Nickel(0)-Catalyzed N-Allylation of Amides and p-Toluenesulfonamide with Allylic Alcohols under Neat and Neutral Conditions

Article abstract of DOI:10.1002/ejoc.201600500

Nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols took place in the presence of Ni⁰–diphosphine complexes. The corresponding N-allylated (and/or N,N-diallylated) products were obtained in moderate to high yields under neutral conditions.

Full text of DOI:10.1002/ejoc.201600500

DOI: 10.1002/ejoc.201600500
Full Paper
Amide Allylation
Nickel(0)-Catalyzed N-Allylation of Amides and p-
Toluenesulfonamide with Allylic Alcohols under Neat and
Neutral Conditions
Mohamed Salah Azizi,[a] Youssef Edder,[b] Abdallah Karim,[b] and Mathieu Sauthier*[a]
Abstract: Nickel(0)-catalyzed direct N-allylation of amides and allylated (and/or N,N-diallylated) products were obtained in
p-toluenesulfonamide with allylic alcohols took place in the
moderate to high yields under neutral conditions.
presence of Ni0–diphosphine complexes. The corresponding N-
Introduction
Direct N-allylation ranks among the most studied of N-alkyl-
ation reactions.[1] This reaction is usually performed with allyl
acetates, carbonates, halides, sulfonates, or phosphonates, as
substrates generating stoichiometric amounts of salt waste. Rel-
ative to these activated substrates, the use of allylic alcohols[2]
has several advantages. One important feature is that, with this
reagent, the reaction only releases molecules of water as easy
to separate, non-toxic side products. In addition, it is notewor-
thy that allylic alcohols are often less expensive than alkyl hal-
ides and, in fact, are generally used to synthesize allylic sub-
strates with good leaving groups (acetates, phosphonates).
However, it is well known that the reactivity of allylic alcohols is
usually lower than that of the allylic derivatives featuring good
leaving groups, especially when considering the need for an
oxidative addition step with a low-valent organometallic spe-
cies. A key issue in developing clean allylation reactions entails
the use of appropriate catalysts and reaction conditions that
favor this elemental step with allylic alcohols, particularly with-
out the use of activating additives (Scheme 1).[3]
Scheme 1. Nickel-catalyzed allylation reactions with allylic alcohol.
Following the pioneering studies by Tsuji and Trost,[4] the
direct amination of allylic alcohols has been frequently studied
using transition-metal catalysts; a predominant focus has been
on the application of palladium.[5] The N-allylation with allylic
alcohols of electron-poor nitrogen nucleophiles has been the
topic of only a few publications because of their poor nucleo-
philicity.[6,7] The direct N-protection of an amide with an allyl
group is, however, an important reaction in organic synthesis,
notably in total synthesis, enabling one to avoid competitive
reactions.[8] On the basis of traditional procedures for N-allyl-
ation
of
amides
with
allyl
acetates, carbonates, halides, sulfonates, and phosphonates, un-
der neutral conditions, the use of a strong base such as sodium
hydride before treatment with the allylating agent would ap-
pear to be necessary. This type of synthesis usually leads to
mixtures of N- and O-allylated products.[9,6c]
Notably, Ni0/phosphine complexes are efficient catalysts for
the reaction of various allylic alcohols with nucleophiles such as
ꢀ-keto esters, ꢀ-diketones, malonates or amines under neutral
conditions.[10]
[a] Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 – UCCS –
Unité de Catalyse et Chimie du Solide,
59000 Lille, France
E-mail: mathieu.sauthier@univ-lille1.fr
http://uccs.univ-lille1.fr/index.php/annuaire/15-fiches-personnels/
207-sauthier-mathieu
[b] Équipe de Chimie de Coordination et de Catalyse, Département de Chimie,
Faculté des Sciences Semlalia, Université Cadi Ayyad, BP 2390 Marrakech,
Marocco
Results and Discussion
To date, no nickel(0)-catalyzed direct N-allylation of amides and
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600500.
sulfonamides with allylic alcohols has been reported. Other
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transition metals[6a–6i] or Lewis and Brønsted acids[7] have been was obtained in low yield (Table 1, Entry 1). Investigations into
applied such as palladium combined with strongly π-accepting the use of different solvents revealed that the reaction is more
diphosphines,[6a–6c] molybdenum,[6d,6e] bismuth,[6f] mercury[6g] efficient in more polar solvents such as THF and CH3CN (Table 1,
and gold complexes.[6h–6i] Unfortunately, most such N-allylation Entries 1–4). Interestingly, little to no product was obtained in
reactions of amides and sulfonamides necessitate significant water and methanol; these solvents very likely acted as compet-
loading of precious metals, high reaction temperatures and re- itive nucleophiles (Table 1, Entries 5 and 6). Worth noting is
quire the use of additives. Lewis acids have proven to be highly that yields of desired product further improved without use of
efficient for the conversion of allylic alcohols substituted any solvent (Table 1, Entry 7 versus Entries 1–3). Both the use
with aryl groups that transiently allow formation of stabilized of a polar medium and the high concentrations of substrate
carbocations. Allyl alcohol is typically never involved with this explain this improvement.
family of catalysts. Therefore, we present herein, the first
nickel(0)-catalyzed systems for direct N-allylation of amides and
sulfonamides using allylic alcohols and a selection of acetanil-
ide, benzamide, benzanilide derivatives and p-toluenesulfon-
amide under neutral and additive-free conditions. The nickel(0)-
catalyzed direct N-allylation of acetanilide (2a) with allyl alcohol
(1a) was chosen as a model for the optimization of the reaction
conditions (Table 1). Amide N-allylation with 3 equiv. of allyl
alcohol in the presence of Ni(dppmb)2 in toluene (as solvent)
proved successful. However, after 18 h at 80 °C, the product
We then turned our attention to understanding the effects
of phosphine ligands on the catalytic elements of N-allylation.
For this purpose, the catalyst was obtained in situ using the
combination of Ni(cod)2 and the ligand (Scheme 2) with a
P/Ni ratio of 4:1. 1,2-Bis[(diphenylphosphino)methyl]benzene
(dppmb, L1) was identified as the most promising ligand com-
pared to other monodentate and/or bidentate phosphines such
as 1,4-bis(diphenylphosphino)butane (dppb, L2), 1,2-bis(di-
phenylphosphino)ethane (dppe, L3), triphenylphosphine (PPh3,
L4), Xantphos (L5), and 1,1′-ferrocenediylbis(diphenylphos-
phine) (dppf, L6) (Table 1, Entries 8–15). The cod ligands are
easily replaced (in situ) by diphosphines; the Ni(dppb)2 complex
is, for example, synthesized fromby a ligand exchange reaction
between 1 equiv. of Ni(cod)2 and 2 equiv. of dppb.[5c] Notably,
this ligand effect is a common feature in catalytic transforma-
tions that involve allylic nickel intermediates, and a similar trend
has been observed in the case of diene hydroalkoxylations.[11]
With dppmb, a ligand/Ni ratio of 2 or 3 is necessary to ensure
stabilization of the catalytic species and the formation of 3a
with the highest yield (Table 1, Entries 9–11).
Table 1. Nickel(0)-catalyzed direct N-allylation of acetanilide with allyl alcohol
under various conditions.[a]
Entry
Catalyst
[2 mol-%]
Solvent x[b]
T
[°C]
Additive
(mol-%)
Yield[c]
[%]
1
2
3
4
5
6
7
8
9
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppb)2
toluene
CH3CN
THF
Et2O
H2O
MeOH
neat
neat
3
3
3
3
3
3
3
3
3
80
80
80
80
80
80
80
80
80
none
none
none
none
none
none
none
none
none
4
65
55
0
10
5
90
16
79
dppmb/Ni(cod)2
(1:1)
neat
10
11
dppmb/Ni(cod)2
(2:1)
dppmb/Ni(cod)2
(3:1)
neat
neat
3
3
80
80
none
none
90
90
Scheme 2. Ligands used in the study.
12
13
14
15
16
17
18
19
20
21
22[d]
23
24
25
dppe/Ni(cod)2 (2:1)
Xantphos
neat
neat
neat
neat
neat
neat
neat
neat
neat
neat
neat
neat
neat
neat
3
3
3
3
3
3
3
1
2
4
3
3
3
3
80
80
80
80
60
90
100
80
80
80
80
80
80
80
none
none
none
none
none
none
none
none
none
50
3
2
In order to further delineate the best catalytic conditions, the
effects of temperature as well as the number of allylic alcohol
equivalents were studied. Temperatures higher than 90 °C lead
to a loss of catalytic activity, which can be attributed to catalyst
degradation (Table 1, Entries 17 and 18). At 60 °C, lower yields,
as explained by insufficient catalytic activities, were obtained
(Table 1, Entry 16). Although amide monoallylation was tar-
geted in this study, it should be emphasized that 2 or 3 equiv.
of allylic alcohol are necessary to achieve high yields (Table 1,
Entries 19–21). This is essentially explained by the fact that, as
evidenced by GC analysis of the crude mixtures, the allylic alco-
hol is partially converted into diallyl ether as a side product of
the reaction (Scheme 3). This etherification reaction is known
in nickel chemistry[12,10b] and is more commonly observed if
dppf
PPh3/Ni(cod)2 (4:1)
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
Ni(dppmb)2
4
73
90
67
76
77
90
47
14
0
none
NaOH (20)
NEt3 (20)
PTSA (20)
B(OH)3 (20)
0
[a] Reaction conditions: 1 (9.75 mmol, if using 3 equiv.), 2a (3.25 mmol,
1 equiv.), if using a solvent (0.5 mL), 1–2 mol-% of Ni(dppmb)2, 60–100 °C,
18 h. [b] Equiv. of allyl alcohol employed in the reaction. [c] Isolated yield.
[d] Formation of aniline (yield: 2 %) and N-allylaniline (yield: 14 %).
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allylic alcohol is used in the absence of a nucleophile. The for-
mation of this side product is in line with the rather low reactiv-
ity/nucleophilicity of amides. In order to improve our insight
into the importance of this side reaction on the course of the
desired reaction, diallyl ether was treated with acetanilide un-
der the optimized reaction conditions. No product (3a) was
formed, thus indicating that this side reaction competes with
amide N-allylation. From a practical point of view, the formation
of diallyl ether is not a major drawback as this compound is
easily removed from the reaction medium during workup and
evaporation of the volatiles.
Table 2. Nickel(0)-catalyzed direct N-allylation of acetanilide and benzanilide
derivatives.[a]
Scheme 3. Self-etherification of allylic alcohol.
Various acids and bases that can either activate the hydroxy
group of the allylic starting material or improve the nucleophil-
icity of the amide have been evaluated as additives. Bases were
found to completely deactivate the catalyst (Table 1, Entries 22
and 23), whereas acids did not lead to any further improve-
ments (Table 1, Entries 24 and 25). After optimization, the
nickel-catalyzed reaction afforded N-allylated acetanilide in an
isolated yield of 90 % under neutral conditions.
The reactions of various acetanilide and benzanilide deriva-
tives were then examined. The results of the catalytic N-allyl-
ation are summarized in Table 2. Derivatives of acetanilide with
electron-donating groups at the para position of the phenyl
group were readily converted into the corresponding allylated
derivatives (Table 2, Entries 2 and 3). The use of the p-hydroxy
group (paracetamol, 2d) led to a rather low product yield, al-
though it is noteworthy that no allylation on the phenolic oxy-
gen atom occurred (Table 2, Entry 4). This can likely be corre-
lated to the good leaving ability of the phenoxy group in allyl-
phenoxy substrates; these species have been used elsewhere
as substrates in allylation reactions.[13] Although the oxidative
addition of aryl halides to low-valent nickel species can effect
substrate decomposition, p-chloro- and o-bromo-substituted
acetanilides were converted into the corresponding allylated
derivatives 3e and 3f with isolated yields of 56 % and 60 %,
respectively (Table 2, Entries 5 and 6). Sterically more hindered
derivative 2g, which was prepared by acetylation of 2-phenyl-
aniline, was very efficiently converted into 3g (Table 2, Entry 7).
Benzanilides were also evaluated as nitrogen donors, and deriv-
atives 6a–c were isolated with yields ranging from 48 % to 74 %
(Table 2, Entries 8–10).
The scope of the reaction was further enlarged to other am-
ides, and our interest focused on the conversion of primary
amides (Table 3). The reaction of benzamide (7a) afforded a
mixture of monoallylated 8a and diallylated 8b derivatives that
[a] Reaction conditions: 1 (9.75 mmol), 2a–g and 5a–c (3.25 mmol), 2 mol-%
of Ni(dppmb)2, 80 °C, 18 h. [b] Yields of isolated products. [c] Determined by
GC.
were efficiently purified by silica gel column chromatography ated and diallylated derivatives were additionally obtained us-
(Table 3, Entry 1). Improved selectivity for monoallylated deriva- ing substrates 7c and 7d (Table 3, Entries 3 and 4). The use of
tives can be achieved by using fewer equivalents of allylic alco- substrate 7d, bearing both an amino and an amido group
hol. The monoallylated derivative was obtained from the reac- clearly reveals the difference in reactivity between the two
tion with N-methylbenzamide (7b) (Table 3, Entry 2). Monoallyl- nitrogen atoms. Product 8f, allylated on the amino group, was
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Table 3. Reaction scope of the nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols.[a]
[a] Reaction conditions: 1a–c (9.75 mmol), 7a–i (3.25 mmol), cat. (2 mol-%), 80 °C, 18 h. [b] Isolated yields. [c] The reaction was carried out in CH3CN.
obtained as a mixture with diallylated (on the amino and amido
Importantly, the selectivity of the reaction could not be
groups) compound 8g, thus demonstrating the higher reactiv- tuned by reducing the number of equivalents of allyl alcohol.
ity of the aniline nitrogen atom relative to that of the amide For instance, primary sulfonamide 7f was efficiently converted
group (Table 3, Entry 4). A low yield of product was obtained into its diallylated derivative by using 3 equiv. of allylic alcohol.
using phthalimide, a widely used reactant in the chemistry of However, a mixture of mono- and diallylated derivatives was
N-acyliminium ions (Table 3, Entry 5).[14] However, p-toluenesul- obtained when using 1 equiv. allylic alcohol (Scheme 4).
fonamide (7f) was found to efficiently react with allyl alcohol
yielding selectively diallylated 8i (Table 3, Entry 6).
The reaction showed limited success with substituted allylic
derivatives such as 2-methyl-2-propen-1-ol (1b) and cinnamyl
alcohol (1c). Neither of these allylic alcohols reacted with acet-
anilide (2a) or nicotinamide (7c) under our optimized reaction
conditions. However, these substituted allylic derivatives were
elsewhere efficiently treated with p-toluenesulfonamide (7f).
The reaction of 7f with substituted allyl alcohol 1b led to select-
ive
formation
of
monoallyl-
ated 8j (Table 3, Entry 7); the bulkiness of this substrate very
likely prevented the generation of the diallylated derivative.
Conversely, the reaction of 1c yielded selectively diallylated de-
rivative 8k (Table 3, Entry 8).
Scheme 4. Allylation selectivity of 7f as function of allyl alcohol equivalents.
The use of amides as nucleophiles in metal-catalyzed allylic
alkylation reactions is rather uncommon. This is due to the poor
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using an MBRAUN Solvent Purification Systems (MB-SPS-800) and
degassed under nitrogen prior to use. All glass apparatus was oven-
dried and cooled under vacuum before use; the dppmb ligand was
prepared according to a procedure described by Li et al., from tri-
phenylphosphine and 1,2-bis(bromomethyl)benzene in the pres-
ence of lithium[16] or potassium.[17] Ni(dppmb)2 and other catalysts
were prepared in a glove box (MBRAUN). Acetanilide derivatives
2a–g were prepared using a classical method of acetylation of the
corresponding anilines with acetic anhydride and sodium acetate
in acetic acid. Benzanilide derivatives 5a–d were prepared from
nucleophilicity of the nitrogen atom. This reduced reactivity rel-
ative to that of amines results from partial delocalization of the
nitrogen lone pair of electrons with the carbonyl group.[15]
Amide nucleophilicity can, however, be enhanced by N-depro-
tonation; this elemental step typically requires the use of strong
bases.[9] In the case of the nickel-catalyzed allylation reaction,
it can be expected that the nickel–hydroxy species generated
from oxidative addition of allyl alcohol to an Ni0 intermediate
acts as a catalytic base[6a] assisting in the formation of an allylic
nickel amide complex and subsequent release of water (see commercially available anilines according to the Schotten–Bau-
mann conditions[18] with benzoyl chloride. The reaction takes place
Scheme 5).
in a basic medium in the presence of NaOH, and ethanol as solvent.
All reactions were monitored by GC analysis using a Shimadzu
GC2014 apparatus. Analytical thin layer chromatography (TLC) was
performed with commercial silica gel 60 by way of fluorescent indi-
cator UV absorbance 254 (Merck). Detection was accomplished by
irradiation with a UV lamp and by an ethanolic solution of p-anis-
aldehyde. Distilled solvents were used as eluents for column chro-
matography. Chromatographic purifications were realized using sil-
ica gel columns (silica 60 Å, 40–63 μm) usually with a petroleum
ether/ethyl acetate eluent system. Melting points were determined
1
using a Stuart Scientific SMP 10 analyzer. H and 13C NMR spectra
were recorded with a Bruker AC 300 spectrometer. Chemical shifts
(δ) are reported in parts per million (ppm) relative to internal Me4Si
(TMS). High-resolution mass spectra (HRMS) were measured with a
Thermo Scientific Exactive spectrometer at the CUMA-Pharm. Dept.,
University Lille Nord de France.
General Procedure A for the Synthesis of Ni(dppmb)2. Synthesis
of Ni(dppmb)2: In a Schlenk tube were placed dppmb (1.172 g,
2 equiv.) and a magnetic stirring bar. The Schlenk tube was then
placed in a glove box to weigh the Ni(COD)2 (air-sensitive reagent)
(342 mg). The Schlenk tube was removed from the glovebox and
connected to a vacuum/nitrogen line. Under nitrogen, toluene
(20 mL) was added. The mixture was stirred at room temperature
overnight, and the solvent was evaporated to give a yellow solid.
For the catalytic runs, Ni(dppmb)2 was weighed in air but kept
stored in the Schlenck tube under nitrogen after each use.
Scheme 5. Proposed mechanism for amide N-allylation.
A reductive elimination step leads to the formation of the N-
allylated amide with subsequent generation of a low-valent Ni0
precursor that can initiate a new catalytic cycle. Alternatively,
an outer-sphere attack of the amide on the allylic moiety of the
Ni(allyl)(hydroxy) intermediate with subsequent release of water
directly affords the product along with the same Ni0 precursor.
General Procedure B for the Nickel(0)-Catalyzed N-Allylation of
Amides and Sulfonamide with Allylic Alcohols: In a Schlenk tube
Both pathways (inner-sphere and outer-sphere) are driven by were placed freshly prepared Ni(dppmb)2 (2 mol-%), amide
(3.25 mmol, 1 equiv.), and a magnetic stirring bar. The reagents
were degassed, and then freshly distilled and degassed allyl alcohol
(3 equiv.) was added. The reaction mixture was stirred without sol-
vent at 80 °C for 18 h. At the end of the reaction, the reaction
mixture was cooled to room temperature, and anisole (250 μL) was
added and used as internal standard for the gas-chromatographic
(GC) analysis. The reaction mixture was concentrated under reduced
pressure; the residue was purified by silica gel column chromatogra-
phy using ethyl acetate/petroleum ether as eluent.
deprotonation of the amide by the hydroxy ligand; this logic is
consistent with the superior reactivity observed with acidic am-
ides such as tosylamides.
Conclusions
We have reported that Ni0-based catalysts stabilized with the
dppmb ligand promote direct N-allylation of amides and p-tolu-
enesulfonamide with allylic alcohols. The reaction has been
shown to compete with the nickel-catalyzed self-etherification,
which affords volatile diallyl ether. This synthetic pathway thus
Analytical Data of Products
N-Allyl-N-phenylacetamide (3a):[19] The general procedure B was
allows for clean protection of amides with an allylic moiety in applied to amide 2a (440 mg, 3.25 mmol, 1 equiv.) and allyl alcohol
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
an eco-friendly fashion. The reaction is performed under neutral
conditions, no additive is needed to activate the allyl alcohol,
and water is generated as an easily removed byproduct.
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25;
1
yield 90 %. H NMR (300 MHz, CDCl3, °C): δ = 1.75 (s, 3 H), 4.20 (dt,
J = 6.2, J = 1.2 Hz, 2 H), 4.97 (m, 2 H), 5.75 (m, 1 H), 7.07 (d, J =
8.4 Hz, 2 H), 7.29 (m, 3 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C):
δ = 21.6, 51.0, 116.7, 126.8, 127.0, 128.5, 132.1, 142.0, 169.1 ppm.
Experimental Section
General Remarks: All catalytic reactions were performed with stan- N-Allyl-N-(p-tolyl)acetamide (3b):[19] The general procedure B was
dard Schlenk techniques under nitrogen. Solvents were dried by
applied to amide 2b (485 mg, 3.25 mmol, 1 equiv.) and allyl alcohol
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(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25; chromatography: petroleum ether/ethyl acetate, 100:0 to 50:50;
1
1
yield 38 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 1.78 (s, 3 H), 2.30
yield 48 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 4.46 (d, J = 6.0 Hz,
(s, 3 H), 4.20 (dt, J = 6.2, J = 1.2 Hz, 2 H), 5.00 (m, 2 H), 5.78 (m, 1 2 H), 5.11 (m, 2 H), 5.92 (m, 1 H), 6.94 (m, 2 H), 7.08 (m, 6 H), 7.26
H), 6.95 (d, J = 8.2 Hz, 2 H), 7.11 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 20.0, 21.6, 51.0, 116.6, 126.8, 129.1,
132.2, 136.7, 139.4, 169.2 ppm.
(dd, J = 6.8, J = 1.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C):
δ = 53.2, 117.6, 120.2, 124.5, 126.5, 127.0, 127.5, 127.7, 128.7, 128.8,
129.0, 129.1, 129.6, 131.8, 133.2, 169.8 ppm.
N-Allyl-N-(4-methoxyphenyl)acetamide (3c):[19] The general pro-
cedure B was applied to amide 2c (536 mg, 3.25 mmol, 1 equiv.)
and allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the
flash column chromatography: petroleum ether/ethyl acetate, 100:0
N-Allyl-N-(4-methoxyphenyl)benzamide (6b):[23] The general pro-
cedure B was applied to amide 5b (368 mg, 1.62 mmol, 1 equiv.)
and allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the
flash column chromatography: petroleum ether/ethyl acetate, 100:0
1
1
to 75:25; yield 70 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 1.76 (s, 3
to 50:50; yield 74 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 3.66 (s, 3
H), 3.73 (s, 3 H), 4.17 (dt, J = 6.3, J = 1.4 Hz, 2 H), 4.99 (m, 2 H), 5.75
H), 4.40 (d, J = 6.0 Hz, 2 H), 5.11 (m, 2 H), 5.89 (m, 1 H), 6.64 (d, J =
8.8 Hz, 2 H), 6.86 (d, J = 8.8 Hz, 2 H), 7.17 (m, 3 H), 7.24 (m, 2 H)
(m, 1 H), 6.82 (d, J = 8.9 Hz, 2 H), 6.98 (d, J = 8.9 Hz, 2 H) ppm. 13C
NMR (75 MHz, CDCl3, 25 °C): δ = 22.5, 52.0, 55.3, 114.6, 117.7, 129.1, ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 53.3, 55.3, 114.2, 117.7,
133.2, 135.7, 158.9, 170.4 ppm.
127.7, 128.6, 128.8, 129.4, 133.2, 136.2, 152.1, 158.0, 170.2 ppm.
N-Allyl-N-(4-hydroxyphenyl)acetamide (3d):[20] The general pro- N-Allyl-N-(4-chlorophenyl)benzamide (6c):[23] The general proce-
cedure B was applied to amide 2d (491 mg, 3.25 mmol, 1 equiv.)
and allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the
flash column chromatography: petroleum ether/ethyl acetate, 100:0
dure B was applied to amide 5c (375 mg, 1.62 mmol, 1 equiv.) and
allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash
column chromatography: petroleum ether/ethyl acetate, 100:0 to
1
1
to 75:25; yield 20 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 2.08 (s, 3
50:50; yield 61 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 4.42 (dt, J =
H), 4.44 (dt, J = 5.2, J = 1.4 Hz, 2 H), 5.20 (dd, J = 10.5, J = 1.3 Hz,
1 H), 5.33 (dd, J = 17.2, J = 1.5 Hz, 1 H), 5.97 (m, 1 H), 6.79 (d, J =
8.9 Hz, 2 H); 6.97 (s, 1 H), 7.30 (d, J = 9.0 Hz, 2 H) ppm. 13C NMR
6.0, J = 1.3 Hz, 2 H), 5.10 (m, 2 H), 5.87 (m, 1 H), 6.88 (d, J = 8.7 Hz,
2 H), 7.10 (m, 2 H), 7.15 (m, 3 H), 7.24 (m, 2 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 53.1, 117.8, 122.1, 122.5, 127.7, 128.6,
(75 MHz, CDCl3, 25 °C): δ = 24.1, 68.9, 115.1, 117.6, 121.8, 133.6, 128.7, 128.8, 129.4, 132.1, 133.1, 131.7, 136.0, 155.1, 155.7,
143.0, 153.8, 168.1 ppm.
165.8 ppm.
N-Allyl-N-(4-chlorophenyl)acetamide (3e):[19] The general proce-
dure B was applied to amide 2e (551 mg, 3.25 mmol, 1 equiv.) and
allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash
column chromatography: petroleum ether/ethyl acetate, 100:0 to
75:25; yield 56 %. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 1.79 (s, 3 H),
4.19 (dt, J = 6.2, J = 1.2 Hz, 2 H), 5.04 (m, 2 H), 5.75 (m, 1 H), 7.03
(d, J = 8.5 Hz, 2 H); 7.29 (d, J = 8.6 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3, 25 °C): δ = 22.6, 51.9, 118.1, 129.4, 129.8, 132.8, 133.7, 141.4,
169.8 ppm.
N-Allylbenzamide (8a):[24] The general procedure B was applied to
amide 7a (393 mg, 3.25 mmol, 1 equiv.) and allyl alcohol (663 μL,
9.75 mmol, 3 equiv.). Eluent used for the flash column chromatogra-
phy: petroleum ether/ethyl acetate, 100:0 to 75:25; yield 54 %. 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 4.01 (m, 2 H), 5.11 (d, J = 10.2 Hz,
1 H), 5.19 (d, J = 17.1 Hz, 1 H), 5.86 (m, 1 H), 6.22 (s, br., 1 H), 7.36
(m, 3 H), 7.71 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ =
41.4, 115.4, 125.9, 127.4, 130.4, 133.2, 133.4, 166.4 ppm.
N,N-Diallylbenzamide (8b):[25] The general procedure B was ap-
plied to amide 7a (393 mg, 3.25 mmol, 1 equiv.) and allyl alcohol
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25;
N-Allyl-N-(2-bromophenyl)acetamide (3f):[21] The general proce-
dure B was applied to amide 2f (347 mg, 1.62 mmol, 1 equiv.) and
allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash
column chromatography: petroleum ether/ethyl acetate, 100:0 to yield 8 %. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 3.76 (s, br., 2 H),
75:25; yield 60 % (determined by GC), NMR spectra showed that
the isolated product is a mixture with the starting material [45 %
of N-(2-bromophenyl)acetamide 2f]. 1H NMR (300 MHz, CDCl3,
25 °C): δ = 1.74 (s, 3 H), 3.65 (dd, J = 14.7, J = 7.5 Hz, 1 H), 4.68 (dd,
J = 14.7, J = 5.6 Hz, 1 H), 5.00 (m, 2 H), 5.80 (m, 1 H), 6.91 (m, 1 H),
7.46 (m, 1 H), 7.63 (m, 1 H), 8.25 (d, J = 7.7 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 22.4, 50.8, 118.4, 123.9, 128.4, 129.7,
131.1, 132.8, 133.8, 141.4, 170.1 ppm.
4.06 (s, br., 2 H), 5.13 (m, 4 H), 5.75 (m, 2 H), 7.33 (m, 5 H) ppm. 13
C
NMR (75 MHz, CDCl3, 25 °C): δ = 50.2, 52.4, 117.6, 126.6, 128.3,
129.6, 136.3, 171.7 ppm.
N-Allyl-N-methylbenzamide (8c):[26] The general procedure B was
applied to amide 7b (440 mg, 3.25 mmol, 1 equiv.) and allyl alcohol
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25;
yield 36 %; Existing as a 3:2 mixture of rotamers. 1H NMR (300 MHz,
N-Allyl-N-(biphenyl-2-yl)acetamide (3g): The general procedure B CDCl3, 25 °C): δ = 2.84 (s, br., 3 H, minor), 2.97 (s, br., 3 H, major),
was applied to amide 3g (171 mg, 0.810 mmol, 1 equiv.) and allyl
alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash col-
3.77 (s, br., 2 H, minor), 4.07 (s, br., 2 H, major), 5.17 (m, 2 H), 5.74
(m, 1 H), 7.31 (m, 5 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ =
umn chromatography: petroleum ether/ethyl acetate, 100:0 to 14.1, 21.0, 29.6, 53.9, 60.3, 117.5, 126.6, 128.9, 129.5, 133.0, 136.3,
75:25. Rf = 0.56 (75:25); colorless viscous oil; yield 90 %. 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 1.82 (s, 3 H), 3.07 (dd, J = 14.7, J =
7.6 Hz, 1 H), 4.53 (dd, J = 14.7, J = 5.1 Hz, 1 H), 4.89 (dd, J = 19.5,
J = 7.6 Hz, 1 H), 4.94 (dd, J = 13.8, J = 1.1 Hz, 1 H), 5.57–5.79 (m, 1
H), 7.05–7.41 (m, 9 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ =
22.8, 51.4, 117.7, 127.7, 128.3, 128.41, 128.46, 128.48, 128.5, 128.7,
130.0, 131.4, 133.0, 138.7, 139.6, 140.2, 170.3 ppm. HR-MS (+ESI):
calcd. for C17H18NO [M + H]+ 252.1388, found 252.1375.
136.3, 170.5 ppm.
N-Allylnicotinamide (8d):[27] The general procedure B was applied
to amide 7c (397 mg, 3.25 mmol, 1 equiv.) and allyl alcohol (663 μL,
9.75 mmol, 3 equiv.). Eluent used for the flash column chromatogra-
phy: petroleum ether/ethyl acetate, 100:0 to 75:25; yield 22 %. 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 3.95 (tt, J = 7.2, J = 1.5 Hz, 2 H),
5.08 (m, 2 H), 5.81 (m, 1 H), 7.24 (m, 1 H), 7.59 (s, br., 1 H), 8.06 (dt,
J = 7.9, J = 2.1 Hz, 2 H), 8.56 (dd, J = 4.8, J = 1.4 Hz, 2 H), 8.94 (s, 1
N-Allyl-N-phenylbenzamide (6a):[22] The general procedure B was H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 42.4, 116.5, 123.4,
applied to amide 5a (320 mg, 1.62 mmol, 1 equiv.) and allyl alcohol 130.2, 133.8, 135.2, 148.2, 151.8, 165.7 ppm.
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N,N-Diallylnicotinamide (8e):[28] The general procedure B was ap-
3 equiv.), the reaction is carried out in CH3CN (0.5 mL). Eluent used
plied to amide 7c (397 mg, 3.25 mmol, 1 equiv.) and allyl alcohol for the flash column chromatography: petroleum ether/ethyl acet-
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column ate, 100:0 to 95:05; yield 64 %. 1H NMR (300 MHz, CDCl3, 25 °C): δ =
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25; 2.35 (s, 3 H), 3.93 (d, J = 6.6 Hz, 4 H), 5.92 (m, 2 H), 6.34 (m, 2 H),
yield 69 %. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 3.77 (s, br., 2 H),
4.06 (s, br., 2 H), 5.15 (m, 4 H), 5.72 (m, 2 H), 7.25 (ddd, J = 7.8, J =
4.8, J = 0.8 Hz, 1 H), 7.69 (dt, J = 7.8, J = 1.8 Hz, 1 H), 8.56 (dd, J =
4.8, J = 1.6 Hz, 1 H), 8.62 (dd, J = 1.4, J = 0.7 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 47.3, 50.7, 117.9, 118.1, 123.2, 132.0,
132.4, 132.6, 134.3, 147.4, 150.6, 169.1 ppm.
7.19 (m, 12 H), 7.68 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3, 25 °C): δ = 21.4, 49.0, 123.9, 126.4, 127.3, 127.9, 128.6, 129.7,
134.0, 136.2, 137.6, 143.3 ppm.
Acknowledgments
2-(Allylamino)benzamide (8f):[29] The general procedure B was ap-
plied to amide 7d (442 mg, 3.25 mmol, 1 equiv.) and allyl alcohol
(663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash column
chromatography: petroleum ether/ethyl acetate, 100:0 to 75:25;
We thank the Chevreul Institute for support (Grant No. FR 2638]
as well as the Ministère de l'Enseignement Supérieur et de la
Recherche, Région Nord – Pas de Calais and FEDER for support-
ing and funding this work. Y. E. gratefully acknowledges the
Université de Lille for the financial support.
1
yield 82 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 3.75 (d, J = 5.1 Hz,
2 H), 5.09 (d, J = 10.2 Hz, 1 H), 5.22 (d, J = 17.1 Hz, 1 H), 5.73 (s, br.,
2 H), 5.87 (m, 1 H), 6.52 (t, J = 8.1 Hz, 1 H), 6.63 (d, J = 8.4 Hz, 1 H),
7.24 (t, J = 7.0 Hz, 1 H), 7.31 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 45.5, 112.5, 113.3, 115.0, 116.1, 128.2,
133.4, 134.6, 149.8, 172.1 ppm.
Keywords: Homogeneous catalysis · Nickel · N-Allylation ·
Allylic alcohols · Amides · Electron-poor N atoms
N-Allyl-2-(allylamino)benzamide (8g): The general procedure B
was applied to amide 7e (442 mg, 3.25 mmol, 1 equiv.) and allyl
alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent used for the flash col-
umn chromatography: petroleum ether/ethyl acetate, 100:0 to
75:25. Rf = 0.42 (75:25); brown viscous oil; yield 15 %. 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 3.75 (dt, J = 5.1, 1.6 Hz, 2 H), 3.95 (tt,
J = 5.6, J = 1.0 Hz, 2 H), 5.03–5.27 (m, 4 H), 5.75–5.96 (m, 2 H), 6.10
(s, br., 1 H), 6.52 (t, J = 7.8 Hz, 1 H), 6.61 (d, J = 7.8 Hz, 1 H), 7.21 (t,
J = 1.3 Hz, 1 H), 7.28 (dd, J = 7.8, J = 1.5 Hz, 1 H), 7.78 (s, br., 1 H)
ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 41.0, 44.6, 111.3, 114.0,
114.2, 115.1, 115.4, 126.1, 131.7, 133.2, 133.7, 148.3, 168.5 ppm. HR-
MS (+ESI): calcd. for C13H17N2O [M + H]+ 217.1341, found 217.1330.
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1
yield 33 %. H NMR (300 MHz, CDCl3, 25 °C): δ = 4.22 (d, J = 5.6 Hz,
2 H), 5.14 (m, 2 H), 5.80 (m, 1 H), 7.65 (m, 2 H), 7.78 (m, 2 H) ppm.
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134.2, 167.9 ppm.
N,N-Diallyl-4-methylbenzenesulfonamide (8i):[31] The general
procedure B was applied to the sulfonamide 7f (556 mg, 3.25 mmol,
1 equiv.) and allyl alcohol (663 μL, 9.75 mmol, 3 equiv.). Eluent
used for the flash column chromatography: petroleum ether/ethyl
acetate, 100:0 to 80:20; yield 97 %. 1H NMR (300 MHz, CDCl3, 25 °C):
δ = 2.39 (s, 3 H), 3.78 (d, J = 6.2 Hz, 4 H), 5.13 (m, 4 H), 5.60 (m, 2
H), 7.28 (d, J = 7.9 Hz, 2 H), 7.68 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 21.4, 49.3, 118.8, 127.1, 129.7, 132.7,
137.4, 143.3 ppm.
4-Methyl-N-(2-methylallyl)benzenesulfonamide (8j):[32] The gen-
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3.25 mmol,
1 equiv.) and 2-methylprop-2-en-1-ol (820 μL,
9.75 mmol, 3 equiv.). Eluent used for the flash column chromatogra-
phy: petroleum ether/ethyl acetate, 100:0 to 80:20; yield 62 %. 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 1.59 (s, 3 H), 2.34 (s, 3 H), 3.39 (d,
J = 6.2 Hz, 2 H), 4.74 (m, 3 H), 7.21 (dd, J = 8.5 Hz, 2 H), 7.26 (d, J =
8.3 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 19.0, 20.4,
47.0, 111.7, 126.1, 128.6, 136.0, 139.5, 142.3 ppm.
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Received: April 22, 2016
Published Online: ■
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Amide Allylation
M. S. Azizi, Y. Edder, A. Karim,
M. Sauthier* ......................................... 1–9
Nickel(0)-Catalyzed N-Allylation of
Amides and p-Toluenesulfonamide
with Allylic Alcohols under Neat and
Neutral Conditions
Amides and p-toluenesulfonamide are water as a byproduct. Interestingly,
N-allylated using allyl alcohol in a cata- self-etherification of allylic alcohol is a
lytic fashion. The reaction is promoted competing side reaction that yields di-
by nickel-based catalysts and yields allyl ether.
DOI: 10.1002/ejoc.201600500
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