Catalytic C?C Bond Formation Using a Simple Nickel Precatalyst System: Base- and Activator-Free Direct C-Allylation by Alcohols and Amines

Article abstract of DOI:10.1002/chem.201801241

A “totally catalytic” nickel(0)-mediated method for base-free direct alkylation of allyl alcohols and allyl amines is reported. The reaction is selective for monoallylation, uses an inexpensive Ni^II precatalyst system, and requires no activating reagents to be present.

Full text of DOI:10.1002/chem.201801241

A Journal of
Accepted Article
Title: Catalytic C-C bond-formation using a simple nickel precatalyst
system: base- and activator-free direct C-allylation by alcohols
and amines.
Authors: Joseph B. Sweeney, Anthony Ball, and Luke Smith
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To be cited as: Chem. Eur. J. 10.1002/chem.201801241
Link to VoR: http://dx.doi.org/10.1002/chem.201801241
Supported by

10.1002/chem.201801241
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COMMUNICATION
Catalytic C-C bond-formation using a simple nickel precatalyst system:
base– and activator–free direct C–allylation by alcohols and amines.**
Joseph B. Sweeney,*, † Anthony K. Ball, ¶ and Luke J. Smith¶
Abstract: A 'totally catalytic' nickel(0)-mediated method for base-
free direct alkylation of allyl alcohols and allyl amines is reported.
The reaction is selective for monoallylation, uses an inexpensive
Ni(II) precatalyst system, and requires no activating reagents to be
present.
transformation (since water or ammonia – in the case of primary
allylamines – are the by-products), but the lower reactivity of these
substrates typically demands the presence of stoichiometric
amounts of activators (often Brønsted or Lewis acids). [5], [6] The
ability of nickel complexes to mediate oxidative insertion into C-O
and C-N bonds without the need for activating reagents has led to
Catalytic bond-forming processes have become indispensible tools
in all aspects of synthetic chemistry, for both academic and
industrial chemists, and there has been a recent and increasing
emphasis on methods which avoid catalysts derived from high-cost,
non-abundant metals. Within the diverse research into the
application of catalytic complexes used for synthesis and
manufacturing, this has led to a focus on the use of nickel as a
replacement for palladium in catalytic transformations. In addition
to the cost advantages in using nickel, the differences in character
of this more electropositive metal allow quite different
opportunities for catalytic bond-formation compared with
palladium, facilitating some chemical processes not available to the
more expensive metal.[1 ] Notwithstanding these advantages, the
adoption of nickel catalysis as an alternative to palladium has been
slow, perhaps due to the comparative difficulty in handling Ni(0)
complexes: the most widely used catalytic complex of nickel,
Ni(COD)2 is well-known to be highly air-sensitive, making it
difficult to handle, and compromising the robustness and
practicality of nickel-catalysed processes. To meet this obstacle,
several elegant Ni(0) precatalysts systems have been developed to
these catalysts being used in allylation using alcohols[7],[8] and
[7b], [9],[10]
amines;
to date, the reported processes using alcohols
have required Ni(COD)2, and (where mixtures are possible11
often do not show selectivity for monoallylated products. [12]
)
a. Tsuji-Trost allylation3d
O
O
R5
R4
R5
Pd(0), Ir(I), Rh(0),
Ru(0), Ni(0)
O
R1
O
X
R1
+
O
HO
X
R2 R3
Base
R2 R3 R4
X = Ac, C(O)R,
C(O)OR,
b. Alcohols and amines in catalytic allylation6,7
P(O)(OR)2
O
O
R5
R4
R5
O
R1
Pd(0)
YH
R1
+
O
HY
A
R2 R3
Y = O, NH
Base
Activator
R2 R3 R4
circumvent the use of Ni(COD)2 using either synthesized
2 ]
precatalysts,[
or combinations of simple nickel salts with
stoichiometric reducing agents. Though several reports[3] have
described the use of main group metals as in situ reducing agents to
convert Ni(II) into catalytically active Ni(0), to our knowledge
there has been no ‘totally catalytic’ combination (i.e., where the
reducing agent is present in the same catalytic amount as the nickel
component) and there are no reports of such a method being used
in catalytic alkylation using allyl alcohols and amines. We report
here an air-insensitive Ni(0)-catalyzed allylation process which is
selective for monoallylation using allylic alcohols, and which
employs an inexpensive nickel salt and equimolar elemental zinc as
an effective precatalyst combination.
c. Ni(COD)2 – catalysed diallylation using allyl alcohols11
O
O
R2
O
R2
R3
R1
OH
R1
+
H2O
O
Ni(COD)2
R3
R1 = H, Ph
R1
d. This work: practical Ni(0)-catalysed monoallylation of alcohols and amines
O
O
R4
R
R
O
Catalytic alkylation of allylic acetates[4] and analogous reagents
using Earth-scarce metal complexes is one of the most-employed
synthetic methods for C-C bond formation, but traditional
processes generate stoichiometric amounts of by-products
(typically acids or their salts). The use of allylic alcohols and
amines in such processes represents a more atom-economical
R1
Ni(II)/Zn (5 mol%)
YH
R1
+
H2Y
O
R2 R3
Base – and Activator–free
R2 R3 R4
Figure 1: Catalytic allylation strategies.
We commenced our study with two aims: to develop a nickel-
catalysed method using allyl amines or alcohols which delivered
monoallylated products selectively, and to devise a means of
accessing the crucial Ni(0) catalysts from an inexpensive, air-stable
precursor. We chose to use NiBr2•3H2O, one of the most
inexpensive nickel salts,[13] as our nickel source, and elemental zinc
as the reducing agent (due to its low toxicity compared to other
metal reducing agents, such as manganese); as mentioned, key
goals of our study were to reduce the amount of reducing agent to a
low level, and to avoid the use of a base in the reaction, thereby
simplifying still further the process.
[*]
Prof. J. B. Sweeney, Dr. A. K. Ball, L. J. Smith
†Department of Chemistry, Lancaster University, Lancaster LA1 4YB
¶ Department of Chemical Sciences, University of Huddersfield
Queensgate, Huddersfield, HD1 3DH (UK)
E-mail: j.sweeney1@lancaster.ac.uk
[**] We are grateful to the University of Huddersfield (A. B. and L. J. S.)
for funding, and the Royal Society for an Industry Fellowship
(J.B.S.).
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201801241
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COMMUNICATION
The first conditions examined proceeded with poor conversion, but
in 50% yield based on recovered starting materials) (Figure 2).
optimized conditions, furnishing a library of allylation products 1
and 3a-n (Table 2). As demonstrated by these data, there is a clear
effect of CH acidity upon the product composition, with more
acidic substrates more likely to deliver mixtures of products. H-
bonding[15] seems to enhance diallylation (as seen in preparation of
3l). There is also an effect of steric compression in the ester
component: thus, whilst dimethyl malonate gives only monoallyl
product 1, larger esters tend to give (separable) mixtures of
products (vide 3g and 3j). Quaternary centres can be created in the
reaction, as shown by obtention of 3d–f in good yields.
MeO2C
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
NiBr2•3 H2O (5 mol%)
X
+
Zn (5 mol%), dppb (5 mol%)
DMF, 80 ˚C, 22 h
1
2
X = OAc: <5% conversion <5% yield
X = OH: 28% conversion 14% yield, 1 : 2 = 77 : 23
Figure 2. Ni(0)-mediated 'totally catalytic' allylation using allyl alcohol.
After an extensive analysis of the effects of variation in ligand,
solvent and additive, the optimum conditions for the reaction of
allyl alcohol with malonate were identified (Table 1, entry 16);
using this reagent/catalyst combination, high selectivity for
monoallylated product 1 was observed, in contrast to previously
reported catalytic nickel allylation processes,[11] and despite the use
of two equivalents of the nucleophile (used in excess to improve
yield). Moreover, the relative stoichiometry in the process
described here does not require large excesses of either reagent, or
reducing agent, or ligand. These facts endow this method with
enhanced utility, improved environmental impact and great
practicality.
Table 2: Scope of the Ni-catalysed allylation of nucleophiles with allyl
alcohol
OH
R1
O
O
NiBr2•3 H2O (5 mol%)
R
R1
Zn (5 mol%), dppf (5 mol%)
Bu4NOAc (5 mol%), DMA
50 ˚C, 66h
R
3
Ph
O
Me
O
CO2Me
CO2Me
1 71% yield
Table 1: Reaction optimization
CO2Et
CONHPh
MeO2C
CO2Me
CO2Me
CO2Me
NiBr2•3 H2O (5 mol%)
3a 96%
CO2Me
CO2Me
3b 53%
OH
Zn (5 mol%), ligand (5 mol%)
additive, solvent, temp., time
O
Me
O
1
Entry Ligand Solvent Temp Time Conv/%a Yield/%b Selectivityc
Me
COPh
50d
60d
0
77:23
91:9
-
O
1
2
dppb
dppb
PPh3
DMF 80 °C 18 h
DMF 80 °C 96 h
DMF 80 °C 96 h
DMF 80 °C 96 h
DMF 80 °C 96 h
DMF 80 °C 96 h
DMF 80 °C 96 h
DMF 80 °C 96 h
NMP 80 °C 96 h
MeCN 80 °C 96 h
DMA 80 °C 66 h
DMA 50 °C 66 h
DMA 50 °C 66 h
DMA 50 °C 66 h
DMA 50 °C 66 h
DMA 50 °C 66 h
28
50
OEt
3c 60%
3d 65%a
3e 86%
3
<5
O
4
dppe
dppp
dppf
<5
0
-
Me
O
CO2Me
CO2Et
5
<5
0
-
CO2Et
O
6
90
58
0
82:18
-
Me
3f 68%
CO2Et
XantPhos
BINAP
dppf
7
<5
3g 51%a (88 : 12)b
3h 51% (71 : 29)
8
<5
0
-
Me
O
CO2Me
CO2Bn
9
<5
0
-
10
11
12
13
14
15
16
dppf
23
70d
51
41d
37d, e
44d,f
48g
>95:5
80:20
91:9
95:5
90:10
85:15
>90:10
CN
CO2Bn
dppf
>95
75
3i 99% (24 : 76)
3j 98% (86 : 14)
3k 99% (71 : 29)
dppf
O
dppf
35
CO2Me
CN
Me
O
dppf
70
CONH2
dppf
>95
>95
O
dppf
71g,h
3l 66% (42 : 58)
3m 73%
3n 89%
Estimated from 1H NMR of crude product;
Isolated yield;
a.
b.
c.
d
1
Monoallylated : diallylated (determined from H NMR of crude product);
f
f
Reaction conditions: Allyl alcohol (1.0 mmol), nucleophile (2.0
mmol), NiBr2•3H2O (0.05 mmol), dppf (0.05 mmol), nBu4NOAc (0.05
Yield based on recovered starting material; 5 mol% AcOH present;
5
[
]
mol% NH4OAc present; 5 mol% NBu4OAc 14 present; 2 eq. malonate
g
h
a
mmol) , zinc (0.05 mmol), DMA, 50 ˚C, 66 h, sealed vial. reaction
used.
carried out at 80 ˚C; b Monoallylated : diallylated.
Armed with a robust, operationally simple method for selective
nickel-catalysed monoallylation, we next examined the scope of
the reaction, from the perspective of the nucleophilic component.
Thus, a range of nucleophilic partners were tested using the
Having probed the scope of nucleophile in this nickel-catalysed
processes, the reactions of a range of allyl alcohols with acetamide
4 were next examined: these transformations generally proceeded
in good yields, and with complete selectivity for monoallylated
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10.1002/chem.201801241
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products (Table 3). In all cases, where possible, linear products
were favoured over branched isomers (vide substrates 5b, 5d and
5h, entries 3,5 and 9), and alkene stereochemistry was retained
(entries 6 and 7). The obtention of the same products (3aa, 3ab and
3ae) from isomeric alcohols implies a common intermediate in
each of these reactions.
reactions using allyl amines.[10] We were gratified, therefore, to
observe that our method was also productive when using N,N-
diethyl allylamine or allylamine itself as a π-allyl precursor (Table
4).
Table 4: Ni-catalysed allylation using allylamine
NiBr2•3 H2O (5 mol%)
CO2Me
NR2
+
Table 3: Scope of the Ni-catalysed allylation with various allyl alcohols
MeO2C
CO2Me
Zn (a mol%)
Ligand (5 mol%)
DMF, 80 ˚C, 22h
CO2Me
O
R1
O
OH
NiBr2•3 H2O (5 mol%)
1
R1
+
CONHPh
CONHPh
Yield/%a
89
Selectivityb
85:15
85:15
85:15
85:15
85:15
–
R2 R3
Zn (5 mol%)
dppf (5 mol%)
Entry
R
a
Ligand
R2 R3
Bu4NOAc (5 mol%)
DMA, 50 ˚C, 66h
3a, 3aa-af
1
2
3
4
5
6
Et
Et
Et
Et
H
15
10
5
dppb
dppb
dppb
dppb
dppb
dppf
5
4
80
Entry
Alcohol 5
OH
Product
Yield/%a
96
90
74c
O
5
1
2
5
86
0d
CONHPh
3a
H
5
a.
b
c.
d.
Isolated yield; Monoallylated : diallylated; NiCl•6H2O used;
Me
OH
Complex mixture of products obtained.
O
73
Me
5a
Me
In the process using allylamine, mixtures of mono- and diallylated
products were more often obtained, perhaps being a reflection of
the relative basicity of the leaving group (an amide, rather than
hydroxide), which more rapidly deprotonates the monoallylated
product and thereby encouraging diallylation. Using a range of
active methylene nucleophiles, allylamine reacted to give products
of C-allylation (Table 5).
CONHPh
OH
Me
3
4
Me Me
27
69
3aa
3ab
5b
Me
OH
O
5c
Me
OH
Table 5: Scope of the Ni-catalysed allylation with allyl amine
CONHPh
5
6
56
54
R1
O
Me
O
NiBr2•3 H2O (5 mol%)
NH2
+
5d
R
R1
Zn (5 mol%), dppb (5 mol%)
DMF, 80 ˚C, 22h
R
O
OH
Entry
1
R
R1
Product
Yield % Ratioa
CONHPh
Me
CO2Me
1
CO2Me
OMe
Me
89
53
71 : 29
62 : 38
5e
CO2Me
3ac
3ad
Me
O
O
2
3
CONHPh
CO2Et
3a
Me
OH
CONHPh
7
66
CONHPh
5g
5g
Ph
O
Ph
3b
30b
100:0
CO2Et
Ph
OH
8
9
48
94
CO2Et
O
3g
4
5
CO2Et
OEt
75
84
73 : 27
76 : 24
CO2Et
CO2Bn
Ph
OH
CONHPh
Ph
5h
3ae
3af
3j
CO2Me
OBn
CO2Me
Me
O
O
OH
3k
6
7
CO2Bn
CN
Me
OEt
40
96
100 : 0
27 : 63
Me
10
73
CO2Bn
Me
CONHPh
5k
CO2Et
3i
Reaction conditions: Allyl alcohol (1.0 mmol), N-phenyl
acetoacetamide (2.0 mmol), NiBr2•3H2O (0.05 mmol), dppf (0.05
CN
n
Me
O
mmol), Bu4NOAc (0.05 mmol) , zinc (0.05 mmol), DMA, 50 ˚C, 66
h, sealed vial; a. Isolated yield.
3l
8
CONH2
Me
23
30 : 70
CONH2
Though palladium-mediated processes are well-known,[16] there are
no reports of a general method for nickel-catalysed allylation
Reaction conditions: Allyl amine (1.0 mmol), nucleophile (1.5 mmol),
NiBr2•3H2O (0.05 mmol), dppb (0.05 mmol), zinc (0.05 mmol),
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a
b
DMF, 80 ˚C, 66 h, sealed vial. Monoallylated : diallylated; N,N-
diethylallylamine used.
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In summary, we have described a practical, scalable and cost-
effective method for executing nickel-catalysed C-allylation
reactions using readily available, inexpensive, air-insensitive
reagents. The use of allyl alcohols and amines as substrates in
such reactions offers significant advantages and can be easily
applied to gram-scale preparations. We are currently engaged
in exploring the mechanistic nuances and extending the
boundaries of this highly practical catalytic process.
Keywords: • Catalytic • nickel • C-C bond formation • allylation •
sustainable • quaternary
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10.1002/chem.201801241
Chemistry - A European Journal
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Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
O
O
R
O
R1
R4
Ni(II)/Zn (5 mol%)
= OH, NEt2, NH2
X
R
R1
O
R2 R3
R2 R3 R4
X
• Base – and activator–free • Inexpensive Ni(0) precatalyst system • > 30 examples
Abstract: A 'totally catalytic' nickel(0)-mediated method for
base-free direct alkylation of allyl alcohols and allyl amines is
reported. The reaction is selective for monoallylation, uses
an inexpensive Ni(II) precatalyst system, and requires no
activating reagents to be present.
Catalytic C-C bond-formation using a simple nickel
precatalyst system: base– and activator–free direct C–
allylation by alcohols and amines
Joseph B. Sweeney,* Anthony K. Ball, and Luke J. Smith
Page No. – Page No.
This article is protected by copyright. All rights reserved.