Dual nickel and Lewis acid catalysis for cross-electrophile coupling: The allylation of aryl halides with allylic alcohols

Article abstract of DOI:10.1039/c7sc03140h

Controlling the selectivity in cross-electrophile coupling reactions is a significant challenge, particularly when one electrophile is much more reactive. We report a general and practical strategy to address this problem in the reaction between reactive and unreactive electrophiles by a combination of nickel and Lewis acid catalysis. This strategy is used for the coupling of aryl halides with allylic alcohols to form linear allylarenes selectively. The reaction tolerates a wide range of functional groups (e.g. silanes, boronates, anilines, esters, alcohols, and various heterocycles) and works with various allylic alcohols. Complementary to most current routes for the C3 allylation of an unprotected indole, this method provides access to C2 and C4-C7 allylated indoles. Preliminary mechanistic experiments reveal that the reaction might start with an aryl nickel intermediate, which then reacts with Lewis acid activated allylic alcohols in the presence of Mn.

Full text of DOI:10.1039/c7sc03140h

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Dual Nickel and Lewis Acid Catalysis for Cross-Electrophile
Coupling: Allylation of Aryl Halides with Allylic Alcohols
Received 00th January 20xx,
Accepted 00th January 20xx
Xue-Gong Jia, Peng Guo, Ji-Cheng Duan, Xing-Zhong Shu*
Controlling of the selectivity in cross-electrophile coupling reactions is a significant challenge, particularly when one
electrophile is much more reactive. We report a general and practical strategy to address this problem in the reaction
between reactive and unreactive electrophiles by a combination of nickel and Lewis acid catalysis. This strategy is used for
the coupling of aryl halides with allylic alcohols to form linear allylarenes selectively. The reaction tolerates a wide range of
functional groups (e.g. silanes, boronates, anilines, esters, alcohols, and various heterocycles) and works with various
allylic alcohols. Complementary to most current routes for C3 allylation of unprotected indole, this method provides an
access to C2 and C4-C7 allylated indoles. Preliminary mechanistic experiments reveal that the reaction might start with an
arylnickel intermediate, which then reacts with Lewis acid activated allylic alcohols in the presence of Mn.
DOI: 10.1039/x0xx00000x
www.rsc.org/
overcome the selectivity challenge in cross-electrophile
coupling reactions. Recently, Weix has reported a dual nickel
and palladium catalysis, achieving cross-coupling of two
reactive electrophiles (Ar-Br + Ar-OTf).9 MacMillan and Doyle
demonstrated that the coorperative nickel and photoredox
catalysis enabled the coupling between reactive and
Introduction
Selective cross-electrophile coupling has recently emerged as
an increasingly popular approach for constructing C-C bonds.1
The reaction achieves the union of two different bench-stable
electrophiles (aryl/alkyl halides etc.), avoiding using air and/or
moisture sensitive organometallic reagents (RMgX, RZnX,
RSnR’3, RB(OH)2 etc.).2 Unlike in conventional cross-coupling,
where the selectivity is controlled by oxidative addition of
electrophile and transmetallation of nucleophile, generally
both electrophiles will compete for the oxidative addition at
the catalyst in cross-electrophile coupling. Thus the control of
the selectivity for cross-product over symmetric dimer is of
particular challenge, especially when one electrophile is much
more reactive than the other. Indeed, such a reaction has been
realized very recently3 and significant progress is achieved in
unreactive electrophiles (aryl/alkyl halides
+ carboxylic
acids).10 This strategy, while powerful, is less effective when
non-radical precursor is used. We considered that the use of
LA (Lewis acid) will lower the activation energy of inert C-O
bond,11 offering an opportunity for cross-electrophile coupling
of unreactive O-electrophiles. We report here a general and
practical strategy for cross-electrophile coupling between
reactive and unreactive electrophiles by a combination of
(a) Dual nickel and palladium catalysis (Weix, 2015)9
nickel catalysis with
a
metal reductant4. The substrate,
however, remains to be confined to reactive electrophiles (R-I,
Br, Cl, OTf etc.). Given that inert O-electrophiles (alcohol,
phenol, ether etc.) are more readily available and their
coupling reactions typically require organometallic reagents,5
the development of a strategy to couple these compounds
with electrophiles will be highly attractive but remains
extremely challenge.6
Ni
Pd
Ar1
Ar2
Ar1
Ar2
Br
TfO
+
Zn
reactive electrophile
(b) Dual nickel and photoredox catalysis (MacMillan and Doyle, 2014)10a
Ni
Ir
Br
HO2C
Ar
+
Ar
hν
N
N
Integration of multiple catalytic systems to enhance
reactivity and/or selectivity is a concept often employed by
biological catalysts7 and is an emerging strategy in molecular
catalysis.8 The cooperative effects offer an opportunity to
R
R
unreactive electrophile
(radical precursor)
(c) Dual nickel and Lewis acid catalysis (this work)
Ni
LA
HO
Ar
Br
Ar
+
Mn
unreactive electrophile
(non-radical precursor)
Scheme 1 Dual catalysis to address the selectivity challenge in cross-electrophile
coupling.
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nickel and LA catalysis. The strategy was applied for the
allylation of aryl halides with allylic alcohols to afford
allylarenes.
Results and discussion
We began our investigations by exploring the reaction of 4-
bromotolune 1aa with cinnamyl alcohol 2a 18
The Mizoroki-
.
Allylarenes are ubiquitous motifs in various biologically
active natural products.12 The precise synthesis of these
compounds has been achieved by the coupling reaction of aryl
halides with allyl metals,13 the allylation reaction of aryl metals
with allylic substrates,14 and the reductive allylation reaction of
Ar-Br with allylic acetate.15 These reactions, while are powerful,
the pre-activation of at least one reactant is required. In terms
of atom- and step-economy, the synthesis of allylarenes
directly from non-activated precursors will be much more
attractive, but remains particular challenge, including: (1) the
selectivity for the allylation of electrophiles (Ar-Br) over
Heck reaction product was not observed under reductive
conditions. In the absence of a LA, significant amount of biaryl
dimer was obtained, but no or trace of cross-product
observed (Table S1). Addition of catalytic amount of LA
significantly improved the selectivity for (Table S2). Further
3 was
3
optimization of reaction conditions revealed that the use of
Ni(dppp)Cl2 (10 mol %), bpy (20 mol %), ZrCl4 (10 mol %) and
Mn (3.0 equiv) in DMA afforded 3
in 85% yield.19
With optimized conditions in hand, we then investigated
the reaction scope of aryl bromides. Both electron-rich and
electron-poor aryl bromides gave cross-coupling products in
nucleophiles (C-OH),16 (2) the selectivity for the reaction of Ar-
moderate to good yields (Scheme 2,
the aromatic ring was tolerated (
substitution was tolerated when Ni(diglyme)Br2 was used as a
catalyst ( ). The reaction was selective for functionalization of
Br bond over C-Cl, C-F bonds and styrenyl group, thus
enabling the later available for additional transformation (
3-
10). Substitution around
17
Br with C-OH over C=C bonds.
In this article, we
3-5). A steric hindered
demonstrated such a convenient synthetic route for selective
synthesis of allylarenes from Ar-Br and allylic alcohols.
7
C
−
9-
2a
Ph
HO
Br
13). Functional groups such as tertiary amine, ester, ketone, as
10 % Ni(dppp)Cl2, 20 % bpy
Ph
R
R
well as a strained ring were accommodated and remained
10 % ZrCl4, Mn (3.0 eq.)
intact
(14-18). Heteroarenes and polyarenes, which are
DMA, 20-35 o
C
1aa-at
3-22
prevalent in pharmaceuticals, could be precisely allylated (18
-
22). The reaction could be scaled up to gram scale and gave 22
in a 75% yield.
Steric and electronic effect
Me
While the existing allylation reactions of allylic alcohols are
efficient for allylating nucleophiles,14 this reaction is highly
selective for electrophiles. A broad range of nucleophilic aryl
bromides were then selectively allylated, leaving alcohol,20
amine,21 phenol,22 indole23 and silane intact (Scheme 3). The
utility of this method was illustrated by regiodivergent
synthesis of allylated indoles, which are important structure
Me
MeO
Me
3, 85%
4, 75%
5, 78%
6, 68%
F
Ph
iPr
7, 82%a
F
10, 53%
F
8, 85%
9, 88%
Br
2a (1.0 equiv)
Functional group tolerence
Ph
Nu
Nu
10 % Ni(diglyme)Br2, 20 % bpy
10 % ZrCl4, Mn (3.0 eq.)
23-34
1au-1bf
(1.0 equiv)
DMA, 20-35 o
C
Me2N
F3C
12, 58%
Cl
O
11, 68%
13, 55%
14, 78%
H3C
HO
HO
H2N
24, 61%b
OH
O
23, 79%a
25, 52%c
26, 90%c
O
O
MeO
OMe
Me
16, 42%
4
5
2
17, 84%
18, 49%
15, 59%
N
H
N
H
N
H
TMS
27, 71%b
Hetereocycles and gram-scale reaction
28, 51%b
29, 80%
30, 81%
F
CO2Me
6
O
N
O
N
O
S
21, 68%
7
N
H
N
H
H
H
22, 87%
(1.07 g, 75%)b
19, 90%
20, 84%
32, 94 %
34, 70%c
31, 74 %
33, 45%
Scheme 2 Scope of aryl bromides. All data are the average of two experiments.
1aa-at (1.5 equiv.) and 2a (1 equiv.) were used. Reactions for 32-48 h. Yields are
Scheme 3 Reactions of 2a with nucleophilic aryl bromides. All data are the
average of two experiments. Yields are isolated yields. Reactions for 32-48 h. [a]
Conditions in Scheme 2, reaction for 60 h. [b] Conditions in Scheme 2, amount of
ArBr: 1.0 equiv. [c] Amount of ArBr: 1.5 equiv.
isolated yields. [a] Catalyst: 10% Ni(diglyme)Br2. [b] 95 h.
2 | J. Name., 2012, 00, 1-3
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motif in many bioactive natural products and drugs.24 Being
complementary to conventional methods for the allylation of
indoles at the C3 position,23 our approach provides a direct
access to C2-, C4-, C5-, C6- and C7-allylated indoles (28-34). Of
note, the desired products were obtained in high yields even
when an equal amount of two electrophiles was used.
The reaction proceeded efficiently with a variety of allylic
alcohols and in most cases gave linear (E)-products selectively
(Table 1). In addition to cinnamyl alcohols, unsubstituted and
alkyl-substituted allylic alcohols also coupled with
a
functionalized aryl group (entries 1-5). Although the reaction
with α-ethyl substituted alcohol is less selective, substrate with
phenyl substitution gave only linear (E)-product (entries 6-7).
Table 1 Scope of allylic alcohols.
Prenylated arenes have been found in many bioactive
compounds, and their synthesis has been extensively studied
but requires prenyl-metal species (allylfluorosilanes,
allylstannanes, allylboron derivatives etc.).13 Such a structure,
however, could be efficiently constructed here from isoprenyl
alcohol with a linear/branched ratio of 180:1 (entry 8). Both
nonsymmetrical substrates 2j and 2k gave the same product
42 in useful yields, suggesting the reaction goes through a π-
allyl nickel intermediate.
entry
1
allylic alcohol
product
yield
80%
The cross-electrophile coupling reaction is well
complementary to the Pd-catalyzed reactions, enabling 1-
bromo-4-iodobenzene to be sequentially functionalized with
allylic alcohol 2l to ketone 43 and allylated product 44 (eq. 1).
Our reaction conditions were also compatible with aryl borates
and a sequence of C-Br bond allylation and C-B bond coupling
is possible for the conversion of substrate 1bh to product 46
(eq. 2).
LA was expected to lower the activation energy of C-OH
bond. To confirm this assumption and understand the
mechanistic details of this process, we monitored the reaction
of 1aa with 2j by GC analysis. In the absence of a LA, no cross-
coupling product 42 and side products from 2j was observed in
40 min, but aryl dimer 51 was steadily increasing (Figure S1a).
This result indicates that aryl bromide is reactive towards Ni
catalyst, while allylic alcohol is inert. The use of 15 mol % of
2
3
62%a, b
75%
4
5
73%
58%
OH
6
7
63%a, c
76%
Et
2g
OH
Ph
2h
8
66%a, d
9
56%e
60%
10
42
All data are the average of two experiments. Yields are isolated yields. Reactions
for 48-50 h. Amount of 1am: 2.0 equiv. 1aa were used for 2j and 2k [a] Catalyst:
10% Ni(dppf)Cl2, 20% 3,4,7,8-tetramethyl-1,10-phenanthroline, 20% AlCl3, 1am
Scheme 4 Selectivity of Ar-Br and allylic alcohol in initial oxidative addition to Ni(0). A
mixture of 1aa/2a (1:1) was added to an in situ generated Ni(0) catalytic system.
Samples were collected in each 10 min and analysed by GC. Mn was added in 40 min.
[b]
(1.5 equiv). [l/b] (linear/branched ratio) = 4:1, linear product is a 3:1 E/Z
isomers. [c] [l/b] = 11:1, linear product is a 5:1 E/Z isomers. [d] [l/b] = 180:1. [e] 15
% catalysts were used.
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(L)
NiII
Br
Nu
A
reduction
Br
Nu
1
NiI(L)
(L)Ni0
Nu
B
LA
reduction
OH
C
Figure 1 Relative reactivity of Ar-NiII(bpy)Br (49) and (bpy)Ni0(cod) (50) capable of
catalysing the reaction of 1ae with 2a. Complex 49 or 50 (30 mol %) was added to a
solution of 1ae (1.2 or 1.5 equiv.), 2a (1.0 equiv.), bpy (30 mol %), ZrCl4 (10 mol %) and
Mn (3.0 equiv.) in DMA. Samples were collected, quenched with H2O and analysed by
GC.
(L)
NiIII
Nu
LA
OH
Nu
X
product 3
2
D
Scheme 5 Proposed mechanism for allylation of aryl bromides with allylic alcohols by
dual catalysis.
ZrCl4 significantly promoted the cross-coupling process,
indicating the crucial role of LA in the activation of allylic
alcohols (Figure S1b).
radical scavenger such as butylated hydroxytoluene (BHT),
hydroquinone and 1,1-diphenylethylene did not inhibit the
reaction of 1aa and 2a, no product 3 was obtained when
2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO, 1.5 equiv.) was
employed (Table S8), consistent with the presence of a single-
electron process capable of reducing oxidized Ni catalyst.
Although a detailed mechanistic picture for this reaction
requires further investigation, based on above results, we
tentatively proposed a catalytic cycle as shown in Scheme 5.28
Both aryl bromide and allylic alcohol will undergo oxidative
addition to Ni(0), generating Ar-NiII(L)Br and allyl-NiII(L)X16a,b,21b
In order to determine which intermediate is formed firstly, we
studied the relative reactivity of 1aa and 2a with in situ
generated (bpy)Ni0(cod).25 We would expect, by quenching the
reaction, a Ni(II) intermediate would afford Ar-H (47) or Allyl-H
.
(
48).26 Scheme 4 shows that, in every 10 min before addition
of Mn, 4.6% of Ar-H is obtained in each sample but no Allyl-H is
observed, consistent with Ar-NiII(L)Br forming firstly. While The oxidative addition of Ar-Br to Ni(0) gives an arylnickel(II)
both cross-product and Ar-Ar dimer were steadily increasing
intermediate
by oxidative addition of LA-activated allylic alcohol will give π-
allylnickel(III) intermediate D 29
Reductive elimination of this
A. Reduction of A
to arylnickel(I) B4a-b followed
3
after addition of Mn (3 equiv.), Allyl-H or Allyl-Allyl was still not
observed (Scheme S1), suggesting a mechanism in which Ar-
NiII(L)Br serves as an intermediate.
.
complex will afford the desired product and recycle the
catalyst with Mn. At present, we cannot rule out a radical
mechanism as shown in the reaction of aryl halides with alkyl
halides.30
To take more insight into the mechanism of this process,
27
complex Ar-NiII(bpy)Br
(
49
)
was synthesized from the
reaction of (bpy)Ni0(cod) (50) with aryl bromide 1ae. We
would expect that, if Ar-NiII(bpy)Br (49) is an intermediate, the
initial rate of reaction with complex 49 would be faster than
that of reaction with pre-catalyst 50. Figure 1 shows that, in 6
Conclusions
min, the use of complex 49 (30 mol %) give product
7
7 in almost
30% yield, while only trace of is formed when pre-catalyst 50
In summary, we have reported a dual nickel and Lewis acid-
catalyzed allylation of aryl halides with allylic alcohols. This
approach represents a new strategy for cross-electrophile
coupling between reactive and unreactive electrophiles. The
reaction tolerated a wide range of functional groups including
alcohols, phenols, anilines, silanes, and even borates. In most
(30 mol %) is used (Figure 1). This result further indicates that
Ar-NiII(L)Br is likely the key intermediate in this reaction.
Reduction of Ni(II) complex to Ni(I) by Mn has been
extensively reported.4a-b The stoichiometric reactions of 49
with alcohol 2a gave product
7 in 0% yield (without Mn) and
90% yield (with Mn), suggesting that Ni(II) complex 49 might
be reduced to more nucleophilic ArNi(I) firstly, then reacts
with allylic alcohols (eq. 3). The use of electron-poor aryl
cases, the reaction gave linear (E)-allylarenes highly selectively.
The utility of this method is clearly illustrated by facile access
to C2 and C4-C7 allylated indoles. Preliminary mechanistic
studies revealed that the reaction might start with an
arylnickel intermediate, which then reacted with allylic
alcohols in the presence of Lewis acid and reductant. The
application of this strategy for cross-electrophile coupling of
other unreactive electrophiles is ongoing in our laboratory.
bromides (e.g. 18 vs 19, 32 vs 33) generally gave inferior
results, which is consistent with this process. While the use of
i-Pr
ZrCl4 (1.0 eq.), bpy (1.0 eq.)
Ph
2a
(1.0 eq.)
+
(3)
DMA, rt, 4h
7
(a) without Mn
0%
Ar-Ni(II)(bpy)Br (49, 1.0 eq.)
Ar: 2-i-Pr-Ph
(b) with Mn (2.0 eq.)
90%
Acknowledgements
We thank the financial support from NSFC (21502078), FRFCU
(lzujbky-2015-k06, lzujbky-2016-ct09), and 1000 Talents Plan
4 | J. Name., 2012, 00, 1-3
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Madison), Prof. Wei Wang (LZU, China) for helpful discussion,
Prof. Yixia Jia (ZJUT, China) for his help in obtaining part of
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For limited reports on reductive coupling between
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ARTICLE
Journal Name
Lufford, M. R. Prinsell, D. J. Weix, J. Org. Chem. 2012
77, 9989.
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16 An electrophilic π-allyl metallic intermediate is
generally formed in allylation reactions, which could be
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17 The reactions of organic halides with allylic alcohols
typically give Mizoroki-Heck products rather than
allylation products. For a represented review, see: J.
Muzart, Tetrahedron 2005, 61, 4179.
18 For detailed conditions, see Supporting Information.
19 Although Ni(diglyme)Br2 gave
a comparable yield
(Table S4, S6), the applicability of Ni(dppp)Cl2 for
reactions in Scheme 2 is more general. The role of
phosphine ligand remains unclear at the moment.
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27 CCDC 1515176 (49
)
contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic Data Centre.
28 Alternatively, a mechanism starting with an allyl-Ni(II)X
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Also see: ref. 26.
6 | J. Name., 2012, 00, 1-3
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A dual nickel and Lewis acid catalysis has been developed for the coupling reaction between
reactive and unreactive electrophiles.