Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

Article abstract of DOI:10.1002/anie.201706423

We herein showcase the ability of NHC-coordinated dinuclear Ni^I–Ni^I complexes to override fundamental reactivity limits of mononuclear (NHC)Ni⁰ catalysts in cross-couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a Ni^I dimer. A novel SeCF₃-bridged Ni^I dimer was isolated and shown to selectively react with Ar?I bonds. Our computational and experimental reactivity data suggest dinuclear Ni^I catalysis to be operative. The corresponding Ni⁰ species, on the other hand, suffers from preferred reaction with the product, ArSeCF₃, over productive cross-coupling and is hence inactive.

Full text of DOI:10.1002/anie.201706423

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Accepted Article
Title: Striking Divergence in Reactivity of a Dinuclear
(NHC)Ni(I) Catalyst vs Ni(0) enables Chemoselective
Trifluoromethylselenolation
Authors: Alexander B. Dürr, Henry C Fisher, Indrek Kalvet, Khai Nghi
Truong, and Franziska Schoenebeck
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201706423
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10.1002/anie.201706423
Angewandte Chemie International Edition
DOI: 10.1002/anie.201((will be filled in by the editorial staff))
Dinuclear Catalysis
Striking Divergence in Reactivity of a Dinuclear (NHC)Ni(I) Catalyst
vs Ni(0) enables Chemoselective Trifluoromethylselenolation
Alexander B. Dürr,‡Henry C. Fisher,‡Indrek Kalvet, Khai Nghi Truong and Franziska Schoenebeck*
Abstract: We herein showcase the ability of NHC-derived
dinuclear Ni(I)-Ni(I) complexes to override fundamental
reactivity limits of mononuclear (NHC)Ni(0) catalysts in cross-
coupling. This is demonstrated with the development of a
chemoselective Ni(I) dimer-catalyzed trifluoromethylselenolation
of aryl iodides. A novel SeCF3-bridged dinuclear Ni(I) dimer was
isolated and shown to be selectively reactive with Ar-I bonds. Our
computational and experimental reactivity data suggest dinuclear
Ni(I) catalysis to be operative. The corresponding Ni(0) on the
other hand suffers from preferred reaction with the product,
ArSeCF3, over productive cross-coupling and is hence inactive.
unambiguous mechanistic support and rationale of the direct catalytic
involvement of Ni(I) dimers in cross-coupling is elusive.
D
espite the widespread dissemination of multinuclear metal sites in
naturally occurring catalysts (enzymes), human-made homogeneous
catalysis is dominated by mononuclear metal cores.[1] This might be
due to our still limited understanding of the underlying synergism and
reactivity of multi-metal assemblies. A prominent example is nickel,
which is of significant current synthetic interest and predominantly
investigated as monomer in synthesis,[2,3] although featured in higher
ordered clusters in several enzymes.[ 4 ] While nickel’s greater
sustainability is advantageous, its high reactivity and mechanistic
diversity can make it also difficult to tame in a synthetic context,
impacting in particular chemoselectivity - a key requirement for
applications in synthesis. The relative instabilities of Ni(II)
intermediates and their comparably low propensities towards
transmetallation as required in traditional Ni(0)/Ni(II) catalysis have
been identified as an origin of this reactivity behavior, leading to side
reactions, undesired by-products, multiple potentially reactive
species as well as catalyst deactivation.[ 2a,b,5]
Figure 1. Mononuclear M(0)/M(II) versus dinuclear M(I)-M(I) catalysis concept.
Building on our groups’ research in the area of Pd(I) dimer catalysis[6]
that allowed us to develop the catalytic trifluoromethylselenolation of
aryl iodides,[6c] this report describes our efforts in exploring whether
such a dinuclear catalysis concept is feasible also with the less
precious and more sustainable nickel.
The trifluoromethyl selenide group (SeCF3) features several agro-
chemically and pharmaceutically important properties that are of
relevance to membrane permeability and bioavailability.[
11
]
Consequently, there have been numerous activities in devising
synthetic methods to access this functionality.[12] In particular, the
direct catalytic incorporation of the SeCF3 moiety is of interest, as it
may allow for late-stage manipulation of molecules. Realization of
the latter is rare however:[ 13 ] it has been accomplished for aryl
diazonium salts under Cu-catalysis[14] and dinuclear Pd(I)-catalyzed
coupling of aryl iodides with (Me4N)SeCF3, as developed by our
group.[6c]
We hypothesized that dinuclear Ni-catalysis could be particularly
advantageous in this context, as the elementary steps, i.e. ‘oxidative
addition’ and ‘transmetallation’ would be formally reversed,
circumventing the intermediacy of sluggishly reactive Ni(II) species
that are prone to side reactions (Figure 1). For palladium our group
recently showed this concept to be viable.[6]. However, while Ni(I)
complexes have successfully been synthesized,[7] detected in catalytic
transformations in reactions employing typical Ni(0) catalysts,[8] been
used as pre-catalysts,[9] or implicated as mechanistic intermediates,[10]
We started our investigations with the assessment as to whether a
Ni(0)(cod)2 with an NHC ligand ‘SIPr’ could trigger the
trifluoromethylselenolation of aryl halides. Conversion of 4-
iodoanisole 1 to the corresponding ArSeCF3 product was observed in
59%. The analogous aryl bromide and chloride gave no ArSeCF3
product (see Figure 2). In all cases, biaryl was detected and
dehalogenation. The remainder was unreacted starting material. The
latter observation may appear surprising at first sight, given that Ni(0)
complexes are typically highly reactive, allowing cross-coupling of
unactivated aryl ether or aryl fluorides.[2,5] However, the formation of
biaryl hints toward a possible explanation. Such biaryl products can
be an indication of a change in catalyst, arising from a ligand
exchange between [LnNi(II)(Ar)(X)] intermediates to form
[LnNi(II)(Ar)2] and [LnNi(II)(X)2]. Ultimately, biaryl is obtained upon
reductive elimination. The resulting [LnNi(0)] may then
comproportionate with [Ni(II)(X)2] to [Ni(I)]n.[5a] We speculated that
[∗]
Mr. Alexander Dürr,‡ Dr. Henry Fisher,‡ Mr. Indrek Kalvet, Mr. Khai
Nghi Truong, Prof. Dr. Franziska Schoenebeck
(‡equal contributions; alphabetically ordered)
Institute of Organic Chemistry, RWTH Aachen University,
Landoltweg 1, 52074 Aachen, Germany
E-mail: franziska.schoenebeck@rwth-aachen.de
Homepage: http://www.schoenebeck.oc.rwth-aachen.de/
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/anie.201xxxxxx.
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10.1002/anie.201706423
Angewandte Chemie International Edition
the lack of significant transformation of ArBr and ArCl may be
associated with the intermediacy of [Ni(I)]n, rather than [Ni(0)].
bridged Ni(I) dimer 3 in the presence of (Me4N)SeCF3. Our separate
studies showed that a facile displacement of the iodine bridges in 3
with (Me4N)SeCF3 takes place to give 4, in analogy to our previously
developed Pd(I)-Pd(I) chemistry.[6c] Pleasingly, employing 10 mol% of
[(SIPr)Ni(I)(I)]2 3 and (Me4N)SeCF3 (1.5 equiv.) in benzene at 45 °C
allowed us to successfully couple a range of aryl iodides to the
corresponding Ar-SeCF3 compounds (Table 1). A number of
electron-rich and electron-poor aryl iodides were functionalized in
good to excellent yields. The method proved to be compatible with
various functional groups, such as keto- (5a, d), methoxy- (5f), amine
(5i) functionalities as well as the pharmaceutically interesting
unprotected indole motif (5e).
Table 1. Scope of Ni(I) dimer 3 catalyzed trifluoromethylselenolation.
Figure 2. Direct reactivity of Ni(I)-Ni(I) complex with ArI; X-ray structures of iodine
and Se-CF3 bridged Ni(I) dimers and comparison with Ni(0)
.
Sigman and co-workers synthesized a Cl-bridged SIPr Ni(I) dimerand
[7b]
its unsaturated counterpart, IPr Ni(I)-Cl dimer.
Matsubara and
colleagues very recently showed that the latter triggers Kumada
cross-coupling, and it was suggested that a Ni(I) dimer or monomer
may be involved in the process.[ 15] Smaller NHC-Ni(I) monomers
were also shown to trigger C-C and C-N couplings.[9] A pronounced
ligand effect was observed by Louie as to whether Ni(I) or Ni(II) may
be formed in reactions with (NHC)Ni(0).[16] While the origins are not
understood, the data suggest that the Ni(I) monomer or dimer species
might function as pre-catalysts under these conditions. In this context,
to date, no rationale has been presented, as to why a Ni(I) may
potentially be preferred over a Ni(0) pathway. For phosphine-based
Ni(I) complexes, our group and others recently demonstrated that Ni(I)
is catalytically inactive or serves as pre-catalyst.[ 17 ] To obtain
conclusive insight, we set out to prepare Ni(I) complexes with iodine
and SeCF3 ligands. We succeeded in the synthesis of an iodine- (3)
and a SeCF3-bridged (4) dinuclear Ni(I) complex. The X-ray structures
are illustrated in Figure 2.
Conditions: 3 (0.01 mmol, 10.9 mg), ArI (0.1 mmol), (Me4N)SeCF3 (0.15 mmol,
33 mg), benzene (1.0 mL). Yields determined by 19F-NMR against internal
standard (PhCF3) or upon isolation (shown in parenthesis). [a] 3 equiv. of
(Me4N)SeCF3 used.
Given that we saw significantly more conversion with ArI but
largely only biaryl for ArBr (Figure 2), this may suggest that Ni(I)
forms in these cases and takes over as active catalyst for ArI, but may
not be reactive enough for ArBr. To test this, we subjected our newly
synthesized Ni(I)-SeCF3 bridged dimer 4 (1 equiv.) to ArI and ArBr
(10 equiv.). While for ArI, trifluoromethylselenolation was indeed
seen (and 80% of the total available SeCF3 was incorporated in ArI),
for ArBr, there was no conversion (see Figure 2). Importantly, no
biaryl compounds were detected in these cases, suggesting that the
Ni(I) does not simply serve as a precursor to Ni(0). Moreover, our
kinetic studies under the same conditions gave a first order
dependence in Ni(I) dimer 4, in agreement with the direct reactivity of
the dimer and aryl iodide. These data strongly suggest that Ni(I) is a
competent trifluoromethylselenolating species, and hence also likely
competent species in catalysis when generated from the iodine-
We hypothesized that the formally less electron rich Ni(I) dimer might
offer a platform for selective functionalizations and tested the
potential to trigger also chemoselective catalytic C-SeCF3 bond
formations. Pleasingly, we observed exclusive functionalization of C-
I in the presence of C-Br and C-Cl bonds (Table 1, bottom).
These data showcase the superiority of an isolated dinuclear Ni(I)
complex as catalyst in chemoselective SeCF3-couplings of aryl
iodides without the formation of side products. In this context, it is
unclear why a Ni(I) dimer would be the preferred reactive species in
C-SeCF3 couplings over Ni(0). To address this, we turned to
computational studies.[18]
We initially assessed the feasibility of a [Ni(0)] catalyst to oxidatively
add to PhI, PhBr and PhCl with DFT methods.[20] The activation
barriers for oxidative addition follow the expected trend, i.e. ΔG‡
2
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10.1002/anie.201706423
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follows ArI < ArBr < ArCl. We previously demonstrated that another
important factor for efficiency and scope of Ni-catalyzed
functionalizations is to also assess the likelihood of the reaction of the
catalyst with the desired product.[19] In our case, an activated C-SeCF3
moiety is installed which could be prone to oxidative addition by [Ni]
also. Interestingly, we observed that the oxidative addition of [Ni(0)]
to PhSeCF3 is characterized by a substantially lower activation barrier
than addition to PhI, PhBr and PhCl (see Figure 3). Depending on the
level of theory (we considered M06L, M06 and PBE0-D3)[20] addition
to PhSeCF3 is favored by ΔΔG‡ = 4.0 to 6.6 kcal/mol over addition to
PhI. These data suggest that [Ni(0)] should preferentially react with
the product PhSeCF3, as soon as it is formed, instead of the aryl halide
substrate. The thereby generated [(SIPr)Ni(II)(SeCF3)(Ar)] could then
undergo side-reactions, e.g. the commonly occurring ligand exchange
between two such Ni(II) species to ultimately generate biaryl. In line
with this, our experimental tests indeed gave biaryl (7%) when we
subjected 20 mol% of Ni(0)(cod)2 /SIPr to ArSeCF3 2 in benzene at
45°C for 30 min.
remarkably, the oxidation state (I) follows a different selectivity
pattern than oxidation state (0).[20]
Thus, the reason for the ineffectiveness of Ni(0)(cod)2/SIPr catalyzed
conditions is the higher reactivity of the product, ArSeCF3, towards
oxidative addition by Ni(0) than the corresponding starting material.
With the origin of Ni(0) ineffectiveness being accounted for, we
subsequently set out to assess the reactivity of the Ni(I) dimer. We
succeeded in the location of transition states for the direct oxidative
addition of the Ni(I) dimer to PhI (Figure 3).[20] We optimized the
dinuclear transition state as both, closed-shell singlet and triplet states.
While the singlet state TSs display a high degree of Ni-Ni bonding,
the triplet state TSs show a larger distance between the two Ni centers
(Figure 3) along with pronounced spin densities at both Ni-centers,
indicating open shell biradical character (see SI). Our energy
evaluation of the singlet vs. triplet oxidative addition at various levels
of theory (M06L, M06 and PBE0-D3) suggested the triplet state to be
consistently favored.[20] As such, the computational data suggest that
there will be a spin change from singlet (in the ground state dimer) to
triplet (in the transition state). Following endergonic oxidative
addition, a Ni(II)-Ni(II) intermediate may form and subsequently
eliminate PhSeCF3 under formation of the mixed Ni(I) dimer 8 bearing
an iodine and a SeCF3 bridge. The latter species (8) is predicted to be
more reactive than the doubly SeCF3 bridged Ni(I) dimer 4 and also
favorably adds via the triplet transition state, leading to the
conversion of another equivalent of ArI to ArSeCF3 (see SI for full
path). The transformation is overall calculated to be exergonic (by
ΔGrxn=-10.1 at M06L), and as such, theormodynamically driven.
Figure 3. Top: Relative energy difference between triplet (favored) and singlet
(disfavored) TSs for oxidative addition of a mixed Ni(I) dimer (bearing a SCF3 and
an I bridge) to ArI. Bottom: Selectivity divergence for Ni(0) vs. Ni(I)-Ni(I).[20]
In conclusion, we reported compelling data in support of NHC
derived dinuclear Ni(I) catalysis in cross coupling with aryl iodides.
The first iodine- (3) and SeCF3-bridged (4) Ni(I) dimers were
synthesized, fully characterized, and 4 was shown to be reactive
directly with aryl iodides. Using the Ni(I) dimer as catalyst avoids
undesired biaryl side products through the suppression of alternative
pathways and circumvents mononuclear Ni(II) intermediates that are
prone to side reactions. Selective functionalization of C-I over C-Br,
C-Cl or alternative functionality was possible. The corresponding
Ni(0) was found to be inferior and inactive due to its propensity to
preferentially react with the product, ArSeCF3. Our computational
and experimental reactivity data suggest fundamentally different
reactivity trends, i.e. for Ni(0): ArSeCF3 > ArI > ArBr ~ ArCl and for
Ni(I)-Ni(I): ArI > ArBr > ArCl > ArSeCF3. These data provide an
example of superior reactivity of dinuclear Ni(I) over mononuclear
Ni(0) catalysis and showcase the potential and importance to precisely
control and harness the distinct metal oxidation states in catalysis.
As a mechanistic alternative, a Ni(I) monomer pathway might be
followed. If open shell Ni(I) monomers were to be involved, we would
expect EPR activity. However, our EPR investigations of the reaction
mixture of the catalytic SeCF3 coupling of aryl iodides with 3, the
substoichiometric reaction of Ni(I) dimer 4 with ArI (as shown in
Figure 2) as well as the Ni(I) dimer itself dissolved in solution, showed
no EPR signals.
Lastly, we set out to investigate why the Ni(I) dimer would allow for
productive catalysis, while Ni(0) does not. To address this, we
computationally studied the relative preference for oxidative addition
to the product ArSeCF3 versus ArI, ArBr and ArCl once again. We
employed a range of DFT methods (see SI for details) and all
consistently predicted the same reactivity trend. Interestingly, while
Ni(0) clearly preferred addition to the product ArSeCF3 byΔΔG‡ = 6.3
kcal/mol (with M06L), for Ni(I)-Ni(I) a different reactivity pattern is
seen, substantially favoring addition to the aryl halide over the
product (by ΔΔG‡ = 9.0 kcal/mol at M06L, see Figure 3). As such,
Acknowledgements
We thank the RWTH Aachen, the MIWF NRW and the European
Research Council (ERC-637993) for funding. Calculations were
performed with computing resources granted by JARA-HPC from
RWTH Aachen University under project ‘jara0091’. We are grateful
to Kristina Deckers for technical assistance.
3
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Received: ((will be filled in by the editorial staff))
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Published online on ((will be filled in by the editorial staff))
Keywords: chemoselectivity • fluorine • dinuclear Ni(I) • DFT •
catalysis
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4
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Layout 2:
Dinuclear Catalysis
A. B. Dürr,‡ H. C. Fisher,‡ I. Kalvet, Khai
Nghi Truong, F. Schoenebeck*
__________ Page – Page
Striking Divergence in Reactivity of a
Dinuclear (NHC)Ni(I) Catalyst vs Ni(0)
enables Chemoselective
Trifluoromethylselenolation
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Our calculations of the logP values of N-CF3 versu N-CH3 drugs gave slightly higher or similar values for N-CF3. LogP of Amitriptyline: 5.55 (wet octanol) and 5.56 (dry octanol). LogP of Amitriptyline-CF3: 5.9
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(wet octanol) and 6.06 (dry octanol). LogP of Naftifine: 5.89 (wet octanol) and 5.9
4
(dry octanol). LogP of Naftifine-CF3:
6
.25 (wet octanol) and 6.35 (dry octanol). LogP of Sildenafil: 1.16 (wet octanol) and 0.59 (dry octanol). LogP of Sildenafil-CF3
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1.51 (wet octanol) and 1.02 (dry octanol). LogP of Terbinafine:
6
.96 (wet octanol) and 7.05 (dry octanol). LogP of Terbinafine-CF3: 6.94 (wet octanol) and 7.06 (dry octanol); calculated with CO SMO thermX (F.Eckert, A. K lamt, CO SMOtherm,Version C30_1601, Release 12.15; COSMOlogic GmbH &Co. KG,Germany,2010).
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