(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

Article abstract of DOI:10.1002/anie.201807106

The first catalytic application of well-defined (P,C) cyclometalated gold(III) complexes is reported. The bench-stable bis(trifluoroacetyl) complexes 2 a,b perform very well in the intermolecular hydroarylation of alkynes. The reaction is broad in scope, it proceeds within few hours at 25 °C at catalytic loadings of 0.1–5 mol %. The electron-rich arene adds across the C≡C bond with complete regio- and stereo-selectivity. The significance of well-defined gold(III) complexes and ligand design are highlighted in a powerful but challenging catalytic transformation.

Full text of DOI:10.1002/anie.201807106

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Accepted Article
Title: (P,C) Cyclometalated Gold(III) Complexes: Highly Active
Catalysts for the Hydroarylation of Alkynes
Authors: Charlie Blons, Sonia Ladeira, Abderrahmane Amgoune, and
Didier Bourissou
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201807106
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(P,C) Cyclometalated Gold(III) Complexes: Highly Active
Catalysts for the Hydroarylation of Alkynes
Charlie Blons, Sonia Mallet-Ladeira, Abderrahmane Amgoune,* and Didier Bourissou*
Dedicated to Dr. Joaquim Henrique Teles
Abstract: The first catalytic application of well-defined (P,C)
cyclometalated gold(III) complexes is reported. The bench-stable
bis(trifluoroacetyl) complexes 2a,b perform very well in the
intermolecular hydroarylation of alkynes. The reaction is broad in
scope, it proceeds within few hours at 25°C at catalytic loadings of
Straightforward preparation
New reaction paths

first evidence for oxidative
 migratory insertion[4b,c,g]
addition of aryl‒X[4a]
 b-H elimination[4d]
Gold(III) catalysis ?
0.1–5 mol%. The electron-rich arene adds across the C≡C bond with
New gold(III) species
complete regio- and stereo-selectivity. The significance of well-
defined gold(III) complexes and ligand design are highlighted in a
powerful but challenging catalytic transformation.
 C‒H agostic complex[4e]
 bench-stable and robust catalysts
 efficient, selective, broad in scope
 outperform (N,C) complexes
(
P,C) cyclometallated
 p-arene complex[4g]
nucleophilic carbene complex[4f]
gold(III)

this work
Figure 1. (P,C) Cyclometalated Au(III) complexes.
Gold(III) chemistry has progressed very rapidly over the last
few years and N-based cyclometalated complexes occupy a
forefront position in the field.[1] The luminescent and biological
properties of well-defined Au(III) complexes are attracting great
interest for opto-electronic and therapeutic applications.[2,3]
Comparatively, phosphine-based ligands have been very little
The hydroarylation of alkynes represents an ideal catalytic
transformation to test and apply (P,C) cyclometalated Au(III)
complexes. Since the seminal discovery of Fujiwara in the 2000’s
using Pd and Pt complexes,[10] this reaction, ie the formal addition
of aryl–H bonds to alkynes, has garnered huge interest (Figure 2).
It offers a very attractive alternative to the Heck coupling reaction,
obviating the use of prefunctionalized aryl–X substrates, and the
resulting styrene derivatives are extremely valuable building
blocks in organic synthesis and material science.[
exploited in gold(III) chemistry so far, but our work on (P,C)
cyclometalated complexes A (Figure 1)[4] has challenged the
presumed mismatch between soft P donors and hard Au(III)
centers. The preparation of complexes A is straightforward and
actually provided the first example of oxidative addition of aryl–X
bonds to gold.[4a,5] In addition, complexes A were shown to
possess rich reactivity.[4b-d,6] The stability imparted by the (P,C)
chelate was also leveraged to prepare and characterize new
types of gold(III) species.[4e-g] A forefront goal is now to apply
complexes A in catalysis, taking advantage of their rich and
unique behavior. Despite the increasing variety of stable and
reactive well-defined Au(III) complexes, gold(III) catalysis is still in
its infancy and lacks well behind gold(I) catalysis.[7,8] Exploring
and developing gold(III) catalysis is all the more desirable that the
distinct properties of Au(III) complexes[9] may enable to achieve
transformations which are difficult to perform or limited in scope
and/or efficiency with Au(I) and the other transition metals.
11]
Figure 2. Heck and hydroarylation reactions leading to styrene derivatives.
Gold complexes were recognized early on as potent and
highly active catalysts for the hydroarylation reaction.[
12]
Not
surprisingly, most studies have focused on gold(I) complexes that
actually proved to be extremely powerful for intramolecular
hydroarylation reactions, enabling rapid access to biologically
relevant (poly)cyclic compounds.[
13,14]
By comparison and despite
the known ability of Au(III) complexes to readily activate C≡C and
sp2–H bonds, very few articles deal with the Au(III)-catalyzed
hydroarylation of alkynes. In 2003-2004, He and Reetz explored
independently simple catalytic systems combining AuCl and
silver salts.[15,16] These studies stand as rare examples of
intermolecular hydroarylation of alkynes, but the AuCl /AgX
C
3
[]
C. Blons, Dr. A. Amgoune, Dr. D. Bourissou
CNRS / Université Paul Sabatier, Laboratoire Hétérochimie
Fondamentale et Appliquée (LHFA, UMR 5069). 118 Route de
Narbonne, 31062 Toulouse Cedex 09 (France)
E–mail: amgoune@chimie.ups-tlse.fr, dbouriss@chimie.ups–tlse.fr
Homepage: http://hfa.ups-tlse.fr/LBPB/index_lbpb.htm
3
catalysts are only applicable to activated (electron-poor) and/or
terminal alkynes, and leave little room for optimization.
S. Mallet-Ladeira
Institut de Chimie de Toulouse (FR 2599)
Here we report
a
detailed study of intermolecular
1
18 Route de Narbonne, 31062 Toulouse Cedex 09 (France)
hydroarylation of alkynes catalyzed by well-defined Au(III)
complexes. (P,C) Complexes of type A were discovered to be
highly active. The reaction is highly regio- and stereo-selective, it
works with a wide scope of alkynes. Comparison with other gold
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
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complexes evidences the very strong influence of the ancillary
ligand, highlighting the interest and potential of ligand tuning in
well-defined gold(III) catalysts.
in trans arrangement, as unambiguously established by X-ray
diffraction analysis.[18]
The Au(III) complexes 2a,b (Scheme 1) were identified as
promising precatalysts. They combine the robust (P,C) chelate
with labile trifluoroacetate ligands. Reactions of the related
(
N,C)Au(OAcF)
2
complex B (Scheme 3) with ethylene and
acetylene were reported recently by Tilset et al, and the feasibility
of catalytic trifluoroacetoxylation of acetylene was demonstrated
with TON up to ~20.[17] Iodine to trifluoroacetate exchange readily
afforded the desired complexes 2a,b which were obtained in
excellent yields (94%) as bench-stable and analytically pure
compounds.[18,19] Their structure was unambiguously assessed by
multi-nuclear NMR spectroscopy, high-resolution mass
spectrometry (HR-MS) and single-crystal X-ray crystallography
Scheme 2. Hydroarylation of diphenylacetylene with TMB catalyzed by the
(P,C)Au(III) complexes 2a,b, optimization of the reaction conditions.
The combination of (P,C)Au(III) complexes 2a,b and TFA thus
displays high catalytic activity in the hydroarylation of
diphenylacetylene with TMB. To confirm the key role of the two
components, some control experiments were carried out. In the
absence of gold catalyst, no reaction occurred within 4 h when
mixing the two substrates in a DCM/TFA 1/4 mixture, and even
after 24 h, only 5% conversion was observed. Conversely,
replacing TFA for acetic acid completely shut down the catalytic
activity.
(
in the case of 2a).
At this point, the catalytic behavior of 2a,b was compared with
that of a range of gold complexes with the aim to delineate the
influence of the (P,C) ligand (Scheme 3). Because of the limited
number of stable but reactive Au(III) complexes available, very
little is known yet about how the stereo-electronic effects of
ancillary ligands impact gold(III) reactivity, which hinders the
rational elaboration and development of highly active and robust
Au(III) catalysts. First, it is interesting to compare the two
complexes 2a and 2b. The presence of Ph instead of iPr groups
at phosphorus makes the Au(III) center more electrophilic and
less hindered sterically. This results in a slightly higher activity of
2b in the reaction of diphenylacetylene with TMB, which is most
apparent when the catalytic loading is reduced to 0.1 mol% (Table
S1).[17]
Scheme 1. Synthesis of the (P,C)Au(III) complexes 2a,b and molecular
structure of 2a. Thermal ellipsoids are drawn at 50% probability, hydrogen
atoms are omitted. Selected bond lengths (Å) and angles (°): Au-O1 2.105(3),
Au-O3 2.089(2), Au-C3 2.004(3), Au-P1 2.262(1); P1AuC3 84.11(9), P1AuO3
176.88(6), P1AuO1 97.05(7), C3AuO1 177.91(11).
To start our catalytic studies with complexes 2a,b, we chose
as model reaction the hydroarylation of diphenylacetylene, an
internal unactivated alkyne, with trimethoxybenzene (TMB)
(
Scheme 2). The reaction was monitored by 1H NMR
spectroscopy using hexamethylbenzene as internal standard.
The catalytic loading of 2a,b was initially fixed to 5 mol%. No
reaction was observed after 24 h at 25°C in dichloromethane
(
DCM). Under these silver-free conditions, it is needed to add
trifluoroacetic acid (TFA) to activate the gold(III) complex. Using
a 20/1 mixture of DCM/TFA, both complexes 2a and 2b exhibited
high activities, the hydroarylation product being formed in 82 and
Then, the positive influence of the (P,C) ancillary ligand and
well-defined character of 2a,b was deduced by using the simple
F [15]
two-component catalytic system AuCl
3
/3AgOAc .
Only 23 %
9
0% yields, respectively, within 4 h at 25°C. The (P,C)Au(III)
yield of the hydroarylation product was obtained after 4 h, and
66 % after 24 h. In this case, we noticed the formation of a black
precipitate during the course of the reaction, indicating some
decomposition of the catalytic system. Complexes 2a,b are
comparatively much more robust under the catalytic conditions.
The three (N,C) cyclometalated complexes B, C and D were then
evaluated. Strikingly, complexes B[18] and C[17] proved to be
completely inactive, only traces of the hydroarylation product
being observed after 24 h. Better results were obtained with the
more rigid benzoquinoline fragment, but complex D[18,20] gave only
31% yield after 8 h (59 % after 24 h). Thus, the different electronic
properties of the (P,C) vs (N,C) chelate strongly influence the
catalytic activity of the corresponding gold(III) complexes. To
complete the survey, the pincer complex E[4a] featuring a (P,C,P)
ligand was assessed. It also displayed low catalytic activity, only
11 % yield after 8 h (36 % after 3 d), which has most likely to do
complexes proved to be very robust. The reaction medium was
reloaded four times with new substrates and in each case, the
hydroarylation product was obtained in quantitative yield.[18] The
amount of TFA could be increased to parallel the reaction
conditions developed by Fujiwara et al for Pd and Pt catalysis
(
DCM/TFA 1/4).[10] Gratifyingly, the rate of the hydroarylation was
significantly increased under these conditions and quantitative
yields were obtained with 5 mol% of 2a,b in only 30 min. It is
noteworthy that the catalyst loading could be significantly reduced
while retaining high catalytic performance: the hydroarylation
product was obtained in 98% yield within 3 h at 25°C, using only
.1 mol% of 2b.[
15]
0
Note that the reaction of diphenylacetylene with TMB is fully
stereoselective. It affords a single isomer of the triarylethylene
product in which the trimethoxyphenyl group and the proton are
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with the reduced electrophilicity and steric accessibility of the
Au(III) center as the result of the coordination of the additional
phosphine moiety. Finally, the influence of the gold oxidation state
was probed by considering the gold(I) complex F[18] bearing di-
isopropyl-naphthylphosphine. Only 21 % yield was obtained after
position of the electron-withdrawing group. For internal and
terminal aryl-alkynes (entries 2, 3, 4, 5 and 7), the arylation
proceeds at the -position and gives gem-diaryl alkenes. As in
case of diphenylacetylene, the reaction is generally fully
stereoselective and affords the trans addition product. The only
exceptions are ethyl butynoate (entry 6) and methyl propiolate
(entry 8), for which the hydroarylation products are prone to
isomerize.[
8
h (47 % after 24 h). This difference most likely reflects the lower
electrophilicity of gold(I) vs gold(III) species, making gold(III)
complexes unique in catalyzing intermolecular hydroarylation
reactions.[21]
15b,21c]
The reaction was then extended to other electron-rich arenes
such as 1,3-dimethoxybenzene and 1,2-dialkoxybenzenes
(
entries 9-11), as well as durene and mesitylene (entries 12-16).
Using Fujiwara’s conditions, the hydroarylation products were
obtained in 62-99% yields in short reaction times (5 min – 2 h).
1,3-Dimethoxybenzene reacts very preferentially at the o,p
position (entry 9) while 1,2-dialkoxybenzenes react exclusively at
the m,p positions (entries 10,11). The reaction of mesitylene with
diphenylacetylene is noteworthy: AuCl
3
/AgOAcF showed
[
15]
extremely low reactivity (5% yield after 4 h at 50°C), while the
hydroarylation product was obtained in 76% yield within 1h30
using complex 2b (entry 13). To illustrate the efficiency and
practical interest of the catalytic transformation, the hydroarylation
of mesitylene with ethyl phenylpropiolate (entry 14) was
performed in air with technical solvents. Complete selectivity and
only slight decrease in activity was noticed. It was also scaled-up
to 5 mmol. Using 2 mol% of catalyst 2b, the reaction was
complete in 3 h and the ensuing product was isolated in 94%
yield.[18]
Scheme 3. Comparison of the catalytic activities of a range of gold complexes
in the hydroarylation of diphenylactelyne with TMB.
From a mechanistic viewpoint, two different scenarios may be
envisioned for this gold(III)-catalyzed hydroarylation reaction
(
Figure S0).[18] The first involves electrophilic C–H auration of the
Having demonstrated the superior efficiency of complexes
electron-rich arene followed by migratory insertion of the alkyne
and protodeauration (I). The other involves p-activation of the
alkyne at the electrophilic gold(III) center, followed by nucleophilic
addition of the electron-rich arene and protodeauration (II). All the
elementary steps and key intermediates of these two catalytic
cycles are precedented in gold(III) chemistry, including Csp2–H
activation,[23] migratory insertion[4b,c,g] and p-activation of
alkynes.[24] No intermediate could be detected upon NMR
monitoring, but based on the stereoselectivity of the reaction in
favor of trans addition of the aryl group and H atom across the
alkyne, we assume that the transformation proceeds via the outer-
sphere mechanism II.
2
a,b for the hydroarylation of diphenylacetylene with TMB, we
then screened the scope of alkynes and arenes (Table 1). Two
different DCM/TFA ratios were used, namely 20/1 (conditions A)
and 1/4 (Fujiwara’s conditions B). The optimal reaction conditions
and catalyst (2a or 2b) were selected for each set of substrates
to obtain the best compromise between activity and selectivity. As
shown by entries 1-8 in which TMB was reacted with a series of
alkynes, the reaction proceeds well with internal alkynes featuring
aryl, ester, keto and alkyl substituents, but also with terminal
alkynes such as phenyl acetylene and methyl propiolate. In all
cases, the hydroarylation is fully regioselective.[22] For activated
substrates (entries 2, 3, 6 and 8), the alkyne is arylated at the b-
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Table 1. Scope of the gold(III)-catalyzed hydroarylation of alkynes using 2a,b.a
In summary, the (P,C)Au(OAcF)
complexes 2a,b were found
study gold(III) organometallic chemistry, but also competent and
actually powerful catalysts.
2
to efficiently catalyze the intermolecular hydroarylation of alkynes.
The reaction proceeds rapidly at 25°C with a broad scope of
terminal and internal alkynes. These (P,C) cyclometalated
species are very robust and their catalytic performance is far
superior to that of “naked” gold(III) salts, as well as classical (N,C)
cyclometalated Au(III) complexes. These results demonstrate that
(
P,C) cyclometalated complexes A are not only useful tools to
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3
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This work was supported financially by the Centre National de la
Recherche Scientifique, the Université de Toulouse and IFP
Energies nouvelles. We thank Damien Delcroix and Hꢀlꢁne
Olivier-Bourbigou (IFP Energies nouvelles) for fruitful discussions.
Stéphane Massou (ICT) is acknowledged for his assistance with
the NOESY NMR experiments.
[
[18] See supporting information.
[
19] A three-step silver-free route has also been developed. The (P,C)AuI
2
complex is successively reacted with PhMgBr, NMe
4
OPiv and TFA.[
18]
Keywords: alkynes • catalysis • cyclometalation • gold(III) •
hydroarylation • P-based ligands
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Angewandte Chemie International Edition
10.1002/anie.201807106
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Charlie Blons, Sonia Mallet-
Ladeira, Abderrahmane
Amgoune* and Didier Bourissou*
Yes, Au(III) can do it and the
ancillary ligand counts! The
first catalytic application of
P
O
Au
(
P,C) cyclometalated gold(III)
F
Page No. – Page No.
complexes is reported. They
perform very well in the
hydroarylation of alkynes,
surpassing all known gold
catalysts.
Gold(III) catalysis
(P,C) Cyclometalated Gold(III)
Complexes: Highly Active
Catalysts for the
Key influence of the ancillary ligand: (P,C) outperforms (N,C)
Unprecedented substrate scope (16 examples)
High regio and stereoselectivity
Hydroarylation of Alkynes
This article is protected by copyright. All rights reserved.