Unlocking Mizoroki–Heck-Type Reactions of Aryl Cyanides Using Transfer Hydrocyanation as a Turnover-Enabling Step

Article abstract of DOI:10.1002/chem.201604061

A new transfer hydrofunctionalization strategy to turnover H-M^II-X complexes has enabled both intra- and intermolecular Mizoroki–Heck (MH)-type reactions of aryl cyanides that are challenging to realize under traditional, basic conditions. Initially, a cascade carbonickelation/MH reaction of 2-cyanostyrenes was achieved using a key alkyne transfer hydrocyanation step. Mechanistic experiments supported the proposed catalytic cycle, including the turnover-enabling transfer hydrocyanation step. The reactivity was then extended to the intermolecular MH reaction of benzonitriles and styrenes.

Full text of DOI:10.1002/chem.201604061

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Accepted Article
Title: Unlocking Mizoroki-Heck Type Reactions of Aryl Cyanides Using Transfer Hy-
drocyanation as a Turnover-Enabling Step
Authors: Xianjie Fang; Peng Yu; Gabriele Prina Cerai; Bill Morandi
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To be cited as: Chem. Eur. J. 10.1002/chem.201604061
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Unlocking Mizoroki-Heck Type Reactions of Aryl Cyanides Using
Transfer Hydrocyanation as a Turnover-Enabling Step
Xianjie Fang†, Peng Yu†, Gabriele Prina Cerai and Bill Morandi*
Abstract: A new transfer hydrofunctionalization strategy to turnover
H–M(II)–X complexes has enabled both intra- and intermolecular
Mizoroki-Heck (MH) type reactions of aryl cyanides that are
challenging to realize under traditional, basic conditions. Initially, a
cascade carbonickelation/MH reaction of 2-cyanostyrenes was
achieved using
a key alkyne transfer hydrocyanation step.
Mechanistic experiments supported the proposed catalytic cycle,
including the turnover-enabling transfer hydrocyanation step. The
reactivity was then extended to the intermolecular MH reaction of
benzonitriles and styrenes.
The Mizoroki-Heck (MH)1 coupling between aryl electrophiles
and alkenes has found widespread applications in organic
synthesis.2 The traditional mechanism of this reaction involves
an initial oxidative addition, followed by insertion into an alkene
and β-hydride elimination. The H–M(II)–X species generated at
the end of the catalytic cycle is then commonly converted back
to a M(0) species through the use of a base to enable catalytic
turnover (Scheme 1).2 A wide range of electrophiles, including
halides,3 sulfonates,4 diazonium salts,5 and hydrazines,6 have
been used in this mechanistic manifold. However, the MH
coupling of less traditional electrophiles, such as ethers,7
amides8 or cyanides remains a major challenge in this area.
Herein, we report a transfer hydrofunctionalization approach to
catalyst turnover in MH reactions, a strategy that has enabled,
for the first time, the use of a broad range of Ar–CN electrophiles
in both intra- and intermolecular MH reactions.
Scheme 2. Reaction design.
The MH-type coupling of Ar–CN electrophiles would provide
a complementary methodology for the construction of C–C
bonds because aromatic nitriles are widespread compounds that
can be easily synthesized from inexpensive precursors
(carboxylic acids, amides, aldoximes and methyl arenes) that
are not derived from aryl halides.9 Aromatic nitriles also often
bear substitution patterns that are complementary to aryl halides
because the nitrile group, in contrast to halogens, directs
aromatic ring functionalization reactions to the meta position due
to its strongly electron withdrawing character.9 Additionally, the
cyano group is unreactive under most cross-coupling conditions
and can thus serve as a masked, orthogonal electrophile in a
synthetic sequence.10 To the best of our knowledge, the only
example of efficient MH reaction of cyanides has been realized
by the group of Chatani11 using a Rh catalyst under base-free
conditions, but the scope of this reaction is limited to the use of
vinylsilanes as coupling partners. The development of a MH-
Scheme 1. Traditional MH mechanism compared to new approach.
type coupling that can utilize
a broad range of cyano
electrophiles12 and alkenes has been challenging, in part
because the most efficient catalytic protocols to activate strong
C–CN bonds towards oxidative addition rely on the use of a
Lewis acid co-catalyst (Scheme 2b),13 a strategy potentially
incompatible with the use of bases in the traditional turnover-
enabling step of the MH reaction (Scheme 2a). Accordingly, in
preliminary experiments (Table S1), we did not observe any MH-
type reactivity between benzonitrile and styrene in the presence
[*]
[†]
Dr. X. Fang, M. Sc. P. Yu, M. Sc. G. Prina Cerai, Dr. B. Morandi
Max-Planck-Institut für Kohlenforschung
Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
E-mail: morandi@kofo.mpg.de
These authors contributed equally to this work.
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.
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of a base (Scheme 2c). Low reactivity (<10% yield) was
observed when combining the use of a base with a Lewis acid
As highlighted in our recent work,14 alkene hydrocyanation is
a reversible process under Ni catalysis and Al co-catalysis, a
feature that could complicate the realization of our novel
approach to MH reactions. Therefore, we reasoned that the use
of an alkyne instead of an alkene as acceptor for the transfer
hydrocyanation step might favor the desired process because
alkynes are more reactive towards H–Ni–CN, are less prone to
under
a
wide range of reaction conditions,
a
result
demonstrating that: (1) A Lewis acid is important to activate the
C–CN bond and; (2) it is difficult to combine the use of Lewis
acids with stoichiometric amounts of base due to the low
compatibility of these reagents. In need of a new approach, we
reasoned that transfer hydrocyanation14 could, in principle,
provide a mechanistically distinct alternative to catalyst turnover
in MH reactions (Scheme 2d and 2e) and circumvent the
traditional use of base. Such an approach to regenerate the
active catalytic species (Ni(0) or Pd(0)) is attractive because of
its compatibility with the Lewis acid co-catalyst necessary for
efficient oxidative addition of the C–CN bond. The incorporation
of a transfer hydrocyanation step in the catalytic cycle would
thus enable previously elusive transformations of R–CN and
provide a complementary strategy for catalyst turnover in cross-
coupling reactions.
undesired
oligomerization
and
are
irreversibly
hydrocyanated.14,15 With this idea in mind, we designed an
intramolecular MH-type reaction16 that relies on a domino alkyne
carbonickelation-MH reaction-alkyne hydrocyanation. The
elementary steps of this new reaction consist of an oxidative
addition of the Ar–CN bond, alkyne insertion, alkene insertion, β-
hydride elimination and catalyst regeneration through alkyne
hydrocyanation. The higher reactivity of the alkyne in both the
intermolecular insertion step and the hydrocyanation step should
facilitate the realization of this novel approach to MH-type
reactions.
We could verify our hypothesis experimentally through the
use of 2-cyanostyrene (1a) in the presence of 4-octyne (2a).
Under optimized conditions (substrate 1a, 2.0 equiv. alkyne 2a,
10 mol% Ni(COD)2, 20 mol% PPh3, 40 mol% AlMe2Cl in toluene
at 60 °C for 16 h) the desired benzofulvene product 3aa was
obtained in good yield. Importantly, the transfer hydrocyanation
product 4a was also obtained in good yield, a result that clearly
supports the proposed transfer mechanism. Control reactions
revealed the importance of all the components and confirmed
that the addition of base was detrimental to the reaction (Table
S2). Importantly, the use of 2-bromostyrene in place of 1a led to
rapid, undesired cyclotrimerization of 2a under a range of
conditions, with no formation of desired product 3aa. These
results demonstrate the divergent reactivity and thus, utility, of
the cyano electrophile in this transformation.
We next studied the scope of the reaction (Scheme 3).
Halogens and ethers on substrate 1 were tolerated and afforded
the products in high yields (3ca-3fa). An alkene and an alkyne
were also tolerated as substituents and the desired
benzofulvene products were obtained in good yields (3ga and
3ha). Heterocycles were also tolerated and afforded the
products both when used as substituents or as part of the final
heterocyclic product (3ia and 3ja). Both aliphatic and cyclic
alkynes were efficient partners in the transformation (3ab-3ae,
3ag). Finally, strained alkenes such as norbornene can also be
used in the transformation (3af). Importantly, all the experiments
provided moderate to good yields of the corresponding transfer
hydrocyanation products 4 (see SI for details). The method
provides a practical access to benzofulvene derivatives that are
widely used in polymer chemistry and organic electronics.17
Scheme 3. Scope of the intramolecular MH-type reaction. Reactions carried
out on 0.25 mmol scale in toluene (0.5 mL). Yield of isolated product. Yields of
4 are in the SI. bThis reaction was carried out at 100 oC. cThe isolated yields of
two regioisomers.
Scheme 4. Synthesis of polysubstituted naphthalene compounds.
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When using 2-(2-vinylphenyl)acetonitrile (1k) as a substrate
(Scheme 4), the transformation generated conjugated aromatic
when using labelled substrate 1m (Scheme 5, eq 3). Collectively,
these experiments provide strong support for the proposed
mechanism and clearly establish the transfer hydrocyanation as
the turnover-enabling step in the process.
products. This reaction likely proceeds through
a similar
mechanism, although in this case the initially formed product
undergoes rapid isomerization and aromatization leading to the
thermodynamically more stable product 3ka and 3ke in good
yield.
After having established that transfer hydrocyanation of an
alkyne acceptor is a viable approach to catalyst turnover in MH-
type cyclization reactions, we turned our attention to the use of
less reactive alkene acceptors in intermolecular MH-type
reactions of aryl cyanides. Initial reactions between benzonitrile
(6a) and styrene (7a) under Ni-catalysis proved challenging and
led to low yields of the products. However, after some additional
optimization (Table S3), we identified a Pd-based system
(Scheme 6) that gave 82% yield of the MH product 8aa. The
corresponding hydrocyanation product 9aa was also obtained in
good yield as a mixture of regioisomers. The scope of this
reaction is presented in Scheme 6. A range of benzonitrile 6 and
styrene substrates
7 were successfully employed in the
transformation and led to the formation of the corresponding
stilbenes. The transformation tolerates several functional groups,
including electrophiles (Cl, OMe) that can be used as substrates
for other cross-coupling reactions. The two-step iterative
synthesis of π-conjugated molecule 11 using two fully
orthogonal MH protocols further demonstrates the synthetic
potential of our transformation.
Scheme 5. Proposed catalytic cycle and mechanistic experiments.
We propose a catalytic cycle for the transformation in
Scheme 5. Several control reactions were performed to support
this mechanistic picture. Step (2) was confirmed by the isolation,
at lower temperature, of reductive elimination product 5af
(Scheme 5, eq 1). The intermediacy of alkyl-Ni complex D is
supported by an experiment using a trans-β methyl styrene
derivative 1l as substrate that resulted in the isolation of two
alkene regioisomers (3la and 3la’) derived from the non-
regioselective β-hydride elimination of intermediate D (Scheme 5,
eq 2). Most importantly, the key transfer hydrocyanation of the
HCN molecule generated from the MH cyclization is attested by
a labelling experiment showing the transfer of DCN to the alkyne
Scheme 6. Scope of the intermolecular Heck-type reaction and application in
chemoselective iterative coupling reactions.
In conclusion, we have presented
a
new transfer
hydrofunctionalization approach to catalyst turnover in MH
reactions that has enabled, first the time, a broad range of aryl
cyanides and alkenes to be utilized as substrates. A cascade
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Keywords: Mizoroki-Heck • Alkene • Cyanide • Alkyne •
Transfer Hydrofunctionalization
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Entry for the Table of Contents (Please choose one layout)
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Text for
Table of
Contents
Xianjie Fang, Peng
Yu, Gabriele Prina
Cerai and Bill
Morandi*
Page No. – Page
No.
Unlocking
Mizoroki-Heck
Type Reactions of
Aryl Cyanides
Using Transfer
Hydrocyanation
Layout 2:
COMMUNICATION
A new transfer hydrofunctionalization strategy to turnover H–M(II)–X complexes has
enabled elusive intramolecular and intermolecular Mizoroki-Heck (MH) type reactions of
aryl cyanides. A cascade intramolecular MH-type cyclization under Ni-catalysis, using an
alkyne acceptor, and an intermolecular coupling under Pd-catalysis, using an alkene
acceptor, were realized using this novel concept.
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
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