel complex 9 with 2a. GC yields are given. [a] Yields de-
3
1
1
termined by P{ H} NMR spectroscopy. The formation of 6 (23%) was also
observed. [b] CH Cl was used as solvent.
2
2
[
(
a] Reaction conditions: 1a or 1e (2.6 mmol), amine (3.9 mmol), [Ni(cod)
0.5 mol%), dppf (1.0 mol%), nBu NOAc (2.5 mol%), MS3Š (100 mg), and
CN (0.5 mL) at 608C for 18 h. Yields of isolated product in parenthe-
2
]
4
CH
3
ses, based on allylic alcohol. Diallylated products 4 were detected only in
trace amounts. No other side product was observed, beside remaining
starting reagents. [b] Run at 808C.
Figure 2. Molecular structures of: a) 5, and b) 7. Hydrogen atoms are omit-
ted for clarity. Selected bond lengths [Š]: (a) C1-C2 1.42(1), C2-C3 1.49(1),
Ni-C1 1.9719(9), Ni-C2 1.957(8), P1-Ni-P2 107.13(9); (b) C1-C2 1.420(4), C2-C3
Figure 1. Time-course of yield of 3aa in the direct amination of 1a with 2a
in the presence (*) or absence (*) of tetrabutylammonium acetate.
1.403(5), Ni-C1 2.058(3), Ni-C2 1.982(4), Ni-C3 2.072(4), Ni-O2 1.947(2).
ticles (“nickel black”). We surmise that this is due to the de-
To clarify whether nBu NOAc plays a key role in the amine
4
3
composition of complex 5 under these conditions, that is,
nucleophilic addition step, we synthesized h -allyl nickel
0
3
without excess allyl alcohol or cod to stabilize the Ni center
complexes [(h -allyl)Ni(dppf)(X)] (7: X=OAc, 8: X=Cl) by the
(
see the Supporting Information for details). Hence, the effect
oxidative addition reaction of CH =CHCH X (X=Cl and OAc) to
2
2
of nBu NOAc on the oxidative addition step cannot be dis-
[Ni(cod) ] in the presence of dppf, and their crystal structures
4
2
cussed from these stoichiometric experiments.
were determined by X-ray diffraction analyses. As shown in
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À
À
1
Figure 2b, the OAc anion for 7, as well as the Cl for 8 (see
amine by an h -acetate ligand to give a pentacoordinated 18-
II
II
the Supporting Information), coordinates to the Ni center in
electron Ni intermediate (D), followed by reductive elimination
to give E, and (ii) an outer sphere pathway through a direct
nucleophilic attack of an amine to an h -allyl ligand. However,
[
21]
an inner coordination manner, resulting in charge-neutral 18-
3
3
electron pentacoordinated h -allyl complexes. This is in sharp
contrast with the reported Pd- and Pt-catalyzed systems that
at this point, we cannot conclude which pathway is plausible.
Finally, the reaction of E with allyl alcohol affords the allyl
amine product to regenerate intermediate A. In the actual re-
action cycle, the formation of allylammonium acetate salts is
3
proceed through cationic 16-electron tetracoordinated h -allyl
[
1,19]
complexes.
We next examined the treatment of nickel com-
plexes 7 and 8 with 2a (5 equiv). Scheme 1c indicates that the
[
18a,22]
reaction of acetate complex 7 with 2a in CH CN occurred at
also possible.
For the other acetate-free ammonium salts,
3
room temperature to afford 3aa in 54% yield after 1 h. On the
other hand, the treatment of 8 under the same reaction condi-
that is, nBu NPF , and nBu NBF , which also have beneficial
4
6
4
4
effects on the catalyst activity (Table 1), a different origin from
that proposed in Scheme 2 may be suggested. A possible
explanation is that these ammonium salts favor abstraction of
tions afforded 3aa in only 9%, and the addition of nBu NOH
4
(
5 equiv) had no effect on reaction of 8 with 2a; yet, the addi-
À
tion of nBu NOAc (5 equiv) significantly increased the yield of
OH in hydroxo complex B, stabilizing a cationic allyl nickel
4
À
3
aa (76%), suggesting that bonding of the OAc ligand to the
complex, which is more reactive than charge neutral complex
B. In fact, Nagashima et al. have reported that reducing the
electron density of Ni increased the electrophilicity of the allyl
nickel atom is critical in the nucleophilic addition step. In addi-
tion, complex 7 showed catalytic activity toward direct amina-
3
tion of 1a in CH CN at 608C for 3 h, affording allylamine 3aa
ligand in nucleophilic attack of amine to h -allyl nickel
3
[
23]
in 75% yield [Eq. (1)], suggesting that this complex would be
included in the catalytic cycle. The relatively lower yield is
complexes.
0
probably due to the lack of cod, which can stabilize the Ni
Conclusion
center, and/or the lower amounts of acetate (Table 1, entries 8
and 9). To elucidate the high reactivity of acetate complex 7,
We have studied a nickel-diphosphine-ammonium salt catalytic
system for the direct amination reaction of allylic alcohols. A
variety of primary amines are applicable, affording the corre-
sponding allylamines with high monoallylation selectivity.
Remarkably, the ammonium salt plays a key role in generating
the treatment of 8 with nBu NOAc to give 7 in situ was moni-
4
1
tored by H NMR spectroscopy in CD Cl . We noted an obvious
2
2
change in the spin system of 8 along with a downfield shift of
the resonance of the central allylic CÀH signal from d =
H
3
5
.02 ppm (tt, J =13.0 and 7.0 Hz) for 8 to d =5.14 ppm
a highly reactive charge-neutral pentacoordinated h -allyl-
HH
H
II
(
quin, JHH =10.3 Hz) for 7; this is most likely due to a structural
acetate Ni intermediate, in which the acetate ligand assists a
rearrangement upon the p-to-s allyl interconversion in 7 at
room temperature. We therefore assumed that the genera-
nucleophilic attack of amines. This mechanistic scenario differs
[
19]
[11b]
from the one originally proposed
in which ammonium salts
tion of a highly reactive p-allyl acetate nickel intermediate
were assumed to increase the polarity of the reaction medium
À
3
through an exchange of OH (counteranion or ligand) with the
and hence favor the formation of cationic tetracoordinated h -
À
OAc ligand is key to the reaction progress. The comparison of
allyl Ni intermediates, as usually proposed in allylic substitution
reactions with other metal complexes (Pd). Further application
of our catalytic system involving such reactive carboxylate
intermediates is ongoing.
3
the reactivity of the pentacoordinated h -allyl acetate nickel
3
complex 7 and a known tetracoordinated h -allyl acetate nickel
[
20]
complex (9)
revealed that 7 exhibited higher reactivity
toward 2a, giving 3aa in 71% yield (Scheme 1c), compared
with that of 9, which gave 3aa in 28% yield (Scheme 1d). This
À
Experimental Section
again manifested the importance of the fifth OAc ligand
attached to the nickel center and the bidentate dppf for
stabilizing the pentacoordinated structure.
General
All reactions and manipulations involving air- and moisture-sensi-
tive organometallic compounds were operated by using standard
Schlenk or dry box techniques under inert gas (nitrogen or argon)
atmosphere. 1,4-Dioxane was dried and deoxygenated by distilla-
tion over sodium benzophenone ketyl under argon, and methanol
and ethanol were distilled from corresponding magnesium alkox-
ide under argon. iPrOH and DMF were distilled from calcium hy-
dride. CH Cl , Et O, hexane, THF, and toluene were dried and de-
Scheme 2 shows a plausible reaction mechanism. The coor-
2
2
2
0
dination of allyl alcohol to Ni /dppf leads to the formation of
oxygenated by using Grubbs column (Glass Counter Solvent Dis-
pending System, Nikko Hansen & Co, Ltd.). Deuterated solvents
2
[
(h -allyl alcohol)Ni(dppf)] (A, compound 5), which is in equilib-
(
CD Cl and CD CN) were degassed prior to use. Other chemicals
2 2 3
rium with [Ni(cod)(dppf)] (6) upon the presence of free cod.
1
were purchased and used without further purification. H NMR
0
Oxidative addition of allyl alcohol to the Ni center subse-
13
1
19
(
400 MHz),
C{ H} NMR (100 MHz),
F NMR (376 MHz), and
À
quently affords B, from which ligand exchange of OH with
31
1
P{ H} NMR (162 MHz) spectra were measured on Bruker Avance
À
3
OAc occurs to give an intermediate [(h -allyl)Ni(dppf)(OAc)]
1
III-400 spectrometers. All H NMR chemical shifts were recorded in
(
(
C, compound 7). Two possible subsequent pathways exist:
i) An inner sphere pathway through a proton abstraction from
ppm (d) relative to tetramethylsilane or referenced to the chemical
shifts of residual solvent resonances (CHCl was used as internal
3
Chem. Eur. J. 2015, 21, 14571 – 14578
www.chemeurj.org
14575
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crystallization from THF (including
1
% N,N-dibenzylamine)/hexane at
1
À358C. H NMR (400 MHz, C D ,
6
6
2
28C): d=7.86–7.63 (m, 10H, Ar-
H), 7.09–7.03 (m, 10H, Ar-H), 4.32
s, 1H Cp-H), 4.29 (brs, 1H Cp-H),
.24 (brs, 1H Cp-H), 4.16 (brs, 1H
(
4
Cp-H), 3.88–3.91 (br, 5H, Cp-H (4H)
and CHCHHOH (1H) are over-
lapped), 3.54–3.58 (brm, 2H,
CH CHCH2 (1H) and CHCHHOH
2
(
1H) are overlapped), 2.62 (m, 1H,
CHH=CH), 2.44 (m, 1H, CHH=
CH), 0.90 ppm (m, 1H, CHCH OH).
2
13
1
Recording of the C{ H} NMR of 5
was unsuccessful due to the low
stability of the compound at room
temperature. We also tried to mea-
sure the NMR spectrum at À308C;
however, this also failed due to
a precipitation of the compound.
31
1
P{ H} NMR (162 MHz, C D , 228C):
6
6
d=24.1 (d, J =29.2 Hz), 23.8 ppm
PP
(
d, J =29.2 Hz); elemental analy-
PP
Scheme 2. Plausible reaction mechanism.
sis calcd (%) for C H FeNiOP : C
37 34 2
6
5
6.21, H 5.11; found: C 66.22, H
.01.
3
1
3
1
[(h -allyl)Ni(dppf)(OAc)] (7): A so-
standard, d=7.26 ppm). All C{ H} NMR chemical shifts were re-
lution of allyl acetate (60.1 mg, 0.60 mmol) in THF (5 mL) was
added slowly to a solution of [Ni(cod) ] (138 mg, 0.50 mmol) and
2
dppf (277 mg, 0.50 mmol) in THF (20 mL) at room temperature.
After stirring the reaction mixture for 1 h, all volatiles were re-
moved under reduced pressure to give 7 (351 mg, 0.49 mmol,
corded in ppm (d) relative to carbon resonances in CDCl at d=
7.16 ppm. All F NMR chemical shifts were recorded in ppm (d)
relative to fluorine resonance in a,a,a-trifluorotoluene as an exter-
3
1
9
7
3
1
1
nal standard at d=À63.90 ppm. P{ H} NMR chemical shifts were
recorded in ppm (d) relative to 85% H PO as external standard at
3
4
9
8%) as a brown solid. A single crystal suitable for X-ray diffraction
analysis was prepared by recrystallization from THF/hexane at
d=0.00 ppm. HPLC spectra were recorded on a JASCO UV-2075
and PU-2089. Mass spectra were obtained on Bruker Daltonics Mi-
croTOF II-HB and JEOL JMS-700. All melting points were recorded
on Yanaco micro melting point apparatus. Flash column chroma-
tography was performed using silica gel 60 (0.040–0.0663 nm,
1
À358C. H NMR (400 MHz, CD Cl , À308C): d=7.62–7.66 (m, 8H,
2
2
Ar-H), 7.38–7.49 (m, 12H, Ar-H), 5.20 (brm, 1H, CH CHCH ), 4.54 (s,
2
2
4
H, Cp-H), 4.31 (s, 4H, Cp-H), 3.25 (br, 2H, syn-CH CHCH ), 3.15
2 2
brd, 2H, J =12.4 Hz, anti-CH CHCH ), 1.79 (s, 3H, COCH );
HH 2 2 3
(
2
30–400 mesh ASTM). Elementary analyses were performed at
1
3
1
C{ H} NMR (100 MHz, CD Cl , À308C): d=176.6, 134.7 (d, J
=
CP
2
2
Instrumental Analysis Center, Faculty of Engineering, Osaka Univer-
sity. For some compounds, accurate elemental analysis was prec-
luded by extreme air or thermal sensitivity. X-ray crystal data were
collected with a Rigaku RAXIS-RAPID Imaging Plate diffractometer.
3
7
6
2
9.1 Hz), 133.8 (d, J =9.5 Hz), 130.0, 128.2 (d, J =8.6 Hz), 104.5,
CP CP
7.6 (dd, JCP =41.9, 5.7 Hz), 74.7 (d, J =9.5 Hz), 72.3 (d, JCP =
CP
.7 Hz), 63.0 (m), 26.5; P{ H} NMR (162 MHz, CD Cl , 228C): d=
2 2
0.3 ppm; elemental analysis calcd (%) for C H FeNiO P : C 65.68,
39 36 2 2
31
1
H 5.09; found: C 65.61, H 5.12.
General procedure for direct amination of allylic alcohols
3
[
(h -allyl)Ni(dppf)Cl] (8): A solution of allyl chloride (60.1 mg,
0
.60 mmol) in toluene (5 mL) was added slowly to a solution of
In
a glovebox, [Ni(cod)2] (0.013 mmol), dppf (0.026 mmol),
[
Ni(cod) ] (138 mg, 0.50 mmol) and dppf (277 mg, 0.50 mmol) in
2
nBu NOAc (0.065 mmol), and MS3Š (100 mg) were added in
4
toluene (20 mL) at room temperature. The formation of brown
crystals was observed, which were collected after 12 h by filtration
to give 8 (343 mg, 0.50 mmol, 100%). The molecular structure of 8
a 20 mL Schlenk flask, followed by addition of CH CN (0.5 mL),
3
amine 2 (3.9 mmol), and allylic alcohol 1 (2.6 mmol). After reflux
for a time, the reaction mixture was directly purified by flash
column chromatography to afford the corresponding allyl amine 3.
1
is shown in Figure S5 (the Supporting Information). H NMR
(
400 MHz, CD Cl , 228C): d=7.72–7.76 (m, 8H, Ar-H), 7.35–7.45 (m,
2 2
Reported yields are based on starting allylic alcohols.
2
12H, Ar-H), 5.02 (tt, JHH =13.0, 7.0 Hz, 1H, CH CHCH ), 4.69 (br, 4H,
2 2
[
(h -allyl alcohol)Ni(dppf)] (5): Compound 1a (580 mg, 10 mmol)
Cp-H), 4.29 (br, 4H, Cp-H), 3.50 (dm, JHH =7.0 Hz, 2H, CH CHCH ),
2
1
2
was added slowly to a solution of [Ni(cod)] (275 mg, 1.0 mmol) and
dppf (544 mg, 1.0 mmol) in toluene (40 mL) at room temperature.
Then, hexane (ca., 30 mL) was added to this mixture, and the resul-
tant solution was stored at À608C for a week, which gave an
orange precipitate. After collecting the precipitates by filtration,
compound 1a (580 mg, 10 mmol) was again added dropwise to
the filtrate. After several times of this reprecipitation, compound 5
was isolated as a yellow solid (593 mg, 0.90 mmol, 90%). A single
crystal suitable for X-ray diffraction analysis was prepared by re-
13
3
.08 ppm (dm, JHH =13.0 Hz, 2H, CH CHCH );
C{ H} NMR
2
2
(
1
100 MHz, CD Cl , 228C): d=134.3 (m), 130.3, 128.5, 128.3 (m),
06.6, 75.3 (m), 72.1 (m), 68.1 ppm; P{ H} NMR (162 MHz, CD Cl ,
2 2
2
2
31
1
2
28C): d=24.0 ppm; elemental analysis calcd (%) for
C H FeNiClP : C 64.44, H 4.82; found: C 63.86, H 5.16.
37
33
2
[24] 1
N,N-Dibenzylprop-2-en-1-amine (3aa):
H NMR (400 MHz, CDCl3,
308C): d=7.46–7.26 (m, 10H, aromatic), 6.03–5.94 (m, 1H, CH =
2
CHCH ), 5.28 (dd, 1H, CHH=CHCH ), 5.22 (dd, 1H, CHH=CHCH ),
2
2
2
Chem. Eur. J. 2015, 21, 14571 – 14578
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14576
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
3
.65 (s, 4H, NCH Ph), 3.14 ppm (d, J=6.2 Hz, 2H, CHCH N);
J=15.9 Hz, 1H, CH=CHCH ), 6.50 (td, J=15.9, 6.5 Hz, 1H, CH=
2
2
2
1
3
C NMR (100 MHz, CDCl , 308C): d=139.8, 136.1, 128.9, 128.3,
CHCH ), 3.83 (s, 4H, NCH Ph), 3.43 ppm (d, J=6.4 Hz, 2H, CHCH N);
3
2
2
2
13
1
26.9, 117.4, 57.9, 56.5 ppm.
C NMR (100 MHz, CDCl , 308C): d=139.7, 137.3, 132.6, 128.9,
3
[25]
1
128.6, 128.3, 127.8, 127.4, 127.0, 126.4, 58.1, 55.9 ppm.
N,N-Dibenzylbut-2-en-1-amine (3ba):
H NMR (400 MHz, CDCl3,
[
18a]
3
08C): (E)-3ba: d=7.42–7.23 (m, 10H, aromatic), 5.66–5.54 (m, 2H,
N,N-Dibenzyl-3-(4-methoxyphenyl)prop-2-en-1-amine
(3 fa):
1
CH=CHCH ), 3.60 (s, 4H, NCH Ph), 3.03 (d, J=5.4 Hz, 2H, CHCH N),
H NMR (400 MHz, CDCl , 308C): d=7.73–7.42 (m, 12H, aromatic),
2
2
2
3
1
1
.72 ppm (d, J=5.4 Hz, 3H, CH CH=CH); (Z)-3ba: d=7.42–7.23 (m,
0H, aromatic), 5.71–5.53 (m, 2H, CH=CHCH2), 3.60 (s, 4H,
7.12 (d, J=8.6 Hz, 2H, aromatic), 6.80 (d, J=15.8 Hz, 1H, CH=
CHCH ), 6.50 (td, J=15.8, 6.5 Hz, 1H, CH=CHCH ), 3.99 (s, 3H,
3
2
2
NCH Ph), 3.11 (d, J=5.2 Hz, 2H, CHCH N), 1.60 ppm (d, J=5.2 Hz,
ArOCH3), 3.95 (s, 4H, NCH Ar), 3.54 ppm (d, J=6.5 Hz, 2H,
2
2
2
1
3
13
3
1
1
H, CH CH=CH); C NMR (100 MHz, CDCl , 308C): (E)-3ba: d=
40.0, 128.9, 128.5, 128.3, 126.9, 57.8, 55.6, 18.0 ppm; (Z)-3ba: d=
40.0, 129.0, 128.6, 127.9, 127.1, 126.9, 58.1, 49.8, 13.3 ppm.
CHCH N); C NMR (100 MHz, CDCl , 308C): d=159.1, 139.7, 132.0,
3
3
2
3
130.0, 128.9, 128.2, 127.4, 126.8, 125.3, 114.0, 57.9, 55.9, 55.1 ppm.
N,N-Dibenzyl-3-(4-trifluoromethylphenyl)prop-2-en-1-amine
[26]
1
N-Benzylprop-2-en-1-amine (3ab):
H NMR (400 MHz, CDCl3,
[18a] 1
(3ga):
H NMR (400 MHz, CDCl , 308C): d=7.66–7.33 (m, 14H,
3
3
08C): d=7.36–7.27 (m, 4H, aromatic), 6.01–5.92 (m, 1H, CH =
2
aromatic), 6.68–6.63 (m, 1H, CH=CHCH ), 6.50–6.45 (m, 1H, CH=
2
CHCH ), 5.26–5.25 (m, 1H, CHH=CHCH ), 5.16–5.14 (m, 1H, CHH=
2
2
CHCH2), 3.76–3.74 (m, 4H, NCH Ar), 3.37–3.34 ppm (m, 2H,
2
CHCH ), 3.83 (s, 2H, NHCH Ph), 3.32 (d, J=5.8 Hz, 2H, CHCH N),
13
2
2
2
CHCH N); C NMR (100 MHz, CDCl , 308C): d=140.8, 139.6, 131.0,
2
3
1
3
1
1
.64 ppm (s, 1H, NH); C NMR (100 MHz, CDCl , 308C): d=148.1,
3
129.2 (q, J =32.3 Hz), 128.9, 128.4, 127.1, 126.5, 125.5 (q, J =
C
F
C
F
35.6, 129.3, 117.7, 116.3, 113.2, 46.7 ppm.
19
3
.9 Hz), 124.5 (q, J =272.2 Hz), 58.3, 55.9 ppm; F NMR (377 MHz,
CF
[27] 1
N-Allylaniline (3ac):
H NMR (400 MHz, CDCl , 308C): d=7.21–
CDCl , 308C): d=62.0 ppm.
3
3
7
1
1
.18 (m, 2H, aromatic), 6.75–6.64 (m, 3H, aromatic), 6.03–5.93 (m,
H, CH =CHCH ), 5.33–5.28 (m, 1H, CHH=CHCH ), 5.20–5.17 (m,
[18a]
N,N-Dibenzyl-3-(2-methylphenyl)prop-2-en-1-amine
(3ha):
1
2
2
2
H NMR (400 MHz, CDCl , 308C): d=7.55–7.28 (m, 14H, aromatic),
.89 (d, J=15.8 Hz, 1H, CH=CHCH ), 6.31 (td, J=15.8, 6.5 Hz, 1H,
3
13
H, CHH=CHCH ), 4.17–3.47 (m, 3H, NH and CHCH N); C NMR
2
2
6
2
(
100 MHz, CDCl , 308C): d=140.0, 136.5, 128.6, 128.4, 127.2, 116.5,
3
CH=CHCH ), 3.79 (s, 4H, NCH Ph), 3.39 (d, J=6.4 Hz, 2H, CHCH N),
2
2
13
2
5
3.2, 51.7 ppm.
2
.46 ppm (s, 3H, PhCH3); C NMR (100 MHz, CDCl , 308C): d=
139.7, 136.5, 135.1, 130.5, 130.3, 129.0, 128.9, 128.3, 127.3, 127.0,
126.1, 125.9, 58.0, 56.0 ppm.
3
[26] 1
N-Allyl-4-methylaniline (3ad):
d=6.99 (d, J=8.2 Hz, 2H, aromatic), 6.59 (d, J=8.3 Hz, 2H, aromat-
ic), 5.97 (tdd, J=17.1, 10.2, 5.0 Hz, 1H, CH =CHCH ), 5.28 (d, J=
1
4
3
1
H NMR (400 MHz, CDCl , 308C):
3
2
2
[29]
1
N,N-Dibenzyl-2-methylprop-2-en-1-amine
(3ia):
H NMR
7.1 Hz, 1H, CHH=CHCH ), 5.16 (d, J=10.2 Hz, 1H, CHH=CHCH ),
2 2
(
400 MHz, CDCl , 308C): d=7.50–7.32 (m, 10H, aromatic), 5.11–4.99
3
.02 (brs, 1H, NH), 3.76 (d, J=5.4 Hz, 2H, CHCH N), 2.25 ppm (s,
2
(
1
1
m, 2H, CH =CCH ), 3.63 (s, 4H, NCH Ph), 3.05 (brs, 2H, CHCH N),
1
3
2
2
2
2
H, ArCH3); C NMR (100 MHz, CDCl , 308C): d=145.9, 135.8,
13
3
.90 (s, 3H, CH C=CH ); C NMR (100 MHz, CDCl , 308C): d=144.0,
3
2
3
29.7, 126.7, 116.0, 113.2, 46.9, 20.4 ppm.
40.0, 128.8, 128.3, 126.9, 112.9, 60.9, 58.1, 20.9 ppm.
[27] 1
N-Allyl-4-methoxyaniline (3ae):
d=6.82 (d, J=8.8 Hz, 2H, aromatic), 6.63 (d, J=8.8 Hz, 2H, aromat-
ic), 6.00 (tdd, J=17.2, 10.3, 5.1 Hz, 1H, CH =CHCH ), 5.31 (d, J=
1
3
H NMR (400 MHz, CDCl , 308C):
3
[30]
1
N-Cinnamyl-N-methylaniline (3di):
H NMR (400 MHz, CDCl3,
08C): d=7.45–7.28 (m, 7H, aromatic), 6.89–6.59 (m, 3H, aromatic),
.61 (d, J=15.8 Hz, 1H, CH=CHCH ), 6.37–6.30 (td, J=15.8, 5.3 Hz,
3
6
2
2
2
7.3 Hz, 1H, CHH=CHCH ), 5.19 (d, J=10.3 Hz, 1H, CHH=CHCH ),
2 2
CH=CHCH ), 4.16 (d, J=5.3 Hz, 2H, CHCH N), 3.06 ppm (s, 3H,
2
2
.77 (s, 3H, ArOCH ), 3.75 (d, J=5.3 Hz, 2H, CHCH N), 3.49 ppm
3
2
13
1
3
NCH
3
); C NMR (100 MHz, CDCl
3
, 308C): d=149.7, 137.0, 131.4,
(
brs, 1H, NH); C NMR (100 MHz, CDCl , 308C): d=152.3, 142.3,
3
1
29.3, 128.6, 127.5, 126.4, 125.8, 116.7, 112.7, 54.9, 38.1 ppm.
1
35.9, 116.1, 114.9, 114.4, 55.8, 47.6 ppm.
[26]
1
[27]
1
N,N-Diethyl-3-phenylprop-2-en-1-amine
(3dj):
H NMR
N-Allyl-4-trifluoromethylaniline (3af):
3
matic), 5.93 (tdd, J=17.2, 10.3, 5.1 Hz, 1H, CH =CHCH ), 5.29 (m,
1
3
1
H NMR (400 MHz, CDCl3,
(
400 MHz, CDCl , 308C): d=7.39–7.20 (m, 5H, aromatic), 6.52 (d,
J=15.7 Hz, 1H, CH=CHCH ), 6.30 (td, J=15.8, 6.7 Hz, 1H, CH=
CHCH ), 3.26 (d, J=6.8, 2H, CHCH N), 2.59 (q, J=7.2 Hz, 4H,
3
08C): d=7.41 (d, J=8.4 Hz, 2H, aromatic), 6.65 (d, 8.4 Hz, 2H, aro-
2
2
2
2
2
H, CHH=CHCH ), 5.21 (m, 1H, CHH=CHCH ), 4.64 (brs, 1H, NH),
2 2
1
3
1
3
NCH CH ), 1.08 ppm (t, J=7.2 Hz, 6H, NCH CH );
C NMR
2
3
2
3
.82 ppm (m, 2H, CHCH N); C NMR (100 MHz, CDCl , 308C): d=
2
3
(
100 MHz, CDCl , 308C): d=137.3, 132.3, 128.6, 127.7, 127.4, 126.3,
3
50.7, 134.6, 129.2, 126.7 (q, J =3.7 Hz), 125.2 (q, J =270.0 Hz),
CF
CF
1
9
55.7, 46.8, 11.8 ppm.
119.1 (q, J =32.5 Hz), 116.8, 112.2, 46.1 ppm; F NMR (377 MHz,
CF
[30] 1
CDCl , 308C): d=60.1 ppm.
1-Cinnamylpiperidine (3dk):
H NMR (400 MHz, CDCl , 308C):
3
d=7.39–7.19 (m, 5H, aromatic), 6.50 (d, J=15.8 Hz, 1H, CH=
CHCH ), 6.31 (td, J=15.8, 6.7 Hz, 1H, CH=CHCH ), 3.12 (dd, J=6.8,
.3 Hz, 2H, CHCH N), 2.43 (brs, 4H, NCH CH ), 1.64–1.59 (m, 4H,
2 2 2
NCH CH ), 1.48–1.44 ppm (m, 2H, NCH CH CH ); C NMR (100 MHz,
3
[28]
1
N-Allyl-2-methoxyaniline (3ag):
d=6.89–6.64 (m, 4H, aromatic), 6.00 (tdd, J=17.1, 10.3, 5.0 Hz, 1H,
CH =CHCH ), 5.29 (dd, J=17.3, 3.1 Hz, 1H, CHH=CHCH ), 5.17 (dd,
J=10.2, 3.1 Hz, 1H, CHH=CHCH ), 4.65 (brs, 1H, NH), 3.86 (s, 3H,
ArOCH ), 3.81 ppm (m, 2H, CHCH N); C NMR (100 MHz, CDCl3,
H NMR (400 MHz, CDCl , 308C):
3
2
2
1
2
2
2
13
2
2
2
2
2
2
1
3
CDCl , 308C): d=137.2, 132.7, 128.6, 127.4, 127.3, 126.4, 62.0, 54.7,
3
3
2
2
6.1, 24.5 ppm.
4-Cinnamylmorpholine (3dl):
d=7.39–7.22 (m, 5H, aromatic), 6.55 (d, J=15.8 Hz, 1H, CH=
CHCH ), 6.31–6.24 (td, J=15.9, 6.8 Hz, 1H, CH=CHCH ), 3.76 (t, J=
4.5 Hz, 4H, NCH CH O), 3.19 (d, J=6.8 Hz, 2H, CHCH N), 2.55 ppm
(brs, 4H, NCH CH O); C NMR (100 MHz, CDCl , 308C): d=136.7,
133.3, 128.5, 127.5, 126.3, 125.9, 66.8, 61.3, 53.6 ppm.
3
4
08C): d=146.8, 138.0, 135.6, 121.2, 116.5, 115.8, 110.1, 109.4, 55.3,
6.2 ppm.
[30] 1
H NMR (400 MHz, CDCl , 308C):
3
[27] 1
N-Allyl-2-methylaniline (3ah):
d=7.15–7.06 (m, 2H, aromatic), 6.70–6.63 (m, 2H, aromatic), 6.02
H NMR (400 MHz, CDCl , 308C):
3
2
2
(
tdd, J=17.2, 10.3, 5.2 Hz, 1H, CH =CHCH ), 5.30 (dd, J=17.1,
2
2
2
2
2
13
3
.1 Hz, 1H, CHH=CHCH ), 5.20 (dd, J=10.4, 3.1 Hz, 1H, CHH=
2
2
3
2
CHCH ), 4.12–3.74 (m, 3H, NH and CHCH N), 2.18 ppm (s, 3H,
PhCH3); C NMR (100 MHz, CDCl , 308C): d=146.0, 135.7, 130.1,
2
2
1
3
[30]
1
3
1-Cinnamyl-4-methylpiperazine (3dm):
H NMR (400 MHz,
CDCl , 08C): d=7.37–7.18 (m, 5H, aromatic), 6.51 (d, J=15.8 Hz,
1H, CH=CHCH ), 6.27 (td, J=15.8, 6.8 Hz, 1H, CH=CHCH ), 3.15 (d,
J=6.8 Hz, 2H, CHCH N), 2.47 (brs, 8H, methylene), 2.28 ppm (s,
2
1
27.2, 122.0, 117.2, 116.2, 110.1, 46.6, 17.5 ppm.
N,N-Dibenzyl-3-phenylprop-2-en-1-amine
400 MHz, CDCl , 308C): d=7.61–7.36 (m, 15H, aromatic), 6.72 (d,
3
[26]
1
(3da):
H NMR
2
2
(
3
Chem. Eur. J. 2015, 21, 14571 – 14578
www.chemeurj.org
14577
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
1
3
3
1
H, NCH3); C NMR (100 MHz, CDCl , 308C): d=137.0, 133.2, 128.6,
[8] D.-M. Cui, N. Hashimoto, S.-i. Ikeda, Y. Sato, J. Org. Chem. 1995, 60,
3
5752–5756.
27.5, 126.6, 126.4, 61.1, 55.2, 53.2, 46.1 ppm.
[
31]
1
[9] S. Son, G. C. Fu, J. Am. Chem. Soc. 2008, 130, 2756–2757.
10] a) J. Muzart, Tetrahedron 2005, 61, 4179–4212; b) Y. Tamaru, Eur. J. Org.
Chem. 2005, 2647–2656; c) J. Muzart, Eur. J. Org. Chem. 2007, 3077–
3089; d) B. Sundararaju, M. Achard, C. Bruneau, Chem. Soc. Rev. 2012,
41, 4467–4483.
4
-Cinnamylpyrrolidine (3dn):
H NMR (400 MHz, CDCl , 308C):
3
[
d=7.39–7.20 (m, 5H, aromatic), 6.54 (d, J=15.8 Hz, 1H, CH=
CHCH ), 6.34 (td, J=15.8, 6.7 Hz, 1H, CH=CHCH ), 3.28 (d, J=
.7 Hz, 2H, CHCH N), 2.59 (brs, 4H, NCH CH ), 1.84–1.80 ppm (m,
2 2 2
H, NCH CH ); C NMR (100 MHz, CDCl , 308C): d=127.3, 132.2,
28.7, 127.6, 127.5, 126.5, 58.5, 54.2, 23.7 ppm.
2
2
6
4
1
1
3
2
2
3
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Straightforward Synthesis” (23105546) from MEXT, and ACT-C
from the Japan Science and Technology Agency (JST). Y.H.
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Published online on August 26, 2015
Chem. Eur. J. 2015, 21, 14571 – 14578
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