Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols

Article abstract of DOI:10.1002/chem.201704037

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.

Full text of DOI:10.1002/chem.201704037

A Journal of
Accepted Article
Title: Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed
Alkylation and Olefination of Alkylnitriles with Alcohols
Authors: Junjun Li, Yuxuan Liu, Weijun Tang, Dong Xue, Chaoqun Li,
Jianliang Xiao, and Chao Wang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Chem. Eur. J. 10.1002/chem.201704037
Link to VoR: http://dx.doi.org/10.1002/chem.201704037
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Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed
Alkylation and Olefination of Alkylnitriles with Alcohols
Junjun Li,[a] Yuxuan Liu,[a] Weijun Tang,[a] Dong Xue,[a] Chaoqun Li,[a] Jianliang Xiao[a,b] and Chao
Wang*[a]
In memory of Professor Takao Ikariya
Abstract: The chemoselective alkylation and olefination of
alkylnitriles with alcohols have been developed, by simply controlling
the reaction atmosphere. A binuclear rhodium complex catalyzes the
alkylation reaction under argon via a hydrogen-borrowing pathway
and the olefination reaction under oxygen through aerobic
dehydrogenation. Broad substrate scope is demonstrated, permitting
the synthesis of some important organic building blocks. Mechanistic
studies suggest that the alkylation product may be formed via
conjugate reduction of an alkene intermediate by a rhodium hydride,
while the formation of olefin product may be due to the oxidation of
the rhodium hydride complex with molecular oxygen.
Dehydrogenation has been used in organic synthesis as a
strategy to activate inert molecules.[1] A metal catalyst is
generally employed to dehydrogenate a substrate to generate a
more reactive intermediate and a metal hydride (Scheme 1, top).
The activated intermediate could couple with other molecules to
form more complex molecules, the unsaturated bonds of which
could then be reduced to finish a hydrogen-borrowing/hydrogen
autotransfer process.[1d, 2] Alternatively, the metal hydride could
be protonated to release hydrogen gas or accepted by an
oxidant to accomplish a dehydrogenative coupling process
(Scheme 1, middle).[1a-c, 1e, 2e] The selectivity between these two
Scheme 1. Controlling the chemoselectivity between hydrogen-borrowing and
dehydrogenative coupling reactions.
processes has rarely been addressed but appears to be
determined by the nature of catalyst used, and different catalysts
group recently demonstrated that iridacycle catalysts could also
enable both hydrogen-borrowing reaction and dehydrogenative
coupling of amines and alcohols.[7] Herein, we present a
binuclear Rh complex-catalyzed chemoselective alkylation and
olefination of alkylnitriles with alcohols, with the selectivity
controlled by simply altering the reaction atmosphere (Scheme 1,
bottom). The alkylation reaction performed under Ar is a
hydrogen-borrowing reaction, whilst the olefination reaction
under O2 is a dehydrogenative coupling variant.
are required to achieve either hydrogen-borrowing or
dehydrogenative coupling. The chemoselective access to both
hydrogen-borrowing and dehydrogenative coupling products
with
a single catalyst is mechanistically interesting and
practically useful. However, such catalysts are rare. Kaneda and
co-workers reported a heterogeneous Ru catalyst for the α-
alkylation of nitriles with alcohols via hydrogen borrowing under
argon at 180 oC.[3] The Ru catalyst could also catalyze the
formation of olefin products under an oxygen atmosphere, but
this necessitates a two-step operation.[4] Zhang and Hanson
Nitriles are useful building blocks in organic synthesis.[8] With
water as the only by-product, the alkylation of alkylnitriles with
alcohols via hydrogen borrowing provides a “green” route for the
showed that
4
Å
molecular sieves could alter the
chemoselectivity between imines[5] and amines[6] in a cobalt
pincer complex catalyzed coupling of amines and alcohols. Our
synthesis of new nitrile compounds. Transition metal catalysts,
9]
including Ru,[3,
Os,[10] Ir,[11] Rh,[12] and Pd,[13] have been
employed for this reaction. The olefination of alkylnitriles with
alcohols could afford α,β-unsaturated nitriles, which are also
valuable intermediates in organic synthesis.[14] However, this
transformation is less explored.[4, 9b, 13, 15] Very recently, Milstein
and co-workers reported a remarkable example of Mn-catalyzed
olefination of nitriles by alcohols under base free conditions.[15]
Despite the progress, how to control the selectivity between
alkylation and olefination of alkylnitriles with alcohols remains to
be answered. The protocol described here provide a simple
solution to this challenging problem.
[a]
[b]
J. J. Li, Y. X. Liu, Prof. Dr. W. J. Tang, Prof. Dr. D. Xue, Prof. Dr. C.
Q. Li, Prof. Dr. J. L. Xiao, Pro. Dr. C. Wang
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry
of Education and School of Chemistry and Chemical Engineering,
Shaanxi Normal University, Xi’an, 710119 (China)
E-mail: c.wang@snnu.edu.cn
Prof. Dr. J. L. Xiao
Department of Chemistry
University of Liverpool
Liverpool, L69 7ZD, (UK)
Supporting information for this article is given via a link at the end of
the document.
Recently, the binuclear Rh catalyst 1 (Table 1) was found to
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Table 1. Binuclear Rh complex 1 catalyzed alkylation of 2-phenylacetonitrile
Table 2. Alkylation of 2-phenylacetonitrile with alcohols catalyzed by 1.
with 4-methylbenzyl alcohol.
[a] Reaction conditions: 4-methylbenzyl alcohol (0.5 mmol), 2-
phenylacetonitrile (0.5 mmol), base (0.25 mmol), catalyst (0.5 mol%), toluene
(2 mL), 110 oC, under Ar in a sealed tube. [b] Determined by 1H NMR
spectroscopy with 1,3,5-trimethoxybenzene as internal standard. See SI for
more optimization data.
be an effective catalyst for acceptorless dehydrogenative
coupling[16] as well as dehydrogenation[17] of alcohols by our
group. In continuing our effort in dehydrogenation-related
transformations, the catalytic activity of 1 in the alkylation of
alkylnitriles with alcohols was studied. To begin with, 4-
methylbenzyl alcohol and 2-phenylacetonitrile were chosen as
model substrates to test the catalytic activity of 1 (0.5 mol%)
(Table 1). In the presence of NaOH (0.5 equivalent), the
monoalkylated product 2a was formed in 93% yield in toluene at
o
110 C in 12 h (Table 1, entries 1). Other solvents and bases
General reaction conditions: alcohol (0.5 mmol), 2-phenylacetonitrile (0.5
mmol), NaOH (0.25 mmol), 1 (0.5 mol%) toluene (2 mL), 110 oC under Ar in a
sealed tube, isolated yield. See SI for more details.
afforded poorer yield (See SI for details). Without 1 or NaOH,
the coupling reaction did not take place (Table 1, entries 2 and
3). The reaction time could be shortened to 6 h without affecting
the yield (Table 1, entry 4). Other Rh complexes showed no or
little activity in this reaction (Table 1, entries 5-7).
Table 3. Alkylation of various alkylnitriles with 4-methylbenzyl alcohol
catalyzed by 1.
The substrate scope of this catalytic protocol was then
explored. Both benzylic and aliphatic alcohols can react with 2-
phenylacetonitrile generally in the presence of 0.5 mol% of 1
and 0.5 equivalent of NaOH in toluene at 110 oC under Ar (Table
2). Benzylic alcohols bearing substituents with varying electronic
and steric properties on the phenyl ring are all viable substrates
(2a-2l). Alcohol containing a heterocycle gave low yield even
with increased catalyst loading (2l). Aliphatic alcohols showed
better activity with longer chain length (2m-2p). Notably, ethanol
could be used as substrate, affording α-ethylated nitrile in
excellent yield without the formation of dialkylated products (2m).
Cyclopropyl and cyclohexyl rings could be tolerated (2q-2r). 2-
Phenylethan-1-ol afforded moderate yield of 2s, which can serve
as an intermediate for the synthesis of drug molecules (vide
infra). One hydroxyl group of diols can react selectively to form
molecules containing both a hydroxy and a cyano group, when
the diols are added in excess (See SI for details). These
molecules have not been reported previously and could be used
for the synthesis of more complex compounds (vide infra). The
C=C double bond and the chiral centre remain intact, when (S)-
(-)-β-citronellol was used as substrate, although the newly
The reaction conditions are the same as those of Table 2. See SI for details.
formed chiral centre is essentially racemic (2v). The
preservation of the isolated C=C double bond showed that the
catalyst reduces polarized C=C double bond selectively,
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2, see SI for more optimization data). Differing from the
alkylation protocol, an excess amount of alcohol was used in the
olefination reaction to ensure the full consumption of nitrile
substrate, as part of the alcohol was oxidized to the
corresponding carboxylic acid under the reaction conditions.
The substrate scope of the dehydrogenative coupling
protocol was also examined (Table 4). A rang of benzylic
alcohols and 2-arylacetonitriles could be used, producing Z-
nitrile olefins in moderate to excellent yields (4a-4p).[18] These
nitrile olefin products could be employed as key intermediates
for the synthesis of natural products[19] or as substrates for
asymmetric hydrogenation.[20]
Scheme 2. Olefination of 2-phenylacetonitrile with 4-methylbenzyl alcohol
catalyzed by 1.
indicative of a conjugated reduction pathway for the reduction of
the nitrile olefin intermediate (vide infra).
The utility of the alkylation reaction has been further
demonstrated by large scale reactions and transformation of the
alkylated products into useful organic molecules (Scheme 3).
The reaction of 4-methylbenzyl alcohol and 2-phenylacetonitrile
was performed at a gram scale, and the corresponding alkylated
product was in situ hydrolyzed to a carboxylic acid product 5 in
excellent yield (Scheme 3, top). This type of carboxylic acid may
serve as intermediate for the preparation of biologically active
compounds, e.g. inhibitors of transient receptor potential
canonical (TRPC) channel activity.[21] Product 2s, derived from
2-phenylethan-1-ol and 2-phenylacetonitril, can be conveniently
converted to 2-phenyl tetralone 6 (Scheme 3, middle), which
Different nitriles were then examined (Table 3). Moderate to
good yields were obtained for various 2-arylacetonitriles (3a-3f).
Acetonitrile could also react, albeit showing a lower activity (3g).
The alkylation reactions above were carried out in an inert
atmosphere of argon. Our previous study showed that 1 could
catalyze the oxidation of alcohols under either Ar or air, but via
different mechanisms.[17] Under air, the rhodium hydride
intermediate is probably consumed by reacting with oxygen,
affording water and so becoming unavailable for hydrogenation.
Thus, we envisioned that switching the atmosphere of the
alkylation reaction from Ar to O2 could change the reaction
pathway from hydrogen-borrowing to dehydrogenative coupling,
as the rhodium hydride intermediate would be intercepted by
oxygen. Indeed, upon changing the reaction vessel from a
sealed tube to a Radleys Carousel tube equipped with a O2
balloon, the reaction of 2-phenyl acetonitrile and 4-methylbenzyl
alcohol produced the olefin product 4a as the major product in
the presence of 1 mol% of 1 and 1 equivalent of NaOH (Scheme
could
be
used
for
the
synthesis
of
hexahydrobenzo[c]phenanthridine alkaloids.[22] The hydroxyl
nitrile compound 2u, derived from a diol and 2-phenylacetonitile,
was transformed into an amino nitrile compound 7 via an iridium-
catalyzed hydrogen-borrowing reaction.[23] Hydrolysis of
7
afforded a ε-amino acid 8 in high yield (Scheme 3, bottom),
showcasing the usefulness of the method in the synthesis of
some unique amino acids, which may find important biological
applications.[24]
Table 4. Olefination of nitriles with alcohols catalyzed by 1.
Preliminary mechanistic studies were carried out to shed
light on the reaction pathways. The olefin product 4b could be
General reaction conditions: alcohol (0.75 mmol), nitrile (0.25 mmol), NaOH
(0.25 mmol), catalyst (1 mol%), toluene (2 mL), 110 oC under O2 balloon in a
Radleys Carousel tube, isolated yield. See SI for more details.
Scheme 3. Gram-scale α-alkylation of 2-phenylacetonitrile and application of
products.
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reduced to 2b using benzyl alcohol as hydrogen source under
the catalysis of 1 (Scheme 4, top). However, the yield of 2b
varies with the atmosphere applied. Thus, under argon 44%
yield of 2b was obtained with 0.5 mol% of 1 and 0.5 equivalent
of NaOH in 15 minutes under Ar (Scheme 4, top), whilst less
than 5% yield of 2b was detected even in a prolonged time of 12
h, when the reaction atmosphere was switched from Ar to O2
(Scheme 4, top). Without 1, 4b could not be reduced by benzyl
alcohol under the condition employed (Scheme 4, top). These
results suggest that the olefin products are intermediates for the
alkylated products under Ar and the presence of O2 stops the
reduction of olefin products. Upon replacing benzyl alcohol with
deuterium-labelled benzyl alcohol 9, 4b was reduced to product
10 in 27% yield in 15 minutes. The deuterium atom goes almost
exclusively to the β-position of the cyano group in 10, suggesting
that the formation of 10 goes through a conjugated reduction
process by the rhodium-deuteride intermediate generated from
dehydrogenation of 9.
atmosphere, the rhodium hydride intermediate B reacts
preferentially with O2 to complete the catalytic cycle, thereby
giving C as the reaction product.
In conclusion, by harnessing the unique catalytic activity of a
binuclear rhodium complex, we have realized the
chemoselective alkylation and olefination of alkylnitriles with
alcohols by simple controlling of the reaction atmosphere. The
alkylation reaction has broad substrate scope and could be
applied to the synthesis of some important organic molecules.
Mechanistic studies suggest that the conjugate reduction of an
alkene intermediate by a rhodium hydride is responsible for the
formation of the alkylation product, whilst the interception of the
rhodium hydride by molecular oxygen results in the formation of
the olefin product. The notion of being able to switch the reaction
mode of hydrogen-borrowing vs dehydrogenative coupling by
simply changing the reaction atmosphere provides one of the
easiest means to access two different classes of products and
would be expected to find broader applications.
Based on the above mechanistic studies, reaction pathways
for both the alkylation and olefination reactions are suggested
(Scheme 4, bottom). The active rhodium catalyst
A
Acknowledgements
dehydrogenates an alcohol to produce a rhodium hydride
intermediate B and an aldehyde with the aid of a base. The
aldehyde intermediate could be detected by 1H NMR and thin
layer chromatography (TLC) during the courses of both
alkylation and olefination reactions. Moreover, in the absence of
the nitrile substrate, aldehyde products could also be detected
by 1H NMR. For example, 4-methoxybenzyl alcohol was oxidized
to the corresponding aldehyde with a NMR yield of 14% under
Ar and 54% under O2 in the presence of 0.3 equivalent of NaOH
with 0.3 mol% of 1 in refluxed toluene for 12 h. The carboxylic
acid product could also be observed in small amounts, which
differs from our previous system in water.17 The aldehyde then
condenses with the alkyl nitrile to give the olefin product C via
nucleophilic addition and dehydration promoted by a base.
Indeed, the olefin product could be observed by NMR, when
reacting benzaldehyde with 2-phenylacetonitrile under the
alkylation conditions in the absence of 1. Under an Ar
atmosphere, C is reduced by B to afford the alkylated product D
and regenerate the active catalyst A. In contrast, under an O2
This research was supported by the National Natural Science
Foundation of China (21473109, 21773145), Science and
Technology Program of Shaanxi Province (2016KJXX-26), the
Program for Changjiang Scholars and Innovative Research
Team in University (IRT_14R33), the 111 project (B14041) and
Projects for the Academic Leaders and Academic Backbones,
Shaanxi Normal University (16QNGG008).
Keywords: dehydrogenation • nitrile • alcohol • rhodium • cross
coupling
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Junjun Li, Yuxuan Liu, Weijun Tang,
Dong Xue, Chaoqun Li, Jianliang Xiao,
Chao Wang*
Page No. – Page No.
Atmosphere-Controlled
Chemoselectivity: Rhodium-
Catalyzed Alkylation and Olefination
of Alkylnitriles with Alcohols
A binuclear rhodium complex catalyzes the chemoselective alkylation and
olefination of alkylnitriles with alcohols, with the selectivity controlled solely by the
reaction atmosphere. The reactions have broad substrate scope and could be
applied to the synthesis of unique amino acids.
This article is protected by copyright. All rights reserved.