Anchoring Triazole-Gold(I) Complex into Porous Organic Polymer to Boost the Stability and Reactivity of Gold(I) Catalyst

Article abstract of DOI:10.1021/acscatal.6b03211

Stability and reactivity have been recognized as some critical issues for gold(I) catalysts. Such issues can be well-circumvented by anchoring the gold(I) complex onto the backbones of porous organic polymer (POP) followed by coordination with a triazole ligand as illustrated in the present work via a series of gold(I)-catalyzed reactions. In this strategy, 1,2,3-triazole was used as the special "X-factor" to avoid the formation of solid AgCl involved in typical gold-activation processes. The catalyst could be readily recycled without loss of reactivity. Moreover, compared with the PPh₃-modified polystyrene beads, the POP support was advantageous by providing high surface area, hierarchical porosity, and better stabilization of cations. In some cases, significantly improved reactivity was observed, even more so than using the homogeneous system, which further highlighted the great potential of this heterogeneous gold catalyst.

Full text of DOI:10.1021/acscatal.6b03211

Subscriber access provided by UB + Fachbibliothek Chemie | (FU-Bibliothekssystem)
Letter
Anchoring Triazole-Gold(I) Complex into Porous Organic
Polymer to Boost the Stability and Reactivity of Gold(I) Catalyst
Rong Cai, Xiaohan Ye, Qi Sun, Qiuqin He, Ying He, Shengqian Ma, and Xiaodong Shi
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b03211 • Publication Date (Web): 30 Dec 2016
Downloaded from http://pubs.acs.org on December 30, 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.
ACS Catalysis 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 7
ACS Catalysis
1
2
3
4
5
6
7
8
9
Anchoring Triazole-Gold(I) Complex into Porous Organic Pol-
ymer to Boost the Stability and Reactivity of Gold(I) Catalyst
†
†
†
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
Rong Cai,b Xiaohan Ye,a Qi Sun,a Qiuqin He,a Ying He,a Shengqian Ma* a and Xiaodong
Shi* a
a The Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, Tampa, Florida 33620,
United States
b C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506,
United States
Supporting Information Placeholder
ABSTRACT: Stability and reactivity have been recognized as some critical issues for gold(I) catalysts. Such issues can
be well-circumvented by anchoring the gold(I) complex onto the backbones of porous organic polymer (POP) followed
by coordination with a triazole ligand as illustrated in the present work via a series of gold(I) catalyzed reactions. In this
strategy, 1,2,3-triazole was used as the special “X-factor” to avoid the formation of solid AgCl involved in typical gold
activation processes. The catalyst could be readily recycled without loss of reactivity. Moreover, compared with the
PPh3-modified polystyrene beads, the POP support was advantageous by providing high surface area, hierarchical po-
rosity, and better stabilization of cations. In some cases, significantly improved reactivity was observed, even more so
than using the homogeneous system, which further highlighted the great potential of this heterogeneous gold catalyst.
KEYWORDS: heterogeneous gold catalysis, porous organic polymer, triazole-gold catalyst, recyclable gold catalyst,
alkyne activation
Gold catalysis has flourished over the past decade, en-
abling access to a wide range of transformations. In par-
ticular, as an efficient carbophilic Lewis acid, gold(I) cat-
alysts have facilitated numerous interesting transfor-
mations through the activation of alkynes, allenes and
alkenes.1 However, besides the cost of gold, the utiliza-
tion of gold(I) catalysts for practical applications in
chemical industry has been mainly impeded by two hur-
dles: A) sensitivity of cationic gold(I) catalysts and B)
catalyst activation. As shown in Scheme 1A, catalytical-
ly active [L-Au]+ cation often suffers from poor stability
and may decompose into gold colloids. In homogeneous
gold(I) catalysis, stable L-Au-Cl complexes are typically
applied as the catalyst precursor along with activation
reagents, such as Ag+ cation2 or NaBArF4 salt.3 One effec-
tive method to engender enhanced stability and catalytic
activity of gold(I) catalysts is through confining the ac-
tive species into heterogeneous systems.4
In 2009, our group reported 1,2,3-triazole as a special
dynamic ligand to form stable gold complexes (TA-Au).5
Using this new coordination strategy, Yu and coworkers
first reported a solid-supported gold using a triazole-
functionalized polystyrene resin to trap the [PPh3Au]+
cation (Scheme 1B).6 Although this catalyst showed
good reactivity towards some interesting transfor-
mations (such as the enyne cyclization), it suffered from
gold leaching each cycle due to the dynamic coordination
of triazole ligand. To avoid this problem, later on, they
reported another heterogeneous gold(I) catalyst with
polystyrene-supported phosphine ligand using Ag+ as an
activation reagent (Scheme 1B).7 Although this catalyst
could catalyze several alkyne and allene activation reac-
tions, significantly reduced reactivity was observed after
each cycle, likely caused by gold decomposition and a
potential influence from AgCl. Thus, the avoidance of
AgCl waste in catalyst activation and the improvement of
ACS Paragon Plus Environment

ACS Catalysis
Page 2 of 7
the stability of [L-Au]+ are essential towards the realiza-
tion of highly efficient heterogeneous gold(I) catalysts.
POPs represent an emerging class of porous materials
1
2
3
4
5
6
7
8
possessing high surface areas, tunable pore sizes, and
high water/chemical stability;10 they have been inten-
sively investigated for potential applications in gas stor-
age/separation, carbon capture,11 contaminant removal,12
catalysis etc.13 Considering the broad application of
phosphine ligands in gold catalysis, we envision that the
porous organic polymer (POP) synthesized from
polymerization of tris(4-vinylphenyl)phosphine (POP-
PPh3), featuring excellent spatial continuity of PPh3 moi-
eties, large surface and hierarchical porosity, may offer a
new opportunity for the development of novel heteroge-
neous gold catalysts with improved reactivity and cata-
lyst stability.14 To test our hypotheses, we anchored tria-
zole-gold(I) complex on POP-PPh3 (POP-TA-Au) as
shown in Figure 2.
9
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
Scheme 1. Challenges in solid-supported gold(I) cata-
lyst
Our interest in developing a solid-supported gold(I)
catalyst was initiated from the idea of using triazole as an
activation strategy to access active gold(I) catalyst. As
shown in Figure 1, NH-triazole can replace chloride
anion under basic conditions. The resulting gold com-
plex (triazole anion gold, TAA-Au) can be further acti-
vated through treatment with an acid, such as HOTf,
forming the reactive cationic TA-Au catalyst. Using this
strategy, a catalytically active solid-supported TA-Au
complex can be easily prepared without the formation of
solid AgCl during the process.
Figure 2. Synthesis of heterogeneous gold(I) complex
With this heterogeneous catalyst POP-TA-Au in hand,
we explored its reactivity towards the Teles hydration
reaction.15 Initial studies revealed that the employment
of POP-PPh3 as a modification ligand has a profound
effect on the catalyst durability. As shown in Figure 3,
POP-TA-Au demonstrated impressive reactivity with
similar reaction kinetics to the homogeneous TA-Au cat-
alyst. Catalysts with different phosphine ligand and gold
ratio (P: Au) were prepared and examined. With higher
P:Au (2:1), gold decomposition was observed over time,
suggesting that not all P atoms in POP are accessible.
The POP-TA-Au with 5:1 P:Au ratio gave the optimal
results (see SI for details). The anionic triazole complex
POP-TAA-Au gave almost no reaction without acid acti-
vation. Notably, a higher yield was obtained with POP-
TA-Au (95%) over homogeneous catalyst TA-Au (80%)
because of improved catalyst stability. Reactions at a
higher concentration (0.5 M) resulted in a much faster
rate with excellent yield (>90%).
Figure 1. Synthesis of PS-TA-Au
The commercially available triphenylphosphine resin
was first tested for this design and the PS-TA-Au was
obtained in good yield. With this new catalyst in hand,
we tested its reactivity toward phenyl acetylene hydra-
tion. Although the desired phenyl methyl ketone was
formed at elevated temperature, significantly lower reac-
tivity was observed with PS-TA-Au when comparing with
the homogeneous TA-Au. More importantly, the for-
mation of gold nanoparticles was observed with this gold
complex using STEM (see SI). Though this 1,2,3-triazole
activation strategy could avoid the formation of AgCl,
developing a better solid support is necessary and crucial
for achieving a practical heterogeneous gold(I) catalysis.
Cycle 1
1% POP-TA-Au, 0.5 M
100
80
1% POP-TA-Au, 0.1 M
Cycle 2
[Au] treated
with HOTf
Porous materials could stabilize the corresponding
metal complexes and provide a microenvironment for
the substrates, which may lead to different reactivity
compared with homogeneous catalysts.8 To tackle the
aforementioned issues encountered for existing solid-
support gold(I) catalysts, we propose that the gold(I)
complex could be anchored into the backbones of porous
organic polymers (POPs), followed by coordination with
a triazole ligand.9
1% TA-Au, 0.1 M
60
40
Cycle 2
[Au] treated with triazole
1% PS-TA-Au, 0.1 M
1% POP-TAA-Au, 0.1 M
Cycle 2
[Au] non treated
20
0
0
0
1
2
3
4
5
6
7
20
40
60
100
120
80
Time / h
Time / min
Figure 3. POP-TA-Au catalyzed Teles hydration
ACS Paragon Plus Environment

Page 3 of 7
ACS Catalysis
After confirming the good reactivity of POP-TA-Au, we
excellent isolated yield. To test whether POP-TA-Au still
maintain this chemoselectivity, we treated propargyl
alcohol 1 with this heterogeneous catalyst in dry DCE
(Table 2). At room temperature, no reaction proceeded
(comparing with 95% yield for homogeneous TA-Au).
1
tested its recyclability. As shown in Figure 3, a slower
reaction rate was observed after separating the hetero-
geneous catalyst POP-TA-Au and subsequent resubmis-
sion to another portion of starting material (cycle 2),
albeit good yield (>90%) was still obtained. This may be
caused by two potential reasons: A) the loss of triazole
ligand, leading to catalyst decomposition, and B) for-
mation of POP-TAA-Au (loss of HOTf). To test our hy-
pothesis, we treated the gold catalyst after the first cycle
with either triazole or triflic acid, followed by washing
with methanol to remove extra additives. To our delight,
the catalyst treated with triflic acid was activated again
and catalyzed the reaction in the same efficiency as the
first cycle. The catalyst treated with triazole ligand did
not show any improvement of reactivity, suggesting no
significant triazole ligand loss from the polymer catalyst
was occurring. With this simple re-activation strategy,
the POP-TA-Au catalyst has been recovered and recycled
7 times without any loss of reactivity. Hydration reac-
tions of other representative alkynes were also tested
with this POP-TA-Au and the results are summarized in
Table 1.
2
3
4
5
6
7
8
9
o
Raising the temperature to 60 C, allene acetate 2 was
obtained in 92% yield without further activation of the
allene product (formation of indene).18 This result con-
firmed the good chemoselectivity of TA-Au in this heter-
ogeneous catalytic system.
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
Table 2. Evaluating the chemoselectivity of POP-TA-
Aua,b
Yield of 2
Cycle 1 Cycle 2
Conditions
Time Conversion
Cycle 3
1% TA-Au (homogeneous), rt 2 h
100%
<5%
100%
95%
ND
92%
-
-
-
-
1% POP-TA-Au, rt
24 h
2 h
1% POP-TA-Au, 60 oC
80%c 55% (70%)d
aGeneral conditions: 1 mol% gold catalyst, dry DCE (0.01 M). bYields deter-
mined by GC. c16 h. d24 h, 70% conversion of propargyl acetate.
Hydroboration, preventing gold from decomposition:
One interesting transformation recently developed by
our group is the TA-Au catalyzed hydroboration.19 Alt-
hough cationic gold is a highly reactive -acid, it suffers
greatly from poor stability, especially with the presence
of a reductant, which will cause the formation of Au(0).
The discovery of TA-Au revealed a new class of gold cata-
lyst with improved stability. However, when conducting
the hydroboration reaction shown in Table 3, Ph3P-TA-
Au gave only 30% yield even with 10% catalyst loading.
This was clearly due to the decomposition of gold (54%
conversion) under this reductive environment. To en-
sure high conversion, much more expensive XPhos-TA-
Au has to be applied.
Table 1. POP-TA-Au catalyzed alkyne hydration.a,b
TA-Au PS-TA-Au
POP-TA-Au (recycles)
C-3 C-4 C-5
C-1
C-2
C-6 C-7
Reaction A 85%
25%
15%
10%
8%
93% 88%
91% 85%
90% 85%
91% 85%
88% 87% 90% 85% 87%
80% 81% 58% 54% ND
89% 81% 83% 82% 91%
86% 83% 82% 88% 90%
Reaction B 45%
Reaction C 90%
Reaction D 89%
aGeneral conditions: 1 mol% POP-TA-Au, MeOH:H2O = 20:1 (0.5 M). bYields
determined by GC..
Table 3. Evaluating the stability of POP-TA-Aua,b
For all four hydration reactions that were tested, the
POP-TA-Au gave better yields than both homogeneous
TA-Au catalysts and the surface modified PS-TA-Au.
Hydration of propargyl alcohol and propargyl acetate
gave enone in excellent yields (Reactions C and D). With
the less reactive internal alkyne (reaction B), higher
Yield (%)
C-3 C-4 C-5 C-6 C-7
Conditions
C-1
30
75
C-2
-
-
10% [PPh3Au(TA)]OTf, 2 h
10% [XPhosAu(TA)]OTf, 12 h
10% POP-TA-Au, 6 h
-
-
-
-
-
-
68
-
-
68
-
-
65
o
temperature (80 C) and longer reaction time (12 h) are
needed for 100% conversion. Excellent yields were ob-
tained for the first four cycles. Catalyst decomposition
was observed after five cycles. However, compared with
homogeneous catalyst TA-Au, this porous polymer sup-
ported gold catalyst gave significantly better reactivity
and excellent recyclability. The POP-TA-Au catalyst was
also successfully recycled in gram scale reactions (see SI
for details). To fully evaluate the potential of this new
heterogeneous catalyst, we explored other gold-catalyzed
reactions, especially the challenging examples that are
difficult to achieve using common gold catalysts.
79
71
69
70
a
b
General conditions: 10 mol% gold catalyst, DCM (0.05 M). Yields deter-
mined by H-NMR.
To our delight, the heterogeneous POP-TA-Au catalyst
could promote this transformation with good efficiency,
even when only a simple PPh3 primary ligand was used.
Compared with the homogeneous TA-Au catalyst (de-
composed before full conversion of starting material),
this newly developed heterogeneous gold(I) catalyst
showed much better performance (79% yield in 6 h),
likely because of the improved stabilization of the gold
cation by the porous scaffold. Moreover, this POP-TA-
Au could be re-activated simply by treating with triflic
acid between each cycle. With this strategy, this catalyst
has been successfully recycled for more than 7 times,
Chemoselectivity: Gold(I) cation can effectively acti-
vate both alkyne and allene.16 A unique reactivity of tria-
zole-gold catalyst (TA-Au) was the excellent chemoselec-
tivity, activating alkyne over allene.17 Thus, treating pro-
pargyl ester with TA-Au can give the desired allene with
ACS Paragon Plus Environment

ACS Catalysis
Page 4 of 7
cycles, better results might be achieved through further
modification of the ligand, which is currently ongoing in
our lab.
which indicated the potential for the application of this
new catalyst into large-scale synthesis.
1
2
3
4
5
6
7
8
Improving TA-Au reactivity through Lewis acid acti-
vation: The discovery of triazole as a good ligand in gold
coordination provides an opportunity to increase the
stability of cationic gold catalyst. However, comparing
with [L-Au]+, TA-Au has lower reactivity, which limits its
application. From recent kinetic studies, we revealed
that an associative ligand exchange between TA-Au and
alkyne was the turnover-limiting step, which could be
accelerated by Lewis acid (LA) through coordination
with the TA ligand.20 Based on this strategy, the combi-
nation of LA and TA-Au was identified as a new catalytic
system, holding both good stability and excellent reactiv-
ity. To test whether this strategy is operable in the POP-
TA-Au catalysis, three representative reactions involving
LA activation of TA-Au were performed: enyne cycliza-
Gold redox catalysis: One of the most important and
recent developments in gold catalysis is gold redox
chemistry. Under proper conditions, Au(I) cation can be
oxidized to Au(III) and give interesting new reactivity
beyond the typical Au(I) π-acid activation.26 However,
one major challenge is ligand oxidation with the pres-
ence of a strong oxidant. Moreover, the formation of
phosphonium cation is one side reaction due to reductive
elimination of substrate with the phosphine ligand from
a reactive Au(III) intermediate.27 Considering all these
potential problems, we were wondering whether POP-
TA-Au is viable in promoting gold redox catalysis. The
gold-catalyzed alkyne oxidative coupling was selected to
evaluate this new heterogeneous catalyst.28 As shown in
Figure 5, using POP-Au-Cl as the catalyst, the desired
conjugated diynes 9a and 9b were prepared in excellent
yields.29
9
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
21
22
tion/isomerization,
alkyne hydroamination5,
and
Nakamura reaction.23
Figure 5. POP-Au-Cl catalyzed oxidative alkyne cou-
pling
Although reduced reactivity was observed after four
cycles, the fact that POP-Au could effectively promote
this transformation clearly suggested that A) the POP-Au
system can survive in the present of the strong oxidant
phenyliodonium diacetate (PIDA), and B) POP ligand is
compatible with gold(III) reductive elimination process.
This success certainly provides new opportunities for
other challenging transformations using this POP-Au
system.
Figure 4. Combination of POP-TA-Au and Lewis acid
Reaction of enyne 5 with TA-Au gave low yield (26%)
without the assistance of LA. With the addition of 2%
Ga(OTf)3, the desired product 6 was formed with a high-
er efficiency and yield (60%). Interestingly, using POP-
TA-Au catalyst alone (no LA), compound 6 was obtained
in 83% yield. The improved stability of the POP-TA-Au
once again proved to be beneficial for challenging trans-
formations. Furthermore, with the addition of LA, much
faster reaction kinetics were observed as expected, as
well as improved yield (88%, Figure 4A). Similarly, the
addition of Lewis acid to POP-TA-Au could effectively
facilitate alkyne hydroamination, giving improved yield
with faster reaction kinetics (Figure 4B).
Recently, we reported the first successful example of
gold-catalyzed intermolecular 1,3-diketone addition to
alkyne (Nakamura reaction) using the combination of
TA-Au and Ga(OTf)3.24 However, as shown in Figure
4C, to achieve a good yield, the expensive primary ligand
XPhos was required. Significantly lower yield (38%) was
obtained with PPh3 ligand. With simply polymerized
PPh3 as the ligand (POP-TA-Au), excellent yield was
achieved (92%). Catalyst recycling for hydroamination
and Nakamura reaction were also performed (see SI).25
Even though the catalyst reactivity was lower after three
In summary, we report herein an efficient porous pol-
ymer-supported triazole-gold catalyst (POP-TA-Au),
which could be easily prepared from simple starting ma-
terials in high yields. In addition to the good chemose-
lectivity of this new heterogeneous triazole-gold catalyst,
it also exhibited much better stability compared with
homogeneous TA-Au. This possibly results from a mi-
croenvironment generated by the flexible porous struc-
ture of the POP-PPh3 ligand. As a recyclable gold cata-
lyst, POP-TA-Au could be further applied into large-scale
syntheses and flow reactions. The development of POPs
using other phosphine ligands is currently ongoing in
our lab to enrich the diversity of this type of heterogene-
ous gold catalyst, which will permit their extension with-
in various applications and new reaction discovery.
ASSOCIATED CONTENT
AUTHOR INFORMATION
Corresponding Author
*Email: xmshi@usf.edu; sqma@usf.edu
ACS Paragon Plus Environment

Page 5 of 7
ACS Catalysis
Author Contributions
†These authors contributed equally to this work.
1
2
(11) Sun, L.-B.; Liu, X.-Q.; Zhou, H.-C. Chem. Soc. Rev. 2015, 44, 5092-
5147.
Supporting Information
3
(12) (a) Li, B.; Zhang, Y.; Ma, D.; Shi, Z.; Ma, S. Nature Commun. 2014,
5, 5537-5545. (b) Yue, Y.; Mayes, R. T.; Kim, J.; Fulvio, P. F.; Sun,
X.-G.; Tsouris, C.; Chen, J.; Brown, S.; Dai, S. Angew. Chem. Int.
Ed. 2013, 52, 13458-13462. (c) Alsbaiee, A.; Smith, B. J.; Xiao, L.;
Ling, Y.; Helbling, D. E.; Dichtel, W. R. Nature 2016, 529, 190-194.
(13) (a) Fischer, S.; Schmidt, J.; Strauch, P.; Thomas, A. Angew. Chem.
Int. Ed. 2013, 52, 12174-12178. (b) Wang, F.; Mielby, J.; Richter, F.
H.; Wang, G.; Prieto, G.; Kasama, T.; Weidenthaler, C.; Bongard,
H.-J.; Kegnæs, S.; Fürstner, A.; Schüth, F. Angew. Chem. Int. Ed.
2014, 53, 8645-8648. (c) Zhao, Q.; Zhang, P.; Antonietti, M.; Yuan,
J. J. Am. Chem. Soc. 2012, 134, 11852-11855. (d) Du, Y.; Yang, H.;
Whiteley, J. M.; Wan, S.; Jin, Y.; Lee, S.-H.; Zhang, W. Angew.
Chem. Int. Ed. 2016, 55, 1737-1741. (e) Ji, G.; Yang, Z.; Zhang, H.;
Zhao, Y.; Yu, B.; Ma, Z.; Liu, Z. Angew. Chem. Int. Ed. 2016, 55,
9685-9689. (f) Hausoul, P. J. C.; Broicher, C.; Vegliante, R.; Göb,
C.; Palkovits, R. Angew. Chem. Int. Ed. 2016, 55, 5597-5601. (g)
Ding, X.; Han, B.-H. Angew. Chem. Int. Ed. 2015, 54, 6536-6539. (h)
Xie, Y.; Wang, T.-T.; Liu, X.-H.; Zou, K.; Deng, W.-Q. Nature
Commum. 2013, 4, 1960. (i) Wu, K.; Guo, J.; Wang, C. Angew.
Chem. Int. Ed. 2016, 55, 6013-6017. (i) Sprick, R. S.; Bonillo, B.;
Clowes, R.; Guiglion, P.; Brownbill, N. J.; Slater, B. J.; Blanc, F.;
Zwijnenburg, M. A.; Adams, D. J.; Cooper, A. I. Angew. Chem. Int.
Ed. 2016, 55, 1792-1796. (j) Sun, Q.; Aguila, B.; Verma, G.; Liu, X.;
Dai, Z.; Deng, F.; Meng, X.; Xiao, F.-S.; Ma, S. Chem. 2016, 1,
628-639.
(14) Sun, Q.; Jiang, M.; Shen, Z.; Jin, Y.; Pan, S.; Wang, L.; Meng, X.;
Chen, W.; Ding, Y.; Li, J.; Xiao, F.-S. Chem. Commun. 2014, 50,
11844-11847.
(15) Teles, J. H.; Brode, S.; Chabanas, M. Angew. Chem., Int. Ed. 1998,
37, 1415-1418.
(16) Sherry, B. D.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 15978-
15979.
(17) (a) Wang, D.; Ye, X.; Shi, X. Org. Lett. 2010, 12, 2088-2091. (b)
Motika, S. E.; Wang, Q.; Ye, X.; Shi, X. Org. Lett. 2015, 17, 290-
293. (c) Hosseyni, S.; Ding, S.; Su, Y.; Akhmedov, N. G.; Shi, X.
Chem. Commun. 2016, 52, 296-299.
(18) Molecular sieve is necessary for preventing the hydration of allene,
but it may have influenced the recycle of POP-TA-Au.
(19) a) Wang, Q.; Motika, S. E.; Akhmedov, N. G.; Petersen, J. L.; Shi,
X. Angew. Chem. Int. Ed. 2014, 53, 5418-5422. (b) Motika, S. E.;
Wang, Q.; Akhmedov, N. G.; Wojtas, L.; Shi, X. Angew. Chem. Int.
Ed. 2016, 55, 11582-11586.
(20) Xi, Y.; Wang, Q.; Su, Y.; Li, M.; Shi, X. Chem. Commun. 2014, 50,
2158-2160.
(21) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc.
2004, 126, 10858-10859.
(22) Hesp, K. D.; Stradiotto, M. J. Am. Chem. Soc. 2010, 132, 18026-
18029.
(23) Nakamura, M.; Endo, K.; Nakamura, E. J. Am. Chem. Soc. 2003,
125, 13002-13003.
(24) Xi, Y.; Wang, D.; Ye, X.; Akhmedov, N. G.; Petersen, J. L.; Shi, X.
Org. Lett. 2014, 16, 306-309.
(25) Nakamura Reaction with 10 mmol scale was performed, see SI for
details.
4
5
6
7
8
9
Experimental procedures and characterization data. This
material is available free of charge via the Internet at
http://pubs.acs.org.
ACKNOWLEDGMENT
We thank the NIH(1R01GM120240-01), NSF (CHE-
1362057) and NSFC (21629201) for financial support.
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
REFERENCE
(1) For reviews of recent development of homogenous gold catalysis:
(a) Hashmi, A. S. K.; Schwarz, L.; Choi, J. H.; Frost, T. M. Angew.
Chem. Int. Ed. 2000, 39, 2285-2288. (b) Hashmi, A. S. K.; Hutch-
ings, G. J. Angew. Chem. Int. Ed. 2006, 45, 7896-7936. (c) Gorin, D.
J.; Toste, F. D. Nature 2007, 446, 395-403. (d) Garcia, P.; Malacria,
M.; Aubert, C.; Gandon, V.; Fensterbank, L. Chemcatchem 2010, 2,
493-497. (e) Hashmi, A. S. K. Angew. Chem. Int. Ed. 2010, 49,
5232-5241. (f) Sengupta, S.; Shi, X. D. Chemcatchem 2010, 2, 609-
619. (g) Garayalde, D.; Nevado, C. ACS Catal. 2012, 2, 1462-1479.
(h) Wang, Y. M.; Lackner, A. D.; Toste, F. D. Acc. Chem. Res. 2014,
47, 889-901. (i) Dorel, R.; Echavarren, A. M. Chem. Rev. 2015, 115,
9028-9072.
(2) (a) Wang, D.; Cai, R.; Sharma, S.; Jirak, J.; Thummanapelli, S. K.;
Akhmedov, N. G.; Zhang, H.; Liu, X.; Petersen, J. L.; Shi, X. J. Am.
Chem. Soc. 2012, 134, 9012-9019. (b) Kumar, M.; Hammond, G. B.;
Xu, B. Org. Lett. 2014, 16, 3452-3455.
(3) Wang, Z.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2014, 136, 8887-
8890.
(4) For selected examples of reported heterogeneous gold catalysis: (a)
Carrettin, S.; Blanco, M. C.; Corma, A.; Hashmi, A. S. K. Adv.
Synth. Catal. 2006, 348, 1283-1288. (b) García-Mota, M.; Cabello,
N.; Maseras, F.; Echavarren, A. M.; Pérez-Ramírez, J.; Lopez, N.
ChemPhysChem 2008, 9, 1624-1629. (c) Hutchings, G. J. Top.
Catal. 2008, 48, 55-59. (d) Neatu, F.; Li, Z.; Richards, R.; Toullec,
P. Y.; Genêt, J.-P.; Dumbuya, K.; Gottfried, J. M.; Steinrück, H.-P.;
Pârvulescu, V. I.; Michelet, V. Chem. Eur. J. 2008, 14, 9412-9418.
(e) Zhu, F.; Zhang, F.; Yang, X.; Huang, J.; Li, H. J. Mol. Catal. A:
Chem. 2011, 336, 1-7. (f) Carriedo, G. A.; López, S.; Suárez-Suárez,
S.; Presa-Soto, D.; Presa-Soto, A. Eur. J. Inorg. Chem. 2011, 2011,
1442-1447. (g) aidya, T.; Cheng, R.; Carlsen, P. N. Org. Lett. 2014,
16, 800-803. (h) Shu, X.-z.; Nguyen, S. C.; He, Y.; Oba, F.; Zhang,
Q.; Canlas, C.; Somorjai, G. A.; Alivisatos, A. P.; Toste, F. D. J. Am.
Chem. Soc. 2015, 137, 7083-7086. (i) Rühling, A.; Galla, H.-J.;
Glorius, F. Chem. Eur. J. 2015, 21, 12291-12294.
(5) Duan, H.; Sengupta, S.; Petersen, J. L.; Akhmedov, N. G.; Shi, X. J.
Am. Chem. Soc. 2009, 131, 12100-12102.
(6) Cao, W.; Yu, B. Adv. Synth. Catal. 2011, 353, 1903-1907.
(7) a) Egi, M.; Azechi, K.; Akai, S. Adv. Synth. Catal. 2011, 353, 287-
290. b) Zhu, Y.; Laval, S.; Tang, Y.; Lian, G.; Yu, B. Asia. J. Org.
Chem. 2015, 4, 1034-1039.
(8) (a) Perego, C.; Millini, R. Chem. Soc. Rev. 2013, 42, 3956-3976. (b)
Du, D. Y.; Qin, J. S.; Li, S. L.; Su, Z. M.; Lan, Y. Q. Chem. Soc.
Rev. 2014, 43, 4615-4632. (c) Umegaki, T.; Xu, Q.; Kojima, Y.
Materials 2015, 8, 4512-4534. (d) Qiu, J. H.; He, M.; Jia, M. M.;
Yao, J. F. Prog. Chem. 2016, 28, 1016-1028
(9) For example of Heterogeneous gold catalyst with POPs backbones,
see: Wang, W.; Zheng, A.; Zhao, P.; Xia, C.; Li, F. ACS Catal.
2014, 4, 321-327.
(10) a) Slater, A. G.; Cooper, A. I. Science 2015, 348. 988-998. (b) Kaur,
P.; Hupp, J. T.; Nguyen, S. T. ACS Catal. 2011, 1, 819-835. (c)
Zhang, Y. G.; Riduan, S. N. Chem. Soc. Rev. 2012, 41, 2083-2094.
(d) Xu, Y.; Jin, S.; Xu, H.; Nagai, A.; Jiang, D. Chem. Soc. Rev.
2013, 42, 8012-8031. (e) Sun, Q.; Dai, Z.; Meng, X.; Xiao, F.-S.
Chem. Soc. Rev. 2015, 44, 6018-6034.
(26) For reviews: (a) Wegner, H. A.; Auzias, M. Angew. Chem. Int. Ed.
2011, 50, 8236-8247. (b) Hopkinson, M. N.; Gee, A. D.;
Gouverneur, V. Chem. Eur. J. 2011, 17, 8248-8262. (c) Wegner, H.
A.; Auzias, M. Angew. Chem. Int. Ed. 2011, 50, 8236-8247. For
selected examples: (a) Ball, L. T. Science 2012, 337, 1644-1648. (b)
Cai, R.; Lu, M.; Aguilera, E. Y.; Xi, Y.; Akhmedov, N. G.; Petersen,
J. L.; Chen, H.; Shi, X. Angew. Chem. Int. Ed. 2015, 54, 8772-8776.
(c) Huang, L.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K.
Angew. Chem. Int. Ed. 2016, 55, 4808-4813.
(27) Kawai, H.; Wolf, W. J.; DiPasquale, A. G.; Winston, M. S.; Toste, F.
D. J. Am. Chem. Soc. 2016, 138, 587-593.
(28) (a) Peng, H.; Xi, Y.; Ronaghi, N.; Dong, B.; Akhmedov, N. G.; Shi,
X. J. Am. Chem. Soc. 2014, 136, 13174-13177. (b) Leyva-Pérez, A.;
Doménech-Carbó, A.; Corma, A. Nature Commun. 2015, 6, 6703-
6712.
ACS Paragon Plus Environment

ACS Catalysis
Page 6 of 7
1
2
(29) Homo-coupling of 3-fluorophenylacetylene with 10 mmol scale was
performed, see SI for details.
3
4
5
6
7
8
9
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

Page 7 of 7
ACS Catalysis
1
2
3
4
5
6
7
8
9
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