An efficient and convenient palladium catalyst system for the synthesis of amines from allylic alcohols

Article abstract of DOI:10.1002/cssc.201200247

A novel catalyst system for efficient amination of allylic alcohols with aryl and alkyl amines is presented. By applying a convenient combination consisting of Pd(OAc)₂/1,10-phenanthroline, a variety of allylic alcohols reacted smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity. The usefulness of our protocol is demonstrated in the one-step synthesis of the antifungal drug naftifine and the calcium channel blocker flunarizine. One pot is all it takes: By applying a convenient combination consisting of Pd(OAc)₂/1,10- phenanthroline, a variety of allylic alcohols reacts smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity (see picture).

Full text of DOI:10.1002/cssc.201200247

DOI: 10.1002/cssc.201200247
An Efficient and Convenient Palladium Catalyst System for
the Synthesis of Amines from Allylic Alcohols
Debasis Banerjee, Rajenahally V. Jagadeesh, Kathrin Junge, Henrik Junge, and
Matthias Beller*[a]
A novel catalyst system for efficient amination of allylic alco-
hols with aryl and alkyl amines is presented. By applying a con-
venient combination consisting of Pd(OAc)2/1,10-phenanthro-
line, a variety of allylic alcohols reacted smoothly to give the
corresponding secondary and tertiary amines in good to excel-
lent yields with high regioselectivity. The usefulness of our pro-
tocol is demonstrated in the one-step synthesis of the antifun-
gal drug naftifine and the calcium channel blocker flunarizine.
Introduction
Amines and their derivatives are widely used for the synthesis
of a variety of pharmaceuticals, dyes, agrochemicals, and poly-
mers.[1] A variety of them have significant importance as funda-
mental building blocks for the bulk- and fine-chemical indus-
tries, as well as for the synthesis of numerous bioactive mole-
cules such as alkaloids, amino acids, and nucleotides.[2] Among
the different types of amines allylic amines also represent
a common structural motif present in various biologically
active compounds. Selected examples include the antifungal
drug naftifine[3a,b] and the calcium channel blocker flunarizi-
ne.[3c] Furthermore, allylic amines are of interest as advanced
intermediates for ring-closing metathesis,[4a] asymmetric iso-
merization,[4b] and the total synthesis of several natural prod-
ucts.[2] Therefore, the development of novel and improved cat-
alysts for the synthesis of allyl amines is of continuing interest.
Transition-metal-catalyzed substitution reactions of activated
allylic alcohol derivatives with nitrogen nucleophiles have
become the most attractive synthetic tool for their synthesis.[5]
These reactions are known to proceed through a p-allyl metal
intermediate generated by the oxidative addition of the allylic
substrate to a low-valence metal center, followed by addition
of the nitrogen nucleophile to form the new CÀN bond in
a regio-, stereo-, and enantioselective manner. The pioneering
work in this area was reported by Tsuji and Trost.[5a,b] There-
after, palladium-catalyzed allylation reactions have become
one of the most powerful methods for the construction of al-
lylic CÀC and carbon–heteroatom (N, O, S) bonds.
geously, the use of allylic alcohols as substrates might also
avoid additional activation and (de)protection steps.
In the last two decades, significant progress has been ach-
ieved in the direct amination of alcohols mainly by using
ruthenium- and iridium-based catalysts. Applying these cata-
lysts in so-called “borrowing hydrogen”[8] or “hydrogen auto-
transfer” reactions,[9] the alcohol is dehydrogenated in situ fol-
lowed by subsequent formation of the respective imine. Final
re-hydrogenation leads to the desired amine. Alternatively, al-
lylic alcohols can be activated by palladium and related cata-
lysts, which often requires the addition of catalytic or stoichio-
metric amounts of additives, such as As2O3,[10] B2O3,[11] BPh3,[12]
BEt3,[13] SnCl2,[14] CO2,[15] Ti(iOPr)4,[16] Nb(OEt)5,[17] and carboxylic
acids,[6] to activate the CÀO bond and promote the leaving
ability of the hydroxyl group.
Notably, in the last decade, several reports showed that pal-
ladium- and platinum-catalyzed reactions of allylic alcohols
were possible without the use of activators. In this respect, the
recent work of Ghosh and Sarkar[18a] as well as Mashima and
co-workers[18b,c] is of special interest. Ozawa and co-workers re-
ported an atom-economic synthesis of allyl amines using p-al-
lylpalladium complexes with the diphosphinidenecyclobutene
ligand (DPCB).[19] Particularly, le Floch and co-workers studied
the reactivity of a range of cationic palladium complexes in
combination with variety mono- or bidentate phosphine li-
gands for the amination of allyl alcohols.[20] Moreover, the re-
search groups of Ikariya,[21] Shinokubo and Oshima,[22] and
Berit[23] also considerably contributed to the development of
this methodology. Nevertheless, limited substrate scope and
A considerable disadvantage of most reported metal-cata-
lyzed allylic substitution reactions is the required preactivation
of the hydroxyl group[6] because of its poor leaving ability.
Hence, in general, these reactions are performed with allylic
halides, acetates, carbonates, phosphonates, and related com-
pounds with better leaving groups. In contrast, the direct use
of readily available allylic alcohols would represent a cost-effec-
tive, salt-free, atom-economic, more benign CÀN bond-forming
process.[7] In such a transformation water is formed as the only
byproduct, whereas conventional allylic esters and halides pro-
duce stoichiometric amounts of undesired salt waste. Advanta-
[a] Dr. D. Banerjee, Dr. R. V. Jagadeesh, Dr. K. Junge, Dr. H. Junge,
Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse e. V. an der Universitꢁt Rostock
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
Fax: (+49)-381-1281-5000
E-mail: matthias.beller@catalysis.de
Homepage: http://www.catalysis.de
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201200247.
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M. Beller et al.
selectivity in terms of mono- and diallylations are limitations of
most protocols. So far, no systematic studies have been per-
formed for aminations of aliphatic allyl alcohols and primary
aliphatic amines showed only poor reactivity. Importantly, in all
reported reactions the use of fancy phosphorus ligands was
necessary to achieve efficient allylic aminations.[24]
Table 1. Palladium-catalyzed amination of cinnamyl alcohol (1a) with ani-
line (2a).[a]
Entry Catalyst
Amount Solvent
[mol%]
T
Ratio
Yield[b]
[8C] 1a/2a [%]
To the best of our knowledge, to date, there are no reports
for catalytic aminations of readily available allylic alcohols in
the presence of nitrogen donor ligands. Herein, we show that
the combination of Pd(OAc)2 with 1,10-phenanthroline (L5)
allows for efficient conversion of a variety of aromatic and ali-
phatic allylic alcohols.
1
2
3
4
5
6
7
8
Pd(OAc)2
[Pd(acac)2]
[Pd(dba)2]
Pd(OCOCF3)2
PdCl2
5
5
5
5
5
5
5
5
toluene
toluene
toluene
toluene
toluene
dioxane
n-octane
n-heptane
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.5
80
21
20
0
0
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
no catalyst
Pd(OAc)2
60
65
55
25
62
85
69[c]
87
89
50
35
15
0
Results and Discussion
9
5
1
t-amyl alcohol 100 1:1.5
10
11
12
13
14
15
16
17
18
19
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
100 1:1.5
100 1:1.5
100 1:1.5
100 1:1.2
100 1:1.1
80 1:1.1
60 1:1.1
25 1:1.1
100 1:1.1
100 1:1.1
Based on our work on the borrowing-hydrogen methodology
using alcohols and amines,[25] we became interested in the re-
action of allylic alcohols with primary and secondary amines.
In our initial investigations, we chose cinnamyl alcohol (1a)
and aniline (2a) as model substrates. Different active catalysts
were generated in situ in the presence of 5 mol% Pd(OAc)2
and 10 mol% of L1–L11 in toluene at 1008C (Scheme 1). Good
isolated yields of the desired product 3a (75–80%) were ob-
tained by using L5 and its derivatives (L6–L8). Other mono-,
bi-, tri-, and multidentate nitrogen ligands were inefficient and
showed poor or no reactivity towards the amination reaction.
2.5
2.5
2.5
2.5
2.5
2.5
2.5
–
2.5
10[d]
[a] Reaction conditions: 1a (1 mmol), 2a (1–1.5 mmol), catalyst (1–
5 mol%), L5 (5–10 mol%), solvent (3 mL), 17 h. acac=acetylacetonate,
dba=dibenzylideneacetone. [b] Isolated yields. [c] 20 mol% of L5 used.
[d] No ligand used.
solvent from toluene to 1,4-dioxane, linear alkanes,
or t-amyl alcohol, the product yield decreased to 25–
65% (Table 1, entries 6–9). Testing different Pd con-
centrations revealed that a catalyst concentration of
2.5 mol% of Pd(OAc)2 was optimal and afforded 85%
isolated yield of 3a (Table 1, entries 10 and 11). Inter-
estingly, a large excess of ligand is not necessary for
successful conversion and a Pd/L5 ratio of 1:2 was
optimal to achieve an excellent yield of N-cinnamyla-
niline (3a; Table 1, entries 11 and 12).
With respect to atom economy, it is interesting to
note that 1 equivalent of 1a reacted well with
1.1 equivalents of 2a to afford 3a in 89% yield
(Table 1, entries 13 and 14). It is possible to run the
amination process even at room temperature, albeit
with lower yield of product (Table 1, entry 17). As ex-
pected, we did not observe any product in the ab-
sence of palladium (Table 1, entry 18). In all reactions
Scheme 1. Ligand screening for the palladium-catalyzed amination of cinnamyl alcohol
(1a) and aniline (2a) (isolated yields are presented in parentheses).
in which we observed lower yields of 3a, unreacted
1a and 2a could be recovered from the reaction mix-
ture. In all these cases we also recovered some
amount of the corresponding imine.
Due to its availability and best reactivity, we chose L5 as the
Encouraged by the results obtained in the model reaction,
ligand for further optimization studies (Table 1). A survey of dif-
ferent Pd precursors under similar reaction conditions showed
that Pd(OAc)2 was optimal, whereas PdCl2 and Pd(OCOCF3)2
gave no product 3a at all (Table 1, entries 1, 4, and 5). Reac-
tions in the presence of [Pd(acac)2] and [Pd(dba)2] proceeded
with low product yield (Table 1, entries 2 and 3). Changing the
we were interested to check the compatibility of our protocol
with a range of aromatic and aliphatic allylic alcohols. The re-
sults are summarized in Table 2. We also studied the regiose-
lectivity of a variety of allylic alcohols with phenyl or methyl
substituents at the a-, b-, or g-positions. In all cases, only the
linear substituted amines were obtained and we did not ob-
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Synthesis of Amines from Allylic Alcohols
Next, we studied the reaction of allylic alcohols with more
challenging alkyl amines. Especially for primary amines, the re-
sulting secondary products are more prone to undergo further
allylation; hence, it is more difficult to achieve regio- and ste-
reoselective monoallylation. To our delight, when applying the
combination of Pd(OAc)2 with L5 under the previously opti-
mized conditions, various primary aliphatic amines reacted
well with 1a. As shown in Table 3, we did not observe either
any undesired higher alkylated products or any branched iso-
mers of the corresponding aliphatic amines in any of these re-
actions. For example, the reaction of 1a with diphenylmethan-
amine (2 f), 1-naphthylmethylamine (2g), and 1-phenylethyl-
amine (2h) proceeded in 64–70% yield of the monoallylation
products (Table 3, entries 1–3). Monoallylation of cyclohexyla-
mine (2i) and cyclooctylamine (2j) gave 79% and 82% isolated
yields of 3l and 3m, respectively (Table 3, entries 4 and 5).
Further reactions of 1a with 1-octylamine (2k) and 2-octyl-
amine (2l) delivered the corresponding monoallylated prod-
ucts with similar efficiency (Table 3, entries 6 and 7). As expect-
Table 2. Palladium-catalyzed amination of various allylic alcohols.[a]
Entry Allylic alcohol Amine
Product
Yield[b]
[%]
1
2
3
1a
1a
1a
2a
89
80
76
4
1a
1a
79
5
73
77
50
Table 3. Palladium-catalyzed amination of 1a with various aliphatic ami-
nes.[a]
6
2b
2e
7[c]
Entry
Aliphatic amine
Product
Yield[b]
[%]
8[c]
2e
60
1
2
70
64
9[c]
2e[d]
59[e]
[a] Reaction conditions: allylic alcohol (1 mmol), amine (1.1 mmol), cata-
lyst (2.5 mol%), L5 (5 mol%), solvent (3 mL), 17 h. [b] Isolated yields. [c]
Alcohols (2 mmol), 40 h. [d] E/Z mixture of 1e (E/Z=96:4) was used.
[e] 3h was obtained as an E/Z mixture (97:3).
3
4
5
65
79
82
serve either branched isomers or bis-allylation products of the
corresponding amines.
The reaction of 1a and a-phenyl-substituted allylic alcohol
(1b) with electron-donating p-anisidine (2b) gave N-(4-me-
thoxy)cinnamylaniline (3b) as the linear product and no
branched isomer or diallylation product was detected by GC–
MS analysis (Table 2, entries 2 and 6). Apparently, both reac-
tions proceed via a common p-allylpalladium intermediate.
Furthermore, reaction of 1a with the electron-withdrawing ani-
line 2c gave the monoallylation product in 76% isolated yield
(Table 2, entry 3). Reactions of 1a with o-toluidene (2d) or the
secondary amine 2e run with comparable efficiency, producing
only linear trans-cinnamyl derivatives (Table 2, entries 4 and 5).
Further reaction of the allylic alcohol 1c with the secondary
amine 2e afforded the tertiary amine 3 f in 50% isolated yield
(Table 2, entry 7). The b- or g-methyl-substituted allylic alcohols
also regioselectively produced the corresponding allylic amines
in moderate to good yields (Table 2, entries 8 and 9).
6
7
65
70
8
84
87
9[c]
10[c]
81
[a] Reaction conditions: 1a (1 mmol), amine (1.1 mmol), catalyst
(2.5 mol%), L5 (5 mol%), solvent (3 mL), 17 h. [b] Isolated yields.
[c] 1.5 equiv amine used.
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M. Beller et al.
(Thermo Electron, Agilent) instrument. IR spectra were recorded by
using an FTIR Nicolet 6700 (Thermo Electron) instrument.
ed, the reactions of 1a with secondary amines gave excellent
yields of the corresponding tertiary amine derivatives (Table 3,
entries 8–10). Again, in some of the reactions with lower prod-
uct yields, we recovered allylic alcohols as well as amine
substrates.
General procedure for the amination of allylic alcohols: Under an
argon atmosphere, an oven-dried Schlenk tube was charged with
allylic alcohol (1 mmol) and amine (1.1 mmol) followed by
Pd(OAc)2 (2.5 mol%, 5.6 mg) and L5 (5 mol%, 9.0 mg). Toluene
(3 mL) and a magnetic stirrer bar were added and the reaction mix-
ture was stirred at 1008C for 17 h. The reaction mixture was then
cooled to RT, diluted with ethyl acetate (10 mL), and dried over an-
hydrous Na2SO4. The filtrate was concentrated under reduced pres-
sure and the residue was purified by silica-gel column chromatog-
raphy using ethyl acetate/hexane as the eluent to afford the corre-
sponding allyl amine.
Finally, we demonstrated the practical utility of our catalytic
amination protocol in the one-step synthesis of the antifungal
drug naftifine (3s) and the calcium channel blocker flunarizine
(3t; Scheme 2). So far, these bioactive products have been syn-
thesized by multiple synthetic steps[3b] or using harsh reaction
conditions. In the presence of Pd(OAc)2 (2.5 mol%) and L5
(5 mol%), the desired products were obtained in 83% and
70% isolated yield, respectively.
1
N-Cinnamylaniline (3a):[18c] Colorless oil; H NMR (300 MHz, CDCl3):
d=7.05–7.29 (m, 7H), 6.48–6.66 (m, 4H), 6.19–6.28 (m, 1H), 3.83
(dd, J=1.5, 6.06 Hz, 2H), 3.48 ppm
(brs, 1H); 13C NMR (75 MHz, CDCl3):
d=148.0, 136.9, 131.6, 129.3,
128.6, 127.6, 127.0, 126.4, 117.7,
113.1, 46.4 ppm; HRMS (ESI-TOF):
m/z calcd for C15H15N: 210.1283
[M+H]+; found: 210.1280; IR (ATR):
n˜ =3411, 3085, 3055, 3020, 2910,
2827, 2735, 1602, 1505, 1413,
1298, 1217, 1170, 976 cmÀ1
.
N-Cinnamyl-4-methoxyaniline
(3b):[18c] White solid; m.p. 66–688C;
1H NMR (300 MHz, CDCl3): d=7.15–
7.31 (m, 6H), 6.72 (d, J=9.0 Hz,
2H), 6.51–6.60 (m, 3H), 6.22–6.31
(m, 1H), 3.82 (dd, J=1.4, 5.8 Hz,
2H), 3.67 ppm (s, 3H); 13C NMR
(75 MHz, CDCl3): d=152.4, 142.1,
Scheme 2. Synthesis of the antifungal drug naftifine (3s) and calcium channel blocker flunarizine (3t).
Conclusions
136.9, 131.5, 128.6, 127.5, 127.2, 126.3, 114.9, 114.6, 55.9, 47.4 ppm;
HRMS (ESI-TOF): m/z calcd for C16H17NO: 240.1388 [M+H]+; found:
240.1386; IR (ATR): n˜ =3387, 3026, 2831, 1625, 1511, 1463, 1296,
We have shown that the combination of Pd(OAc)2 and L5 effi-
ciently catalyzes the direct amination of allylic alcohols. This
catalytic protocol proceeds straightforward with high atom
economy and does not need any additive for the activation of
the alcohol. A variety of aryl and alkyl amines reacted highly
selectively with allylic alcohols with phenyl or alkyl substituents
at the a-, b-, or g-positions. No branched isomers or bis-allyla-
tion products of the corresponding amines were obtained. The
synthetic utility of our catalytic method was successfully ap-
plied in the one-step synthesis of the biologically active mole-
cules naftifine and flunarizine.
1235, 1179, 1118, 1036, 967 cmÀ1
.
N-Cinnamyl-4-trifluoromethylaniline (3c):[18c] White powder; m.p.
72–748C; 1H NMR (300 MHz, CDCl3): d=7.16–7.35 (m, 7H), 6.51–
6.59 (m, 3H), 6.16–6.25 (m, 1H), 4.15 (brs, 1H), 4.03 ppm (d, J=
6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=150.4, 136.5, 132.0, 128.6,
127.7, 126.6, 126.3, 125.9, 112.1, 45.6 ppm; HRMS (ESI-TOF): m/z
calcd for C16H14 NF3: 278.1157 [M+H]+; found: 278.1151; IR (ATR):
n˜ =3421, 3029, 2845, 1889, 1615, 1528, 1479, 1449, 1413, 1319,
1187, 1099, 1059, 965, 825 cmÀ1
.
N-Cinnamyl-2-methylaniline (3d):[18a] Light-yellow oil; 1H NMR
(300 MHz, CDCl3): d=6.99–7.30 (m, 8H), 6.54–6.66 (m, 3H), 6.25–
6.35 (m, 1H), 3.90 (dd, J=1.5, 5.9 Hz, 2H), 2.10 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=145.9, 136.8, 131.6, 130.1, 128.6, 127.6, 127.2,
127.1, 126.3, 122.1, 117.2, 110.1, 46.2, 17.6; HRMS (ESI-TOF): m/z
calcd for C15H17N: 224.1439 [M+H]+; found: 224.1433; IR (ATR): n˜ =
3408, 3058, 3025, 2891, 1677, 1598, 1505, 1447, 1354, 1209, 1118,
Experimental Section
General: Unless otherwise stated, commercial reagents were used
without further purification. Organic solvents were distilled and
dried over molecular sieves. All reactions were performed under an
argon atmosphere by using an oven-dried Schlenk tube. All prod-
ucts were purified by silica-gel column chromatography and char-
1037, 964, 748, 732, 691 cmÀ1
.
1
acterized by using H and 13C NMR spectroscopy, HRMS, and FTIR
spectroscopy. NMR spectra were recorded by using a Bruker AV
300 spectrometer. All chemical shifts (d) are reported in ppm and
coupling constants (J) in Hz. All chemical shifts are related to sol-
vent peaks (chloroform: d=7.26 (1H) and 77.00 ppm (13C)). All
measurements were performed at room temperature unless other-
wise stated. MS were recorded by using a Finnigan MAT 95-XP
N-Cinnamyl-N-methylaniline (3e):[18c] Colorless oil; 1H NMR
(300 MHz, CDCl3): d=7.13–7.29 (m, 7H), 6.62–6.67 (m, 3H), 6.43 (d,
J=16.2 Hz, 1H), 6.12–6.21 (m, 1H), 3.99 (d, J=6.3 Hz, 2H),
2.89 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=149.5, 136.9, 131.2,
129.2, 128.5, 127.4, 126.3, 125.7, 116.6, 112.6, 54.9, 38.0 ppm; HRMS
(ESI-TOF): m/z calcd for C15H17N: 224.1439 [M+H]+; found:
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Synthesis of Amines from Allylic Alcohols
224.1436; IR (ATR): n˜ =3024, 2923, 2851, 1676, 1626, 1605, 1586,
3025, 2923, 2851, 1677, 1598, 1494, 1447, 1374, 1259, 1124, 1070,
963, 908, 889, 729, 690 cmÀ1
1512, 1448, 1316, 1255, 1127, 1051, 967, 746, 691 cmÀ1
.
.
N-Cinnamylcyclooctylamine (3m): Colorless oil; 1H NMR (300 MHz,
CDCl3): d=7.13–7.30 (m, 5H), 6.43 (d, J=15.87 Hz, 1H), 6.17–6.27
(m, 1H), 3.32 (d, J=6.78 Hz, 2H), 2.64–2.71 (m, 1H), 1.38–1.75 ppm
(m, 15H); 13C NMR (75 MHz, CDCl3): d=137.2, 131.2, 128.7, 128.5,
127.3, 126.3, 57.2, 49.5, 32.5, 27.3, 25.8, 24.1 ppm; HRMS (ESI-TOF):
m/z calcd for C17H25N: 244.2065 [M+H]+; found: 244.2064; IR (ATR):
n˜ =3410, 3025, 2916, 2849, 1674, 1598, 1494, 1446, 1360, 1101,
N-Allyl-N-methylaniline (3 f): Light-yellow oil; 1H NMR (300 MHz,
CDCl3): d=7.09–7.18 (m, 2H), 6.52–6.66 (m, 3H), 5.70–5.83 (m, 1H),
5.04–5.12 (m, 2H), 3.84 (d, J=5.22 Hz, 2H), 2.86 ppm (s, 3H);
13C NMR (75 MHz, CDCl3): d=149.6, 133.8, 129.2, 116.3, 116.1, 112.5,
55.4, 38.1 ppm; HRMS (ESI-TOF): m/z calcd for C10H13N: 148.1126
[M+H]+; found: 148.1118; IR (ATR): n˜ =3060, 2925, 2813, 1642,
1505, 1368, 1249, 1210, 1156, 1033, 992, 918, 747, 691 cmÀ1
.
1028, 964, 805, 731, 690 cmÀ1
.
N-(2-Methylallyl)-N-methylaniline (3g): Light-yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.10–7.19 (m, 2H), 6.58–6.62 (m, 3H), 4.71–
4.78 (m, 2H), 3.72 (s, 2H), 2.53 (s, 3H), 1.65 ppm (d, J=0.72 Hz,
3H); 13C NMR (75 MHz, CDCl3): d=149.6, 141.4, 129.0, 116.0, 111.9,
110.6, 53.6, 38.3, 20.1 ppm; HRMS (ESI-TOF): m/z calcd for C11H15N:
162.1277 [M+H]+; found: 162.1274; IR (ATR): n˜ =3004, 2937, 2843,
1670, 1587, 1513, 1444, 1373, 1341, 1323, 1214, 1120, 985, 960,
N-Cinnamyloctylamine (3n): Colorless oil; 1H NMR (300 MHz,
CDCl3): d=7.13–7.31 (m, 5H), 6.50 (d, J=15.12 Hz, 1H), 6.18–6.28
(m, 1H), 3.33 (dd, J=1.5, 6.6 Hz, 2H), 2.57 (t, J=7.5 Hz, 2H), 1.39–
1.46 (m, 3H), 1.18–1.23 (m, 10H), 0.80 ppm (t, J=7.2 Hz, 3H);
13C NMR (75 MHz, CDCl3): d=137.2, 131.1, 128.7, 128.5, 127.3,
126.2, 52.1, 49.6, 32.0, 30.2, 29.6, 29.3, 27.4, 22.8, 14.2 ppm; HRMS
(ESI-TOF): m/z calcd for C17H27N: 246.2216 [M+H]+; found:
246.2219; IR (ATR): n˜ =3411, 3026, 2954, 2923, 2853, 1681, 1599,
742, 694 cmÀ1
.
N-(But-2-enyl)-N-methylaniline (3h): Light-yellow oil; 1H NMR
(300 MHz, CDCl3) for (E)-3h: d=7.09–7.17 (m, 2H), 6.53–6.68 (m,
3H), 5.35–5.54 (m, 2H), 3.76 (d, J=1.2, 5.28 Hz, 2H), 2.82 (s, 3H),
1.60 ppm (dd, J=1.3, 5.3 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=
149.7, 129.3, 127.5, 126.5, 116.3, 112.6, 54.5, 37.9, 17.8 ppm; HRMS
(ESI-TOF): m/z calcd for C11H15N: 162.1277 [M+H]+; found:
162.1274; IR (ATR): n˜ =3024, 2917, 2813, 1677, 1597, 1503, 1449,
1494, 1449, 1377, 1121, 1070, 965, 743, 692 cmÀ1
.
N-Cinnamyl-2-octylamine (3o): Colorless oil; 1H NMR (300 MHz,
CDCl3): d=7.13–7.30 (m, 5H), 6.49 (d, J=15.78 Hz, 1H), 6.18–6.28
(m, 1H), 3.26–3.57 (d, J=6.02 Hz, 2H), 2.57–2.65 (m, 1H), 0.93–1.40
(m, 11H), 0.86–0.92 (m, 3H), 0.78–0.83 ppm (m, 3H); 13C NMR
(75 MHz, CDCl3): d=137.2, 131.0, 128.9, 128.5, 127.3, 126.2, 52.6,
49.4, 37.1, 32.0, 29.6, 26.0, 22.5, 20.3, 14.4 ppm; HRMS (ESI-TOF): m/
z calcd for C17H27N: 246.2216 [M+H]+; found: 246.2219; IR (ATR):
n˜ =3412, 3025, 2956, 2924, 2850, 1683, 1599, 1494, 1449, 1374,
1371, 1349, 1320, 1204, 1117, 990, 966, 747, 691 cmÀ1
.
1
N-Cinnamyl-1,1-diphenylmethylamine (3i): Light-yellow oil; H NMR
(300 MHz, CDCl3): d=7.10–7.35 (m, 15H), 6.41 (d, J=15.99 Hz, 1H),
6.20–6.29 (m, 1H), 4.84 (s, 1H), 3.29 (d, J=6.09 Hz, 2H), 1.68 ppm
(brs, 1H); 13C NMR (75 MHz, CDCl3): d=143.9, 137.2, 131.3, 128.5,
128.4, 127.7, 127.4, 127.1, 126.3, 66.5, 49.9 ppm; HRMS (ESI-TOF):
m/z calcd for C22H21N: 300.1746 [M+H]+; found: 300.1746; IR (ATR):
n˜ =3421, 3058, 3023, 2822, 1948, 1597, 1491, 1448, 1301, 1277,
1155, 1071, 964, 908, 730, 690 cmÀ1
.
N-Cinnamyl-N-methyloctylamine (3p): Colorless oil; 1H NMR
(300 MHz, CDCl3): d=7.13–7.31 (m, 5H), 6.42 (d, J=15.23 Hz, 1H),
6.15–6.24 (m, 1H), 3.05 (dd, J=1.5, 6.8 Hz, 2H), 2.17–2.31 (m, 2H),
1.52 (s, 3H), 1.39–1.44 (m, 2H), 1.00–1.19 (m, 10H), 0.77–0.98 ppm
(m, 3H); 13C NMR (75 MHz, CDCl3): d=137.1, 132.4, 128.5, 127.6,
127.3, 126.3, 60.4, 57.6, 42.3, 31.9, 29.7, 29.2, 27.5, 22.6, 14.2 ppm;
HRMS (ESI-TOF): m/z calcd for C18H29N: 260.2372 [M+H]+; found:
260.2374; IR (ATR): n˜ =3026, 2924, 2853, 2785, 1682, 1599, 1495,
1115, 1072, 964, 741, 691 cmÀ1
.
N-Cinnamyl-naphthalen-1-ylmethanamine (3j): Light-yellow oil;
1H NMR (300 MHz, CDCl3): d=8.04 (d, J=8.12 Hz, 1H), 7.67–7.79
(m, 2H), 7.14–7.45 (m, 9H), 6.49 (d, J=15.12 Hz, 1H), 6.21–6.32 (m,
1H), 4.18 (s, 2H), 3.44 (d, J=6.48 Hz, 2H), 1.53 ppm (brs, 1H);
13C NMR (75 MHz, CDCl3): d=137.1, 135.8, 133.9, 131.8, 131.6,
128.8, 128.6, 128.5, 127.8, 127.4, 126.3, 126.2, 125.7, 125.4, 123.7,
51.8, 50.9 ppm; HRMS (ESI-TOF): m/z calcd for C20H19N: 274.1596
[M+H]+; found: 274.1594; IR (ATR): n˜ =3411, 3024, 2813, 1648,
1596, 1493, 1446, 1355, 1261, 1211, 1114, 1070, 964, 790, 729,
1450, 1359, 1132, 1027, 966, 810, 738, 690 cmÀ1
.
N,N-Dipropylcinnamylamine (3q): Colorless oil; 1H NMR (300 MHz,
CDCl3): d=7.13–7.31 (m, 5H), 6.42 (d, J=15.72 Hz, 1H), 6.16–6.39
(m, 1H), 3.17 (d, J=6.54 Hz, 2H), 2.35 (t, J=7.5 Hz, 4H), 1.35–1.48
(m, 4H), 0.80 ppm (t, J=7.2 Hz, 6H); 13C NMR (75 MHz, CDCl3): d=
137.3, 131.9, 128.5, 128.0, 127.2, 126.2, 56.8, 56.0, 20.2, 12.0 ppm;
HRMS (ESI-TOF): m/z calcd for C15H23N: 218.1903 [M+H]+; found:
218.1906; IR (ATR): n˜ =3026, 2957, 2931, 2871, 2797, 1681, 1599,
690 cmÀ1
.
1495, 1449, 1364, 1298, 1187, 1072, 966, 738, 691 cmÀ1
.
N-Cinnamyl-1-phenylethylamine (3k):[18c] Pale-yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.13–7.29 (m, 10H), 6.38 (d, J=15.72 Hz, 1H),
6.15–6.24 (m, 1H), 3.79 (q, J=5.97 Hz, 1H), 3.27 (d, J=6.2 Hz, 2H),
1.71 (brs, 1H), 1.32 ppm (d, J=6.6 Hz, 3H); 13C NMR (75 MHz,
CDCl3): d=145.3, 137.1, 131.3, 128.5, 128.4, 127.3, 127.0, 126.6,
126.2, 57.6, 49.8, 24.3 ppm; HRMS (ESI-TOF): m/z calcd for C17H19N:
238.1596 [M+H]+; found: 238.1592; IR (ATR): n˜ =3415, 3059, 3025,
2964, 2924, 1681, 1599, 1493, 1449, 1368, 1305, 1205, 1118, 1071,
N-Cinnamylmorpholine (3r):[18c] Colorless oil; 1H NMR (300 MHz,
CDCl3): d=7.15–7.31 (m, 5H), 6.45 (d, J=15.93 Hz, 1H), 6.13–6.48
(m, 1H), 3.66 (t, J=4.6 Hz, 4H), 3.07 (d, J=6.78 Hz, 2H), 2.42 ppm
(t, J=4.59 Hz, 4H); 13C NMR (75 MHz, CDCl3): d=136.8, 133.4,
128.6, 127.6, 126.3, 126.0, 67.0, 61.5, 53.7 ppm; HRMS (ESI-TOF): m/
z calcd for C13H17NO: 204.1382 [M+H]+; found: 204.1384; IR (ATR):
n˜ =3025, 2956, 2853, 2804, 1679, 1598, 1494, 1451, 1350, 1291,
1027, 966, 761, 745, 699 cmÀ1
.
1276, 1114, 1069, 1005, 966, 867, 739 cmÀ1
.
N-Cinnamylcyclohexaneamine (3l):[18c] Colorless oil; 1H NMR
(300 MHz, CDCl3): d=7.13–7.30 (m, 5H), 6.43 (d, J=16.05 Hz, 1H),
6.18–6.28 (m, 1H), 3.36 (d, J=6.42 Hz, 2H), 2.39–2.46 (m, 1H),
1.82–1.86 (m, 2H), 1.53–1.69 (m, 3H), 0.95–1.25 ppm (m, 6H);
13C NMR (75 MHz, CDCl3): d=137.2, 130.9, 129.0, 128.5, 127.3,
126.2, 56.2, 49.0, 33.6, 26.2, 25.1 ppm; HRMS (ESI-TOF): m/z calcd
for C15H21N: 216.1746 [M+H]+; found: 216.1745; IR (ATR): n˜ =3411,
N-Cinnamyl-N-methylnaphthalen-1-ylmethanamine (3s):[18c] Orange
oil; 1H NMR (300 MHz, CDCl3): d=8.22 (d, J=8.67 Hz, 1H), 7.68–
7.78 (m, 2H), 7.14–7.47 (m, 9H), 6.50 (d, J=16.1 Hz, 1H), 6.25–6.34
(m, 1H), 3.88 (s, 2H), 3.21 (dd, J=1.5, 5.9 Hz, 2H), 2.20 ppm (s, 3H);
13C NMR (75 MHz, CDCl3): d=137.1, 134.9, 133.9, 132.7, 132.5,
128.6, 128.4, 127.9, 127.6, 127.5, 127.4, 126.3, 125.9, 125.6, 125.1,
124.6, 60.4, 60.1, 42.5 ppm; HRMS (ESI-TOF): m/z calcd for C21H21N:
ChemSusChem 0000, 00, 1 – 7
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M. Beller et al.
288.1746 [M+H]+; found: 288.1748; IR (ATR): n˜ =3026, 2942, 2853,
2785, 1677, 1597, 1509, 1449, 1362, 1124, 1015, 967, 792 cmÀ1
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1
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´
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Acknowledgements
This research has been funded by the State of Mecklenburg-West-
ern Pomerania, the BMBF, and the DFG (Leibniz Prize). We thank
Dr. W. Baumann, Dr. C. Fischer, S. Buchholz, S. Schareina, A.
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cal and analytical support.
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Keywords: allylic alcohol
catalysis · N-ligands · palladium
·
amination
·
homogeneous
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Received: April 18, 2012
Published online on && &&, 0000
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ChemSusChem 0000, 00, 1 – 7
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These are not the final page numbers!

FULL PAPERS
D. Banerjee, R. V. Jagadeesh, K. Junge,
H. Junge, M. Beller*
&& – &&
An Efficient and Convenient Palladium
Catalyst System for the Synthesis of
Amines from Allylic Alcohols
One pot is all it takes: By applying
a convenient combination consisting of
Pd(OAc)2/1,10-phenanthroline, a variety
of allylic alcohols reacts smoothly to
give the corresponding secondary and
tertiary amines in good to excellent
yields with high regioselectivity (see
picture).
ChemSusChem 0000, 00, 1 – 7
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
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These are not the final page numbers!