Metallomicelle catalyzed aerobic tandem desilylation/Glaser reaction in water

Article abstract of DOI:10.1039/c8gc03815e

PEG-grafted nitrogen ligands were synthesized. The corresponding copper complexes serve as metallomicellar nanoreactors for the aerobic tandem desilylation/Glaser coupling of TMS-protected alkynes in water. The protocol is also suitable for base-free homocoupling of terminal alkynes. The metallomicellar catalyst could be recycled 5 times with minor loss of reactivity.

Full text of DOI:10.1039/c8gc03815e

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DOI: 10.1039/C8GC03815E
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Metallomicelle Catalyzed Aerobic Tandem Desilylation/Glaser
Reaction in Water
Shanyu Tang, Longjia Li, Xuanhe Ren, Jiao Li, Guanyu Yang, Heng Li, and Bingxin Yuan*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
PEG-grafted nitrogen ligands were synthesized. The corresponding synthesis.23 Despite those prominent advances, metallomicelles
copper complexes serve as metallomicellar nanoreactors for the catalyzed dehydrogenative coupling reactions in water are
aerobic tandem desilylation/Glaser coupling of TMS-protected quite rare.
alkynes in water. The protocol is also suitable for base-free
homocoupling of terminal alkynes. The metallomicellar catalyst
could be recycled 5 times with minor loss of reactivity.
Fallis's work:
(5 mL TBAF over 2 h)
From the prospects of green chemistry, water is an ideal solvent
for organic synthesis since it is naturally abundant,
environmentally benign, and inexpensive.1-3 Since Breslow’s
discovery of the acceleration of Diels-Alder reaction in water,4
aqueous media has shown to improve the selectivity and
reactivity.5-8 Water as solvent is promising to provide the
possibility of catalyst recycling and work-up simplification as
quantitative [Cu]
pyridine/ether
R
Si
R
R
Yoshida and Kunai's work:
[Pd], O2
DMSO
R
Si
R
R
3 examples, up to 69%
10
most organic products are insoluble in aqueous media.9,
This work:
However, the low solubility of most organic compounds and
catalysts also is the hindrance to conduct organic synthesis in
water. Inspired by enzymes as highly active water soluble
catalysts in nature, the usage of surfactants under micellar
conditions represents one of the simplest methods to achieve
catalysis in aqueous media.11-15 Aiming at exploring the
recyclability of catalysts, covalently surfactant-modified
catalytic systems were endowed with metallo-surfactants.16-21
Covalent conjugation of surfactant scaffold to a ligand-metal
species bestows interesting surfactant-type features to
catalysts, such as the spontaneous aggregation to form micelles
and act as nanoreactors in water.22 More importantly, such
amphiphilic ligands can produce a highly concentrated catalytic
active species inside the hydrophobic core of the micelles. The
hydrophobic substrates turn to self-enrich inside the micellar
core and increase the chance of substrate to interact with
catalytic center. Metallo-surfactants have been used as green
alternatives to traditional homogeneous catalysts in organic
Cu
R
Si
R
R
O2, H2O
catalyst recycle: 5 times
Figure 1. Pathways for tandem desilylation/Glaser reaction.
1,3-Diynes are a class of conjugated diynes with unique
structures and properties.24 The rod-like molecular shape with
high rigidness enabled both stability and reactivity.25 Diynes can
be widely found in nature and serves as important building
blocks in material chemistry, synthetic chemistry and
pharmaceuticals.26-31 Glaser-Hay coupling of terminal alkynes in
the presence of oxidants represents a typical pathway to
32-34
synthesize 1,3-diynes.29,
The instability of some simple
terminal alkynes and higher polyynes becomes a major
challenge in Glaser coupling as they are prone to decomposition
and polymerization.35, 36 Tandem desilylation/dimerization of
trialkylsilyl-arylacetylene has been developed. The higher
stability of organosilanes compared to the corresponding
terminal alkynes would benefit the synthetic process by utilizing
a. College of Chemistry and Molecular Engineering, Zhengzhou University, China
450001.
† The authors declare no interest conflict.
Electronic Supplementary Information (ESI) available: [Experimental procedures,
characterization data, and 1H and 13C NMR spectra]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1. Optimization of reaction reagents.a
the former as starting material. Furthermore, organosilanes are
mostly synthesized by Sonogashira-type coupling between
trialkylsilylacetylene and aromatic halides, followed by the
deprotection of the trialkylsilyl group. The usage of in situ
generated terminal alkynes can avoid the purification
procedures and any stability concern. Fallis and coworkers
reported a copper-mediated in situ desilylation/dimerization of
TIPS-acetylenes in pyridine/ether, using TABF as a fluoride
source.37 In this protocol, 3 equivalents of Cu(OAc)2 were used
and the TBAF solution was added to the reaction mixture via
syringe pump (5 mL over 2 h). Yoshida and Kunai developed a
palladium-DPPP complex catalyzed homocoupling of
organosilanes in DMSO under oxygen atmosphere.38 However,
only three examples of diynes were obtained in modest yields.
Other progresses have been made by utilizing Pd and Cu as co-
catalytic system to produce 1,3-butadiynes via two steps in
moderate yields.39, 40
Our group has been working on the aerobic dehydrogenative
coupling reaction in aqueous media.41-44 Herein, we considered
synthesizing poly(ethylene glycol)-functionalized nitrogen
ligands and using their copper complex as catalysts to achieve
catalytic transformation of trialkylsilyl-arylacetylenes into the
corresponding diynes via tandem desilylation/dimerization in
one-pot. The amphiphilic instincts of the PEG-modified complex
tend to aggregate and form metallomicelles in aqueous media.
We speculate that metallomicelles can act as nanoreactors and
highly increase the catalyst performance, thus accomplish the
copper-catalyzed instead of copper-mediated tandem
desilylation/dimerization. Herein, in this context, we address
the use of amphiphilic nitrogen ligands (Figure 2), poly(ethylene
glycol)-functionalized 1,10-phenanthrolines ( L1 and L2) and
poly(ethylene glycol)-functionalized2,2’-bipyridines (L3 and L4).
We report an efficient and recyclable metallomicelle catalyzed
tandem desilylation/Glaser reaction with molecular oxygen as
the sole oxidant in water. Moreover, the usage of water as
solvent enables the potential to recycle the metallomicellar
catalyst system and simply the work-up procedure as the
product could be easily collected via filtration. All ligands could
be prepared in high yields in one step (see supporting
information).
View Article Online
DOI: 10.1039/C8GC03815E
catalyst, ligand, base
H2O, O2, 100 oC, 6h
SiMe3
2a
1a
Entry
1
2
3
4
5
6
7
8
Catalyst
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
Base
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
/
Ligand
/
L1
L2
Yield (%)b
0
Trace
98
43
11
63
30
Trace
0
41
1,10- phenanthroline
L3
L4
2,2'-bipyridine
pyridine
9
/
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
10
11
12
13
14
15
16
17
18
19
20
21
CuCl
CuBr
Cu(OAc)2
CuPcS
CoPcS
Pd(OAc)2
CuI
CuI
CuI
CuI
CuI
39
Trace
Trace
0
0
0
33
36
40
23
NaF
KF·2H2O
CsF
K2CO3
TBAF
CuI
77
[a] Reaction conditions: 1a (0.3 mmol), Catalyst (10 mol%), Ligand (10 mol%), Base
(1.0 equiv.), H2O (2 ml ), 0.3 MPa O2, 100 oC, 6 h. [b] Isolated yields.
This disiylation/Glaser coupling protocol was investigated by
using trimethyl(phenylethynyl)silane 1a as the model substrate
in the presence of a copper catalyst, ligand, and base. The
reaction was carried out under 0.3 MPa O2 in neat water. In the
absence of ligand, no product was formed (Table 1, Entry 1).
Interestingly, PEG-functionalized 1,10-phenanthroline ligands
L1 and L2 showed tremendously different catalytic activity. 2,9-
DiMPEG3-1,10-phenanthroline (L1) led to trace amount of
desired product 2a (Table 1, Entry 2), while 4,7-diMPEG3-1,10-
phenanthroline (L2) was able to furnish 2a in nearly quantitive
yield (Table 1, Entry 3, the conversion of substrate was
monitored by GC to get the appropriate reaction hour). A
control experiment with 1,10-phenanthroline as ligand was
performed, producing 2a in 43% yield (Table 1, Entry 4).
Speculatively, when the two PEG chains were grafted on 2,9-
positions of the 1,10-phenanthroline, oxygen atoms on the
chains could also serve as chelates to the transition metal
center, affecting the catalytic performance as well as the
approaching of substrates to the copper center. Also, steric
effect of the PEG chains may hinder the substrate approaching.
Similar outcomes were obtained in the case of PEG-
functionalized 2,2’-bipyridine ligands. Although 6,6’-DiMPEG3-
2,2’-bipyridine (L3) resulted in low yield (Table 1, Entry 5), 4,4’-
diMPEG3-2,2’-bipyridine (L4) and 2,2’-bipyridine led to 63% and
30% of product (Entry 6, 7), respectively. Pyridine as sole ligand
did not work well (Table 1, Entry 8). Screening of transitional
metal salts revealed CuI to be the optimal catalyst (Table 1,
Entry 10-15). The control experiment performed in the absence
3
3
O
O
O
O
N
N
O
O
O
3
O
3
N
N
L2
L1
3
3
O
O
N
O
N
O
O
O
O
3
O
3
N
N
L3
L4
Figure 2. PEG-functionalized nitrogen ligands for disiylation/Glaser couplingin aqueous
media.
2 | J. Name., 2012, 00, 1-3
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of catalyst indicated the necessity of Cu (Table 1, Entry 9). position, such as trifluoromethyl and fluoro goups, led to
View Article Online
Fluoride sources and bases were tested as well, and NaOH modest yields under the optimal reactionDcOonI:d10it.1io0n39(/2Ci8,Gj)C. 0G3C8M15ES
turned to be the optimal desiylation agent (Table 1, Entry 16- results indicated the starting material didn’t undergo
21).
desiylation thoroughly. The yield of 2i reached 94% by the
Other reaction parameters, such as catalyst/ligand amount, replacement of NaOH with TBAF (1.0M solution in THF). The
base equivlents, temperature and oxygen pressure, were attemptation to increase the amount of NaOH to 2 equiv
studied (Table S1 in the supporting information). By keeping the achieved 2j in 94% yield. The homocoupling of
ratio of catalyst/ligand at 1:1, the evaluation of various amount alkylethynylsilanes (1m and 1n) proceeded to provided
of catalyst/ligand showed 10 mol% to be optimal (Table S1, corresponding 1,3-butadiynes (2m and 2n) in moderate yields.
Entry 1-5). Increasing relative quantity of either CuI or L2 The desiylation/heterocoupling of organosilanes was
reduced the product yiled evidently (Table S1, Entry 6, 7). The attempted by using (p-anisylethynyl)trimethylsilane 1e as
reaction atmoshpere evaluation showed that the lowering O2 model substrate (Table 3). The asymmetric products were
pressure led to decresed raction effeciency (Table S1, Entry 8, obtained in 52-71% yields (4a-d).
9). The control experiment under N2 led to no product (Entry 8),
demonstrating the necessity of O2 as oxidant for the
dehydrogenative coupling. The varition of temperature
parameters stated 80 oC to be the most suitable reaction
temperature (Table S1, Entry 11, 12). Furthermore, one
equivalent NaOH proved to be sufficient enough for desilylation
(Table S1, Entry 13-17).
Table 3. Desiylation/ Heterocoupling of TMS-alkynes.a
CuI, L2, NaOH
+
1f
R
SiMe3
R
OCH3
O2, H2O, 80 o
C
1
4
R
pdt
Yieldb
67
R
pdt
Yieldb
63
F
4a
4b
4c
Table 2. Desiylation/Homocoupling of TMS-alkynes.a
S
71
4d
52
CuI, L2, NaOH
R
SiMe3
R
R
O2, H2O, 80 o
C
1
2
[a] Reaction conditions: 1f(0.3 mmol), 1 (0.9 mmol), CuI (10 mol%), L2 (10 mol%),
NaOH (1.0 equiv.), H2O (2 mL), 0.3 MPa O2, 80 oC, 6 h. [b] Isolated yields.
pd
t
R
Yieldb
R
pdt
Yieldb
Table 4. Homocoupling of terminal alkynes.a
Br
CuI, L2
2a
2b
2c
99
2h
2i
93
R
H
R
R
O2, H2O, 80 o
C
1'
2
46(94c)
68 (87d)
F
94
R
pdt
Yieldb
99
R
pdt
Yieldb
87
F
F3C
84
90
2j
2a
2i
2j
F3C
2b
2c
94
83
93
93
2d
2k
87
2k
2l
S
2e
2f
90
91
2l
95
S
2m
5 (61c)
O
2d
96
81
Cl
2e
2f
91
97
2m
2n
75
72
2g
92
2n
74
O
[a] Reaction conditions: 1 (0.3 mmol), CuI (10 mol%), L2 (10 mol%), NaOH (1.0
equiv), H2O (2 mL), 0.3 MPa O2, 80 oC, 6 h. [b] Isolated yields. [c] TBAF (1.0
M solution in THF) as desiylation agent. [d] NaOH (2.0 equiv).
Cl
Br
HO
2g
2h
98
87
2o
2p
84
84
With the optimal conditions in hand, we explored its
applicability for desiylation/homocoupling of TMS-protected
alkynes (Table 2). Organosilanes with various aromatic and
heteroaromatic groups smoothly underwent coupling reaction
and gave the corresponding symmetrical products in up to 99%
yields (2a-l). Arylethynylsilanes bearing electron-donating
substituents at the para- and othro-positions of the aromatic
ring (1b, 1d-h) are more favorable than that with substituent at
the meta-position (1c). Electron-withdrawing groups on para-
Me3Si
[a] Reaction conditions: 1’ (0.3 mmol), CuI (10 mol%), L2 (10 mol%), H2O (2 mL), 0.3
MPa O2, 80 oC, 6 h. [b] Isolated yields.
Encouraged by the success in desiylation/homocouping of
alkynylsilanes, we attempted homocoupling of terminal alkynes.
The homocoupling of terminal alkynes was performed in the
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absence of NaOH since the desiylating agent was not needed
(Table 4). This base-free aerobic oxidative coupling of terminal
alkynes in water displayed high efficiency and extensive
versatility. Except the substrates mentioned in Table 3, base-
View Article Online
DOI: 10.1039/C8GC03815E
sensitive
compounds,
2-methyl-3-butyn-2-ol
and
ethynyltrimethylsilane can be employed to produce the
corresponding diynes (2o and 2p), of which the latters are
significant synthetic motifs. The base-free aerobic
heterocoupling of terminal alkynes was tested with 2-methyl-3-
butyn-2-ol as a fixed substrate (Table 5). The asymmetric
products were produced in 59-71% yields.
Table 5. Heterocoupling of terminal alkynes. a
L2
L2:CuI = 1:1
Figure 4. DLS and TEM results of metallomicelle.
L
CuI,
2
+
1p'
R
OH
H
R
O2, H2O, 80 o
C
1'
5
70
65
60
55
50
45
40
35
R
No.
Yieldb
R
No.
Yieldb
63
F
5a
67
5c
5b
71
[a] Reaction conditions: 1p’ (0.3 mmol), 1’ (0.9 mmol), CuI (10 mol%), L2 (10 mol%),
NaOH (1.0 equiv.), H2O (2 mL), 0.3 MPa O2, 80 oC, 6 h. [b] Isolated yields.
UV-Vis studies of L2 in aqueous solution were carried out
(Figure 3). The L2 solution displayed absorption bands in the
range of 200~380 nm. Upon the addition of CuI (1 equiv.), the
solution turned bluish and the absorption spectrum showed red
shift with an increasing shoulder at 218 nm. This color change
and band shift confirms the coordination of phenanthroline-
nitrogen atom to the central copper ion.
30
-4
-2
lg C (mol/L)
Figure 5. A plot of surface tension γ (mN/m) of the aqueous L2 solution vs. logarithm of
L2 concentration at 286.15 K.
Table 6. Homocoupling of 1a at various ligand concentrations.a
CuI, L2, NaOH
Ph
SiMe3
Ph
Ph
O2, H2O, 80 o
C
1a
2a
H2O (mL)
30.0
15.0
7.5
Conc.( mol/L)b
0.001
Yield (%)c
10
40
99
99
0.002
0.004
0.007
4.3
[a] Reaction condition: 1a (0.3 mmol), CuI (10 mol%), L2 (10 mol%), NaOH (1.0
equiv), H2O, 0.3 MPa O2, 80 oC, 6 h. [b] Concentration (mol/L) of L2. [c] Isolated
yield.
Figure 3. UV-Vis absorption spectra of L2 solutions.
The critical micelle concentration (CMC) was determined by
plotting the surface tension as a function of L2 concentration
(Figure 5). An abrupt change of slope marked the transition
from the pre-micellar state to micellar solution around 0.003
mol/L (CMC). Since the concentration of L2 used in the optimal
reaction condition is 0.015 mol/L, it is reasonable to conclude
the presence of metallomicelle in the reaction mixture.
Furthermore, the aerobic tandem desilylation/Glaser reaction
of TMS-alkyne 1a was performed beyond and below the CMC.
Low yields were obtained at 0.001 and 0.002 mol/L of L2 when
no micelles formed (Table 6, Entry 1, 2), while 99% yields could
be achieved beyond the CMC (Table 6, Entry 3, 4). This might be
To study the structure and morphology of aggregates
assembled form catalyst L2-Cu in water, we conducted dynamic
light scattering (DLS) and transmission electron microscopy
(TEM) studies. DLS experiment with L2 in the absence of Cu
revealed the existence of self-assembled nanostructures (Figure
4a). Upon the addition of 1 equivalent CuI to the L2 solution, the
nanomicelle size increased (Figure 4b), which might be owing to
the entering of copper in the micelle center and its coordination
to the nitrogen chelates. The spherical shape and average size
of nanoscale micelles revealed by TEM was in agreement with
that identified by DLS (Figure 4c, 4d).
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6.
S. Narayan, J. Muldoon, M. G. Finn, V. V. Fokin, H. C. Kolb and
K. B. Sharpless, Angew. Chem. Int. Ed.,D2O0I0:510, 4.140,3V93ie/2wC78A5Gr-ti3Cc2l0e73O98n1.li5nEe
A. Chanda and V. V. Fokin, Chem. Rev., 2009, 109, 725-748.
S. Handa, M. P. Andersson, F. Gallou, J. Reilly and B. H.
Lipshutz, Angew. Chem. Int. Ed., 2016, 55, 4914-4918.
R. Zhong, A. Pöthig, Y. Feng, K. Riener, W. A. Herrmann and F.
E. Kühn, Green Chem., 2014, 16, 4955-4962.
a reflection of the micellar effect contributed by the surfactant-
type ligand L2.
7.
8.
The sustainability of the metallomicelle enabled
transformation was assessed by performing recycle studies of
trimethyl(phenylethynyl)silane 1a and ethynylbenzene 1a’
under the optimal reaction conditions, respectively (Figure 6).
The recovery of micelle solution and product collection could be
completed by simple filtration. The metallomicellar catalytic
system could be reused five times with minor loss of reactivity.
9.
10. G. Zhang, R. Lang, W. Wang, H. Lv, L. Zhao, C. Xia and F. Li,
Adv. Synth. Catal., 2015, 357, 917-922.
11. G. La Sorella, G. Strukul and A. Scarso, Green Chem., 2015, 17,
644-683.
12. S. Polarz, M. Kunkel, A. Donner and M. Schlötter, Chem. Eur.
J., 2018, 24, 18842-18856.
13. L. L. Tang, W. A. Gunderson, A. C. Weitz, M. P. Hendrich, A. D.
Ryabov and T. J. Collins, J. Am. Chem. Soc., 2015, 137, 9704-
9715.
14. S. Serrano-Luginbühl, K. Ruiz-Mirazo, R. Ostaszewski, F. Gallou
and P. Walde, Nat. Rev. Chem., 2018, 2, 306-327.
15. Y. Tu, F. Peng, A. Adawy, Y. Men, L. K. E. A. Abdelmohsen and
D. A. Wilson, Chem. Rev., 2016, 116, 2023-2078.
16. X. Luo, J. Deng and W. Yang, Angew. Chem. Int. Ed., 2011, 50,
4909-4912.
Ph
Ph
TMS
H
17. B. H. Lipshutz, N. A. Isley, R. Moser, S. Ghorai, H. Leuser and B.
R. Taft, Adv. Synth. Catal., 2012, 354, 3175-3179.
18. H. Azoui, K. Baczko, S. Cassel and C. Larpent, Green Chem.,
2008, 10, 1197-1203.
19. L. Monnereau, D. Sémeril, D. Matt and L. Toupet, Adv. Synth.
Catal., 2009, 351, 1629-1636.
Figure 6. Catalyst recycle.
Conclusions
In conclusion, a series of PEG-grafted nitrogen ligands were
synthesized via one-step procedure in excellent yields. The
corresponding water-soluble amphiphilic copper complexes
turn to form nano-sized metallomicelles. An effective and
recyclable metallomicellar catalyst for tandem desilylilation/
Glaser reaction in water with molecular oxygen as the sole
oxidant has been developed. This protocol avoids the work-up
procedure and instability caused by the deprotection of the
trialkylsilyl group to achieve the corresponding terminal alkynes.
At the meantime, these nanoreactors are highly efficient for
base-free aerobic oxidative of terminal alkynes as well. DLS and
TEM studies demonstrate the existence of round-shaped
nanomicelles. The catalytic performance is highly affected by
the size and morphology of metallomicelles. The recyclability of
metallomicellar catalyst could run 5 times in the homocoupling
of TMS-protected and terminal alkynes, respectively.
20. T. Terashima, T. Mes, T. F. A. De Greef, M. A. J. Gillissen, P.
Besenius, A. R. A. Palmans and E. W. Meijer, J. Am. Chem.
Soc., 2011, 133, 4742-4745.
21. J. Li, Y. Tang, Q. Wang, X. Li, L. Cun, X. Zhang, J. Zhu, L. Li and J.
Deng, J. Am. Chem. Soc., 2012, 134, 18522-18525.
22. A. Sorrenti, O. Illa and R. M. Ortuño, Chem. Soc. Rev., 2013,
42, 8200-8219.
23. B. H. Lipshutz and S. Ghorai, Org. Lett., 2009, 11, 705-708.
24. W. A. Chalifoux and R. R. Tykwinski, Nat. Chem., 2010, 2, 967.
25. A. Lucotti, M. Tommasini, D. Fazzi, M. Del Zoppo, W. A.
Chalifoux, M. J. Ferguson, G. Zerbi and R. R. Tykwinski, J. Am.
Chem. Soc., 2009, 131, 4239-4244.
26. S. Eisler, A. D. Slepkov, E. Elliott, T. Luu, R. McDonald, F. A.
Hegmann and R. R. Tykwinski, J. Am. Chem. Soc., 2005, 127,
2666-2676.
27. M. Younus, A. Köhler, S. Cron, N. Chawdhury, M. R. A. Al-
Mandhary, M. S. Khan, J. Lewis, N. J. Long, R. H. Friend and P.
R. Raithby, Angew. Chem. Int. Ed., 1998, 37, 3036-3039.
28. P. Siemsen, R. C. Livingston and F. Diederich, Angew. Chem.
Int. Ed., 2000, 39, 2632-2657.
Acknowledgement
29. W. Shi, Curr. Organocatal., 2015, 2, 2-13.
30. J. Liu, J. W. Y. Lam and B. Z. Tang, Chem. Rev., 2009, 109,
5799-5867.
The authors thank the National Natural Science Foundation of
China (No. 21801229) for the funding support.
31. A. L. K. Shi Shun and R. R. Tykwinski, Angew. Chem. Int. Ed.,
2006, 45, 1034-1057.
32. K. S. Sindhu and G. Anilkumar, RSC Adv., 2014, 4, 27867-
27887.
33. H. Doucet and J.-C. Hierso, Angew. Chem. Int. Ed., 2007, 46,
834-871.
34. W. Shi and A. Lei, Tetrahedron Lett., 2014, 55, 2763-2772.
35. G. N. Patel, R. R. Chance, E. A. Turi and Y. P. Khanna, J. Am.
Chem. Soc., 1978, 100, 6644-6649.
References
1.
T. Kitanosono, K. Masuda, P. Xu and S. Kobayashi, Chem. Rev.,
2018, 118, 679-746.
2.
C. J. Clarke, W.-C. Tu, O. Levers, A. Bröhl and J. P. Hallett,
Chem. Rev., 2018, 118, 747-800.
3.
4.
R. A. Sheldon, Green Chem., 2005, 7, 267-278.
D. C. Rideout and R. Breslow, J. Am. Chem. Soc., 1980, 102,
7816-7817.
36. M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson and T. J. R.
Weakley, J. Am. Chem. Soc., 1997, 119, 2956-2957.
5.
R. N. Butler and A. G. Coyne, Chem. Rev., 2010, 110, 6302-
6337.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 6 of 7
COMMUNICATION
Journal Name
37. M. A. Heuft, S. K. Collins, G. P. A. Yap and A. G. Fallis, Org.
Lett., 2001, 3, 2883-2886. For other copper-mediated
protocols, see: a) K. Ikegashira, Y. Nishihara, K. Hirabayashi, A.
Mori, T. Hiyama, Chem. Commun. 1997, 1039-1040; b) M. M.
Haley, M. L. Bell, S. C. Brand, D. B. Kimball, J. J. Pak, W. B.
Wan, Tetrahedron Lett. 1997, 38, 7483-7486.
View Article Online
DOI: 10.1039/C8GC03815E
38. H. Yoshida, Y. Yamaryo, J. Ohshita and A. Kunai, Chem.
Commun., 2003, DOI: 10.1039/B303852A, 1510-1511.
39. E. Merkul, D. Urselmann and T. J. J. Müller, Eur. J. Org. Chem.,
2010, 2011, 238-242.
40. Y. Gong and J. Liu, Tetrahedron Lett., 2016, 57, 2143-2146.
41. Y. Dou, X. Huang, H. Wang, L. Yang, H. Li, B. Yuan and G. Yang,
Green Chem., 2017, 19, 2491-2495.
42. X. Huang, Y. Chen, S. Zhen, L. Song, M. Gao, P. Zhang, H. Li, B.
Yuan and G. Yang, J. Org. Chem., 2018, 83, 7331-7340.
43. L. Yang, S. Li, Y. Dou, S. Zhen, H. Li, P. Zhang, B. Yuan and G.
Yang, Asian J. Org. Chem., 2017, 6, 265-268.
44. Y. Dou, L. Yang, L. Zhang, P. Zhang, H. Li and G. Yang, RSC Adv.,
2016, 6, 100632-100635.
6 | J. Name., 2012, 00, 1-3
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Green Chemistry
View Article Online
DOI: 10.1039/C8GC03815E
Metallomicelle Catalyzed Aerobic Tandem Desilylation/Glaser Reaction in
Water
Cu
R
Si
R
R
O2, H2O
Metallomicelle as nanoreactor