Evidence for Direct Transmetalation of AuIII-F with Boronic Acids

Article abstract of DOI:10.1021/jacs.6b07763

The underlying reactivity of Au^III-F species with aryl boronic acids has been studied in detail taking advantage of four novel, stable difluoro-[(C^N)AuF₂], arylmonofluoro-[(C^N)AuArF], and alkylmonofluoro-[(C^N)AuAlkF] gold(III) complexes, prepared and isolated in monomeric form. We provide the first experimental evidence for a direct Au^III-F/B transmetalation preceding the Csp²-Csp² or Csp³-Csp² bond formation.

Full text of DOI:10.1021/jacs.6b07763

Subscriber access provided by CORNELL UNIVERSITY LIBRARY
Communication
III
Evidence for Direct Transmetalation of Au-F with Boronic Acids
Roopender Kumar, Anthony Linden, and Cristina Nevado
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b07763 • Publication Date (Web): 29 Sep 2016
Downloaded from http://pubs.acs.org on September 29, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
III
Evidence for Direct Transmetalation of Au -F with Boronic Acids
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Roopender Kumar, Anthony Linden and Cristina Nevado*
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH 8057
Supporting Information Placeholder
[
4f]
[10]
III
calculations. Recently, You et al. managed to establish a
catalytic cycle in which 2-(o-tolyl)pyridine substrates react
with gold in the presence of N-fluorobenzenesulfonimide
ABSTRACT: The underlying reactivity of Au -F species with
aryl boronic acids has been studied in detail taking ad-
vantage of four novel, stable, difluoro-[(C^N)AuF ], aryl-
2
(
NFSI) and aryl boronic acids to produce the corresponding
monofluoro-[(C^N)AuArF]
and
alkylmonofluoro-
cross-coupling products via reductive elimination on biaryl
gold(III) intermediate II (Scheme 1B). Here, the role of
fluorine remains unclear as Csp -Au -F species III can be
proposed to precede transmetalation, or alternatively, non-
coordinated fluoride anions produced in situ might be re-
[(C^N)AuAlkF] gold(III) complexes prepared and isolated in
monomeric form. We provide the first experimental evidence
[10]
2
III
III
2
for a direct Au -F/B transmetalation preceding the Csp -
2
3
2
Csp or Csp -Csp bond formation.
[12]
III
sponsible for the C-B cleavage (IV). Thus, even if Au is
isoelectronic to Pd , our understanding of the interaction
II
III
Transmetalation is a fundamental step in metal catalyzed
Au -F/B and of the specific nature of the individual steps
[1]
cross-coupling reactions. The prominent role of Suzuki
forging the new C-C bonds (direct transmetalation or bimo-
lecular reductive elimination) is still limited and mostly
restricted to indirect experimental evidence. Here we present
the synthesis of monomeric, easy to handle Csp -Au -bis
and mono-fluoride complexes together with a detailed study
on their reactivity with aryl boronic acids. Our results pro-
[2a]
reactions in modern synthetic chemistry
has fostered
efforts towards establishing a detailed mechanistic basis for
II
[2b-e]
2
III
the interaction of boron reagents with Pd species.
Gold-
catalyzed oxidative couplings have recently emerged as pow-
3
erful complementary tools for the efficient formation of Csp -
2
2
2
2
[3]
III
Csp , Csp -Csp and Csp-Csp bonds. Interestingly, boronic
acids are involved as productive reaction partners in many of
vide experimental evidence for the ability of Au -F species to
undergo “classical” transmetalation with aryl boronic acids
by isolation of the corresponding transmetalation products.
We also demonstrate that, in contrast to previously studied
systems, the product formation is indeed governed by both
the electronic and steric features of the organic residue on
the boronic acid (Scheme 1C).
[4]
I
these transformations. While Au -B transmetalation has
[
5]
III
been studied in detail, examples of Au /B transmetalation
[9]
are less abundant. Pioneering studies by Bochmann and co-
3
∧
∧
workers showed that κ -[(C N C)Au(OX)] complexes react
smoothly with aryl boronic acids in the absence of external
base to produce the corresponding arylation products
[
6]
[
[
(C^N^C)AuAr].
Our group also demonstrated that
(Ph P)Au(C F )Cl ] react with electron deficient aryl boronic
3
6
5
2
F
acids (Ar B(OH) ) under neutral conditions to form stable
2
F
[7]
[
(Ph P)Au(C F )Ar Cl] species. These processes showcase
3 6 5
III
the synergistic combination of Au and B, however, most
gold catalyzed oxidative-cross couplings involving boronic
acids as reaction partners employ Selectfluor as stoichio-
III
metric oxidant and thus Au -F species have been invoked as
the key partners of boron species towards the formation of
[4b-f]
III
new C-C bonds.
Such putative Au -F intermediates re-
main largely elusive due to their intrinsic unstable charac-
[8]
III
ter and thus the nature of the interaction Au -F/B is still a
matter of intense discussion. In a seminal contribution to-
wards the understanding of these transformations, Toste et
III
al. showed that in situ generated cis-[(NHC)AuMeF ] species
2
Scheme 1. Synthesis and reactivity of Au -F with bo-
(
NHC: N-heterocyclic carbene), in equilibrium with the
ronic acids.
corresponding dimer, rapidly react with aryl boronic acids to
[9]
produce toluene derivatives (Scheme 1A). Since the elec-
tronics on the boronic acid did not affect the reaction out-
come, a single step bimolecular reductive elimination (I)
rather than a conventional two-step transmetalation and
III
As seen in Scheme 1, methods to produce Au -F species in
situ have mostly relied on the reaction of (NHC)- or (C^N)-
stabilized gold(I) complexes with strong oxidants such as
[8-10]
XeF or NFSI.
Recently, our group reported the synthesis
3
2
reductive elimination pathway was proposed for the Csp -
3
of a novel class of pincer κ -[(N^C^C)AuCl] complexes in
which a facile Cl/F ligand exchange reaction in the presence
2
Csp bond formation, an hypothesis also supported by DFT
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
3
of AgF successfully yielded the corresponding fluorides κ -
B(OH)
2
R
[13]
R
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
[
(N^C^C)AuF]. Aware of the ability of 2-phenylpyridine
R
F
F
F
F
based ligands (C^N) to stabilize electron deprived gold(III)
Au
Au
+
Me
Me
[14]
species,
N
CH
2
Cl
2
, rt
N
cis-dichloro-2-(2-fluorophenyl)- and 2-(3,4,5-
R
trimethoxyphenyl)-3-methylpyridine-gold(III) complexes
1
R
and 2 were treated with AgF in dichloromethane at room
temperature producing the corresponding difluorides 3 and 4
3
R = 2,3,4,5,6-pentafluoro 9a, 81%
R = 4-tert-butyl
10a, -
9b, -
10b, 72%
[15]
in high yields.
Interestingly, [(C^N)AuArBr]
5
and
[16]
Scheme 3. Reaction of [(C^N)AuF
acids.
] 3 with aryl boronic
2
[
(C^N)AuMeBr] 6 were also efficiently transformed under
similar conditions into the corresponding monofluoride
species [(C^N)AuRF] 7 (R = 3,5-(CF ) -C H -) and 8 (R = Me)
3
2
6
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The reaction with (4-tert-butylphenyl)boronic acid yielded
homocoupling product 10b in 72% yield as a result of a facile
reductive elimination between the two electron-rich aro-
matic residues. It is important to note that cross-coupling
products stemming from a reductive elimination with the 2-
phenyl pyridine ligand were not detected in the reaction
mixtures.
The reactivity of monofluoride complexes 7 and 8 was also
investigated. As shown in Table 1, a bimolecular reductive
elimination pathway would deliver the intermolecular cross-
coupling products (12). If a direct transmetalation were to
take place via 11, both intra- and intermolecular reductive
(
Scheme 2).
R
2
R
2
R
2
R
2
R
2
1
R
2
Cl
AgF
Cl , rt
F
F
R
AgF
R
R
1
R
F
F
Au
Au
Au
Au
Me
Me
Me
Me
Cl CH
2
2
Br CH Cl , rt
F
N
N
N
2
2
N
1
, R
2, R
1
= F, R
= H, R
2
= H
= OMe
3, 99%
4, quant.
5,
7, >99%
8, >99%
3 2 6 3
R = 3,5-(CF ) -C H -
1
2
6, R = Me
2
III
Scheme 2. Synthesis of Csp -Au -bis and monofluoride
complexes via halogen/F exchange reactions.
III
The monomeric structure of Au -F complexes 3, 4, 7 and 8
1
9
could be confirmed by F-NMR as well as by successful X-ray
[18]
elimination products (12 vs. 13/14) could be observed. The
[17]
diffraction analysis of the corresponding crystals. As ex-
reaction of 4-(tertbutylphenyl)- and 4-(fluorophenyl)boronic
acids (A, B) with 7 in dichloromethane at room temperature
produced both inter- (12A and 12B) and intramolecular (13)
reductive elimination products in comparable yields (Table 1,
III
pected, the Au -F bond trans to the strong σ-donor aryl
ligand is substantially elongated compared to the one trans
to the pyridino moiety, particularly in the case of electron-
rich (C^N) precursors. Distorted square planar geometries
were observed for all complexes, with a more acute angle
observed in compound 7 compared to that measured in the
1
entries 1, 2). Monitoring by H NMR the reaction of 7 with 4-
(tertbutylphenyl)boronic acid (A) at -40ºC enabled us to
detect a new specie, which was assigned to transmetalation
product 11A. Upon warming to room temperature, reductive
elimination products are observed suggesting that the cross-
coupling products observed in entries 1 and 2 can stem from
1
9
F
difluoride complexes 3 and 4 (Figure 1). Differences in the
NMR of these complexes are also diagnostic, with the signals
of F-trans to the phenyl ring appearing at higher fields com-
pared to those opposite to the pyridino group (3: F(1): -252.4
ppm, F(2): -191.8 ppm. 4: F(1): -281.2 ppm, F(2): -170.8 ppm. 7:
the corresponding direct transmetalation intermediates 11
see SI). Interestingly, the reaction of 7 with (pentafluoro-
[15]
(
[15]
F(2): -208.5ppm. 8: F(1): -220.8 ppm).
phenyl)boronic acid (C) produced preferentially product 13
in 81% yield showing that a sterically encumbered, electron
deprived intermediates favour the corresponding intramo-
lecular reductive elimination process (entry 3). An equally
sterically demanding, but less electronically deprived part-
ner, such as (2,4,6-trifluorophenyl)boronic acid (D), enabled
the isolation of transmetalation product 11D in 51% yield
Figure 1. Solid-state molecular structures of (from left to
(
entry 4). 11D undergoes quantitative reductive elimination
right) [(N^C)AuF ] complexes 3, 4 and [(N^C)AuRF] 7 and 8
[15]
2
to 13 upon heating (see SI). The reaction of complex 8 with
4-(tertbutylphenyl)boronic acid A delivered intermolecular
reductive elimination 12A’, together with homocoupling
with atoms drawn using 50% probability ellipsoids and hy-
drogen atoms have been omitted for clarity. Selected bond
lengths [Å]: 3: Au(1)-F(1) = 2.014(3), Au(1)-F(2) = 1.951(4); 4:
Au(1)-F(1) = 2.025(4), Au(1)-F(2) = 1.940(3); 7: Au(1)-F(2) =
[19]
product 10b (entry 5). In contrast, the reactions with pen-
tafluorophenyl- and 2,3,6-trifluorophenyl boronic acid fur-
nished exclusively intramolecular reductive elimination
products 14C and 14E in high yields (entries 6, 7). As such,
the reaction outcome seems to be governed by both the
electronic and steric features of the organic residue on the
boron counterpart as well as by the electronic nature of the
cycloaurated complex, thus hinting towards the involvement
of transmetalation intermediates 11 in these transformations,
in contrast to a potential bimolecular reductive elimination
pathway in which the electronic features of the boron rea-
2.011(4); 8: Au(1)-F(1) = 2.023(7) and angles [°]: 3: N(1)-Au(1)-
F(1) = 94.80(17); 4: N(1)-Au(1)-F(1) = 93.98(16); 7: N(1)-Au(1)-
F(2) = 91.6(2); 8: N(1)-Au(1)-F(1) = 92.5(3).
2
III
The reactivity of these discrete Csp -Au -F complexes with
different aryl boronic acids was explored next. Interestingly,
the reaction of 3 with two equivalents of (pentafluoro-
phenyl)boronic acid furnished the corresponding bis-aryl
complexes [(C^N)Au(C F ) ] 9a in 81% yield, thus demon-
6
5 2
2
III
strating that Csp -Au -F species can react with boronic acids
via a direct transmetalation (Scheme 3).
[9]
gent would not be expected to play such an important role.
These results highlight the mechanistic diversity underlying
gold-catalyzed oxidative couplings combining Selectfluor
and boronic acids. For preliminary results on a catalytic
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
a
Table 1. Reaction of [(N^C)AuRF] 7 and 8 with aryl boronic acids
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
b,c
Product Distribution
a
Entry
Starting Material
Ar
11
12
13
14
-
d
1
2
3
4
5
6
7
7, R = 3,5-(CF
)
3 2
-C
6
H
3
4-tBu-C
6
H
4
- (A)
-
12A, 57%
40%
68%
81%
19%
traces
-
„
„
„
4-F-C
6
H
4
- (B)
-
12B, 32%
-
C
6
5
F - (C)
-
-
-
-
2,4,6-C
6
F
3
H
2
- (D)
11D, 51%
-
d
e,f
8, R = Me
4-tBu-C
6
H
4
- (A)
-
12A’, 33%
„
„
C
6
5
F - (C)
-
-
-
-
14C, 88%
14E, 74%
2,3,6-C
6
F
3
H
2
- (E)
-
a
[15] b
No intramolecular reductive elimination was observed in complexes 7 and 8 even after prolonged heating at 80 ºC
conditions: ArB(OH) (1.2 equiv.), CH Cl , 25 ºC, 30 min-1 h. “-“: not observed. Transmetalation intermediates 11A (R = 3,5-
CF ) -C H ) and 11A’ (R = Me) were observed when the reaction was performed at – 40 ºC. Warming up the reaction to 25 ºC
3 2 6 3
delivers cross coupling products (see SI). 29% yield of homocoupling product 10b could be isolated. Reaction with boronic acid
B showed a similar outcome.
Reaction
c
d
2
2
2
(
e
f
version of these transformations, see section S6 in the Sup-
These tranformations showcase that a direct transmetalation
Au -F/B is indeed possible regardless of the electronic na-
ture of the boronic acid provided enough stabilization is in
place to prevent the reductive elimination to give a new
Csp -Csp bond. The structures of complexes 9a, 11D, 14C, 15,
16a and 16b could be unambiguously stablished by X-ray
[15]
III
porting Information.
2
III
The ability of Csp -Au -F species to undergo direct
transmetalation with aryl boronic acids was further con-
3
[13]
2
2
firmed with κ -[(N^C^C)AuF] species. As shown in Scheme
, the reaction of 15 with (4-tertbutylphenyl)boronic acid
delivered complex 16a in 62% yield. Pentafluoro-, 3,5-
difluoro- and 2,4,6-trifluorophenyl boronic acids delivered
aryl biscyclometalated complexes κ -[(N^C^C)AuAr] 16b-d
4
[17]
diffraction analysis.
In conclusion we report here the synthesis, isolation and
characterization of four novel, difluoro-[(C^N)AuF ], aryl-
3
2
in high yields.
monofluoro-[(C^N)AuArF]
and
alkylmonofluoro-
[
(C^N)AuAlkF] gold(III) complexes isolated in monomeric
form via facile X/F exchange reactions. The underlying reac-
tivity of the Au -F bond with aryl boronic acids has been
studied in detail under neutral reaction conditions. Im-
portantly, we provide the first experimental evidence for a
III
III
2
2
direct Au -F/B transmetalation preceding the Csp -Csp or
2
3
Csp -Csp bond formation. Our results thus showcase that
different mechanistic scenarios can operate in gold-catalyzed
oxidative couplings involving Selectfluor and boronic acids.
3
Scheme 4. Reaction of κ -[(N^C^C)AuF] 15 with aryl bo-
ASSOCIATED CONTENT
Supporting Information
ronic acids.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
Supplementary information including compound synthesis
and characterization, crystallographic data. This material is
available free of charge via the Internet at
http://pubs.acs.org.
Nolan, S. P. Adv. Synth. Catal. 2012, 354, 2380. (g) Hirner, J.
J., Blum, S. A. Tetrahedron 2015, 71, 4445.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
.
(a) Rosca, D.-A., Smith, D. A., M. Bochmann, Chem. Com-
mun. 2012, 48, 7247. (b) Smith, D. A., Roşca, D.-A.,
Bochmann, M. Organometallics 2012, 31, 5998.
(a) Hofer, M., Gomez-Bengoa, E., Nevado, C. Organometa-
llics 2014, 33, 1328. (b) M. Hofer, C. Nevado, Tetrahedron
2013, 69, 5751.
7.
AUTHOR INFORMATION
Corresponding Author
III
8
.
For transformations invoking Au -F species see ref. 3a, 3d-f,
Cristina Nevado* (cristina.nevado@chem.uzh.ch)
ref. 4 and also: (a) de Haro, T., Nevado, C. Chem. Commun.
2
2
011, 47, 248. (b) de Haro, T., Nevado, C. Adv. Synth. Catal.
010, 352, 2767. (c) Hopkinson, M. N., Ross, J. E., Giuffredi,
Notes
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
G. T., Gee, A. D. Gouverneur, V. Org. Lett. 2010, 12, 4904. (d)
Simonneau, A., Garcia, P., Goddard, J-P., Mouriès-Mansuy,
The authors declare no competing financial interests.
V., Malacria, M., Fensterbank, L. Beilstein J. Org. Chem. 2011,
ACKNOWLEDGMENT
III
7
, 1379. For recent examples of well characterized Au -X
species: e) Guenther, J., Mallet-Ladeira, S., Estevez, L., Mi-
queu, K., Amgoune, A., Bourissou, D. J. Am. Chem. Soc. 2014,
We thank the European Research Council (ERC Starting
grant agreement no. 307948) for financial support. Dr. Oliver
Blacque is acknowledged for the X-ray crystal structure de-
termination of 16a.
1
36, 1778. f) Joost, M., Zeineddine, A., Estevez, L., Mallet-
Ladeira, S., Miqueu, K., Amgoune, A., Bourissou, D. J. Am.
Chem. Soc. 2014, 136, 14654. For examples of well character-
I
ized Au -F species: g) Akana, J. A., Bhattacharyya, K. X., Mül-
REFERENCES
ler, P., Sadighi, J. P. J. Am. Chem. Soc. 2007, 129, 7736. (h)
Nahra, F., Patrick, S. R., Bello, D., Brill, M., Obled, A.,
Cordes, D. B., Slawin, A. M. Z., O'Hagan, D., Nolan, S. P.
ChemCatChem 2015, 7, 240.
1
.
Wendt, O. F. Curr. Org. Chem. 2007, 11, 1417-1433.
2.
(a) Suzuki, A. Angew. Chem. Int. Ed. 2011, 50, 6722. (b) Car-
row, B. P., Hartwig, J. F. J. Am. Chem. Soc. 2011, 133, 2116. (c)
Amatore, C., Jutand, A., Le Duc, G. Chem. Eur. J. 2012, 18,
9
.
(a) Mankad, N. P., Toste, F. D. J. Am. Chem. Soc. 2010, 132,
1
7
2859. (b) Mankad, N. P., Toste, F. D. Chem. Sci. 2012, 3, 72-
6.
6616. (d) Lennox, A. J. J., Lloyd-Jones, G. C. Angew. Chem.
Int. Ed. 2013, 52, 7362. (e) Thomas, A. A., Denmark, S. E. Sci-
ence 2016, 352, 329.
1
0. Wu, Q., Du, C., Huang, Y., Liu, X., Long, Z., Song, F., You, J.
Chem. Sci. 2015, 6, 288.
3
.
For selected examples: (a) Cui, L., Zhang, G., Zhang, L.
Bioorg. Med. Chem. Lett. 2009, 19, 3884. (b) Kar, A., Mangu,
N., Kaiser, H. M., Tse, M. K. J. Organomet. Chem. 2009, 694,
11. a) Wolfe, W. J., Winston, M. S., Toste, F. D. Nat. Chem. 2014,
6, 453.; (b) Winston, M. S., Wolf, W. J., Toste, F. D. J. Am.
Chem. Soc. 2015, 137, 7921. (c) Vicente, J., Dolores Bermudez,
5
24. (c) de Haro, T., Nevado, C. Angew. Chem. Int. Ed. 2011,
M., Escribano, J. Organometallics 1991, 10, 3380.
50, 906. (d) Hopkinson, M. N.,Tessier, A. Salisbury, A., Gou-
verneur, V. Chem. Eur. J. 2010, 16, 4739. (e) Hashmi, A. S. K.,
Ramamurthi, T. D., Todd, M. H., Tsang, A. S.-K., Graf, K.
Aust. J. Chem. 2010, 63, 1619. (f) Ball, L. T., Green, M., Lloyd-
Jones, G. C., Russell, C. A. Org. Lett. 2010, 12, 4724. (g) Ball, L.
T., Lloyd-Jones, G. C., Russell, C. A. Science 2012, 337,
1644.(h) Serra, J., Whiteoak, C. J., Acuña-Pares, F., Font, M.,
Luis, J. M., Lloret-Fillol, J., Ribas, X. J. Am. Chem. Soc. 2015,
III
1
2. Au -F species do not seem to be necessary for a successful
reductive elimination (see equation 5 in ref. 10).
13. Kumar, R., Linden, C. Nevado, Angew. Chem. Int. Ed. 2015,
54, 14287. See also ref. 11b.
4. Henderson, W. in Advances in Organometallic Chemistry,
Vol. 54 (Eds.: W. Robert, F. H. Anthony), Academic Press,
1
2006, pp. 207.
1
5. For experimental details, see Supporting Information.
1
37, 13389. For selected reviews on this topic: (i) Hopkinson,
M. N., Gee, A. D., Gouverneur, V. Chem. Eur. J. 2011, 17, 8248.
j) Wegner, H. A., Auzias, M. Angew. Chem. Int. Ed. 2011, 50,
236. (k) Hopkinson, M. N., Gee, A. D., Gouverneur, V. Isr. J.
16. (a) Langseth, E., Görbitz, C. H., Heyn, R. H., Tilset, M. Or-
ganometallics 2012, 31, 6567. For other examples of ligand ex-
change reactions preferably occurring trans to the pyridine
group, see: (b) Szentkuti, A., Bachmann, M.,. Garg, J. A.,
Blacque, O., Venkatesan, K. Chem. Eur. J. 2014, 20, 2585. (c)
Venugopal, A., Shaw, A. P., Törnroos, K. W., Heyn, R. H., Til-
set, M. Organometallics 2011, 30, 3250. (d) Langseth, E., No-
va, A., Traseth, E. A., Rise, F. Oien, S., W., Heyn, R. H., Tilset,
M. J. Am. Chem. Soc. 2014, 136, 10104.
(
8
Chem. 2010, 50, 675. (l) Boorman, T. C.; Larrosa, I. Chem.
Soc. Rev. 2011, 40, 1910. (m) Nevado, C., de Haro, T. in New
Strategies in Chemical Synthesis and Catalysis, Wiley-VCH
Verlag GmbH & Co. KGaA, 2012, pp. 247.
4
.
(a) Carrettin, S., Guzman, J., Corma, A. Angew. Chem. Int. Ed.
2005, 44, 2242. (b) Zhang, G.; Peng, Y., Cui, L., Zhang, L.
1
7. CCDC-1487417 (1), 1487425 (2), 1486854 (3), 1486862 (4),
487420 (5), 1486864 (7), 1487498 (8), 1486865 (9a), 1486866
11D), 1486867 (14C), 1486905 (15), 1033770 (16a) and 1486892
Angew. Chem. Int. Ed. 2009, 48, 3112. (c) Zhang, G., Cui, L.;
Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474. (d)
Wang, W., Jasinski, J., Hammond, G. B., Xu, B. Angew. Chem.
Int. Ed. 2010, 49, 7247. (e) Brenzovich, W. E.; Benitez, D.;
Lackner, A. D., Shunatona, H. P., Tkatchouk, E., Goddard,
W. A., Toste, F. D. Angew. Chem. Int. Ed. 2010, 49, 5519. (f)
Tkatchouk, E., Mankad, N. P., Benitez, D., Goddard, W. A.,
Toste, F. D. J. Am. Chem. Soc. 2011, 133, 14293.
1
(
(16b) contain the supplementary crystallographic data for
this paper. The data can be obtained free of charge from The
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/structures.
1
8. Note that compound 13 shown in Table 1 is formed from the
corresponding complexes 14 upon purification via column
chromatography in silica gel.
19. For homocoupling products via Au(I)/Au(III) trasmetalation,
see: (a)Leyva-Pérez, A.; Doménech, A.; Al-Resayes, S. I.;
Corma, A. ACS Catal. 2012, 2, 121. (b) Hofer, M.; Nevado, C.
Eur. J. Inorg. Chem. 2012, 9, 1338. (c) Hofer, M.; Nevado, C.
Tetrahedron 2013, 69, 5751.
5
.
(a) Sladek, A., Hofreiter, S., Paul, M., Schmidbaur, H. J. Or-
ganomet. Chem. 1995, 501, 47. (b) Partyka, D. V., Zeller, M.,
Hunter, A. D., Gray, T. G. Inorg. Chem. 2012, 51, 8394. (c)
Maity, A., Sulicz, A. N., Deligonul, N., Zeller, M., Hunter, A.
D., Gray, T. G. Chem. Sci. 2015, 6, 981. (d) Hashmi, A. S. K.,
Ramamurthi, T. D., Rominger, F. J. Organomet. Chem. 2009,
6
94, 592. (e) Hansmann, M. M., Rominger, F., Boone, M. P.,
Stephan, D. W., Hashmi, A. S. K. Organometallics 2014, 33,
461. (f) Dupuy, S., Crawford, L., Bühl, M., Slawin, A. M. Z.,
4
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
TOC
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment