Selective C(sp3)–H Monoarylation Catalyzed by a Covalently Cross-Linked Reverse Micelle-Supported Palladium Catalyst

Article abstract of DOI:10.1002/adsc.201700707

In this work, we illustrate the performance of a solvated micelle-supported ligand as a platform for coordination with palladium for C–H arylation. The micelle-supported ligand is one of the first applications of a micelle-supported ligand for C–H arylation, and provides a tunable support for future elaboration. The use of a spatially constrained system promoted selectivity trends influenced by both the sterics and electronics of the system, differing from the homogeneous catalyst, with high yields and selectivities. (Figure presented.).

Full text of DOI:10.1002/adsc.201700707

Title: Selective C(sp3)–H Monoarylation Catalyzed by a Covalently
Cross-linked Reverse Micelle-Supported Pd Catalyst
Authors: Caroline Hoyt, Li-Chen Lee, Jian He, Jin-Quan Yu, and
Christopher Jones
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700707
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Selective C(sp3)–H Monoarylation Catalyzed by a Covalently
Cross-linked Reverse Micelle-Supported Palladium Catalyst
Caroline B. Hoyt,a† Li-Chen Lee,a† Jian He,b Jin-Quan Yu,b Christopher W. Jonesa*
a
School of Chemistry and Biochemistry, School of Chemical and Biomolecular Engineering, Georgia Institute of
Technology, Atlanta, GA 30332 USA
Email: cjones@chbe.gatech.edu
Department of Chemistry, The Scripps Research Institute, La Jolla, California, 92307, USA
b
Email: yu200@scripps.edu
†
These two authors contributed equally to this work
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. In this work, we illustrate the performance of a
solvated micelle-supported ligand as
a platform for
Keywords: C – H activation; Micelle; Palladium catalysis;
coordination with palladium for C–H arylation. The micelle-
supported ligand is one of the first applications of a micelle-
supported ligand for C–H arylation, and provides a tunable
support for future elaboration. The use of a spatially
constrained system promoted selectivity trends influenced by
both the sterics and electronics of the system, differing from
the homogeneous catalyst, with high yields and selectivities.
Supported catalyst; Monoarylation
One of the first examples of Pd(II)-catalyzed C(sp3)–
H arylation was reported in 2005, where pyridine
acted as a directing group. Considering C(sp3)–H
arylation could be directed by a pyridine moiety, it
was reasoned that bidentate coordination between the
active palladium center and an aminoquinoline
species would benefit the reaction specificity.[23]
Later, the reaction was honed for specific
monoarylation employing substituted aryl iodides not
requiring steric bulk, such as a tert-butyl group,
which allowed for further functionalization strategies.
The Yu group employed a non-natural amino acid
starting material with excess amounts of aryl iodides,
and identified 2-picoline as a ligand for selective
monoarylation using homogeneous palladium(II)
trifluoroacetate.[13]
Introduction
Development of methods for direct insertion into C–
H bonds has attracted substantial attention over the
past two decades due to the abundance of these
bonds. Unfortunately, the typical C(sp3)–H bond is
highly inert and thermodynamically stable, requiring
eloquent catalytic strategies to activate the bond
compared to conventional C–H functionalization
methods.[1,2] Transition-metal-catalyzed directed C–H
activation has been extensively explored by installing
powerful directing groups,[3-12] and the scope of the
transformations can be further expanded through the
incorporation of ligands into the catalysis.[13-22]
Recent studies of specific ligand design for
coordination with palladium have proved to be
critical for C–H activation, and advantageously
require less synthetic steps.[13] Tuning the
coordination environments of palladium catalysts
with various ligands has been used to selectively
activate different types of C(sp3)–H bonds.
While homogeneous Pd catalysts have been
widely used in C(sp3)–H arylation, relatively high
catalyst loadings are often required to obtain good
yields in these C(sp3)–H activation/C–C bond-
forming reactions, since the catalysts are prone to
decomposition under harsh reaction conditions. One
way to enhance the turnover numbers (TONs) and
better utilize the ligand and metal species is to
1
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
recover and recycle these components. However, in
many cases, reuse of homogeneous transition metal
catalysts remains a significant challenge. We have
recently demonstrated the feasibility of reuse of
Pd(II) combined with Yu’s mono-dentate pyridine
ligands and have shown that the catalyst, both ligand
and metal, can be recovered and recycled, modestly
improving the TON. Using soluble polymeric
supports with tailorable structures, we also
demonstrated that the supported Pd species could
impart altered (relative to the homogeneous catalyst)
selectivity trends using several model substrates.[24]
Other types of supported catalysts have also been
utilized in C–H activation, with use of metal organic
framework (MOF) supported Pd,[25,26] and Pd-
nanoparticles embedded in various supports[27,28] as
examples. A particularly attractive support that has
not yet been explored for Pd catalysts in C–H
activation reactions is a micelle, which has classically
been employed with both homogeneous and
heterogeneous catalysts that can exploit this unique
microenvironment,[29-31] but also can provide a very
tunable and recoverable catalytic platform. Solvated
micelles have been used as transition metal catalyst
supports, for example coordinating palladium inside
the micelle core for C–N bond formation and C–C
bond formation; however, the use of a micelle for C–
H activation has not been reported to this point.[32,33]
In this work, we demonstrate the use of micelles as a
reusable support for Pd-catalyzed C–H monoarylation
reactions as an initial example, and subsequently a
cross-linked, reverse micellar design with tunable
spatial constraints around the supported ligands used
to bind palladium that imparts selectivity by
restricting the space around the metal-ligand complex.
Previous reports have used ligand control for
the cross-linked core of our micelles restricts the
internal catalytic core and support from mixing
contents, and helps retain the ligand and palladium
for future reuse.
Scheme 2. General preparation of cross-linked micelle-
supported ligand
As seen above in Scheme 2, polymerizable
surfactant
B
with functionalizable double-tail
surfactant A , or (not pictured) a functionalizable
triple tail analogue were dissolved in a 1:5 ratio of
A:B. This ratio allows the surfactants to cross-link on
their own, rather than add any additional crosslinker,
and ensures surfactant A and B polymerize together,
limiting the self-polymerization of surfactant B,
which would occur if the ratio were larger. Surfactant
A was designed and synthesized to contain a benzyl
bromide functional handle within the core for further
substitution with 4-amino 2-methylpyridine used as
the ligand in the C(sp3)–H monoarylation. The
micelles then self-assembled in H2O and heptane, and
were cross-linked using a photoinitiator at 365 nm to
create DM, the double-tail micelle. The
functionalizable benzyl bromide was substituted with
amine containing ligand moieties to form the double-
tail micelle with ligand (DML) and further
coordinated in situ with a palladium precursor to
yield the precatalyst. Next, optimization of the
reaction conditions with various amounts of DML
(Table S1), palladium, and aryl iodide was completed
(Table S2).
achieving
monoarylation
versus
diarylation
selectivity,[13] and the micelle support creates a well-
defined catalytic nanoenvironment that can be reused
with high selectivity.
The first generation of the cross-linked micelle
provided a tunable platform for catalyst design, and
the first example of micelle-supported Pd(II)-
catalyzed C(sp3)–H monoarylation. The initial
tunable property of the micelle explored was the
surfactant-alkyl density of surfactant B. The alkyl
density played a significant role in the catalytic
activity of the micelle,[35] altering the number of
hydrophobic tails covalently bound to a hydrophilic
head group between two and three. The second
property of the micelle to be evaluated was the size of
the catalytic core. In the synthesis of the catalytic
micelle, various amounts of water were introduced in
the first step of Scheme 2 to vary the size of the
micelle core, known as W0. The combination of
assorted W0 values paired with different numbers of
alkyl hydrophobic tails potentially allows for size
selectivity as well as creation of a diffusive barrier for
substrates and products.
Results and Discussion
Scheme 1. Pd-catalyzed C(sp3)–H monoarylation.
The design of the catalytic micelle began with
identification of key properties to tune, such as the
alkyl density of surfactant tails,[34,35] size of the
hydrophilic core,[34] and ligand functionalization
within that core. After exploiting the hydrophilic
head group and hydrophobic alkyl tail, the resulting
micelles were interfacially cross-linked to provide
thermal stability,[30] necessary for the Pd-catalyzed
C(sp3)–H monoarylation shown above (Scheme 1). In
classic micelles, there is dynamic mixing of
surfactant and internal contents of the core, whereas
2
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
Table 1. Micelle-supported ligands with various W0 and
micelle shell in Pd-catalyzed C(sp3)–H arylation[a,b]
extended reaction time needed to allow for
diffusion into the core (Table 1 below, entries 7
and 8), but no appreciable increased yield was
observed after 48 hours. The DML hydrophobic
shell is less crowded, with double tails compared
to triple, and therefore we hypothesize it
presented a more penetrable barrier to the active
micelle core. After the examination of both the
micelle core size and hydrophobicity of the
micelle shell, the DML micelle with W0 = 5 was
carried through for further exploration in the
C(sp3)–H monoarylation.
Micelle-
Ligand
Yield
(%)[b]
Selectivity
(%)[b]
Entry
W0
2:3[b]
1
2
3
4
5
6
7
8
20:0
24:0
83:17
66:10
24:0
51:4
49:3
DML
DML
DML
DML
TML
TML
TML
TML
(48h)
0
2
5
10
2
5
20
24
99
76
24
55
52
100
100
83
87
100
93
Table 2. Micelles with various pyridine-based ligands in
Pd-catalyzed C(sp3)–H arylation[a,b]
10
94
10
65
61:4
94
[a]
Reaction conditions: substrate (0.05 mmol), Pd(TFA)2
[palladium(II) trifluoroacetate] (0.01 mmol), DML/TML
(10 mg), Ag2CO3 (0.075 mmol), TFA (0.01 mmol),
iodobenzene (0.15 mmol), and cyclohexane (0.3 mL) were
added. The reaction vessel was sealed and the mixture was
Micelle-
Ligand
Yield
(%)[b]
Selectivity
(%)[b]
Entry
W0
2:3[b]
stirred at room temperature for 10 min and then heated to
[b]
100 oC for 20 h with vigorous stirring.
The yield
1
2
3
DML
DML’
DML’(48h)
DML’’
5
5
5
5
99
55
73
26
83:17
50:5
64:9
26:0
83
91
88
1
percentage and ratios of 2 and 3 were determined by H
NMR using CH2Br2 as the internal standard.
4
100
[a]
Reaction conditions: substrate (0.05 mmol), Pd(TFA)2
trifluororacetate] (0.01 mmol),
Table 1 displays the catalytic results highlighting
the optimized micelle shell and core structure,
[palladium(II)
DML/DML‘/DML‘‘ (10 mg), Ag2CO3 (0.075 mmol), TFA
(0.01 mmol), iodobenzene (0.15 mmol), and cyclohexane
(0.3 mL) were added. The reaction vessel was sealed and
the mixture was stirred at room temperature for 10 min and
which is comprised of a 1:5 ratio of surfactant
A
and with differing core diameters, denoted W0.
B
The double tail micelle supported ligand (DML)
maintained the proper amphiphilic characteristics
to form the initial dynamic micelle in solution,
and further provided a stable reverse cross-linked
micelle. Entries 1, 2, and 5 all had small W0, and
corresponding low yields of monoarylated
o
[b]
then heated to 100 C for 20 h with vigorous stirring.
The yield percentage and ratios of 2 and 3 were determined
by 1H NMR using CH2Br2 as the internal standard.
In previous studies, the ligand in DML
(Table 2) was used to carry out the C(sp3)–H
arylation homogeneously,[13] and selectivity
product
2. A larger core, with W0 = 5 or 10,
appeared to allow for an increase in conversion of
starting material, displaying the necessity for a
core large enough to accommodate starting
materials and product. There was not a large
difference in selectivity with core sizes 5 or
larger, which was unexpected. We anticipated
trends for product
2 relative to 3 were also
studied with a linear polymer supported ligand,
which provided a platform for improvement.[24]
The DML micelle with W0 = 5 produced a
selectivity of 83% for the monoarylated product
after 20 h; however, incorporation of a different
ligand in the micelle core could further improve
the selectivity. Ligand DML’ was chosen because
of its similar electronic structure to the original
ligand DML, but also providing added steric
constraints inside the core. With a slightly bulkier
ligand in the core, we hypothesized this would
with the larger core, product
2 would have the
opportunity to interact with the palladium catalyst
and convert to the diarylated product
readily; however, this was not observed.
3 more
The triple tail micelle supported ligand
(TML) displayed lower yields across various W0,
with a higher selectivity. Unfortunately, TML W0
= 10 with extended reaction time did not display
significantly increased yield. This may be
associated with the thick hydrophobic shell the
TML possessed, while increased yield was
demonstrated with the DML. The thick shell
imparted a restriction on transport properties of
substrates into the core, highlighted with the
help force the newly formed product
2 out of the
core, leading to increased selectivity for
monoarylation. As has been seen with previous
reports,[13]
the
monoarylation is highly sensitive to the ligand,
and decreased yield of product was observed
activity
for
C(sp3)–H
2
with the sterically more hindered ligand DML’.
3
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
iodobenzene (0.15 mmol), and cyclohexane (0.3 mL) were
added. The reaction vessel was sealed and the mixture was
DML’’ was also selected to probe the effect of
different electronics around the pyridine ligand,
incorporating a strong electron donating group
ortho- to the pyridine nitrogen, while maintaining
a similar steric influence to DML. The additional
electron density in DML’’ dramatically reduced
yield, and correspondingly high selectivity was
observed. In contrast to the homogeneous case,
the incorporation of all ligand cases did not
stirred at room temperature for 10 min and then heated to
[b]
100 oC for 20 h with vigorous stirring.
The yield
percentage and seelctivities of 2 and 3 in brackets were
determined by 1H NMR using CH2Br2 as the internal
standard.
The monoarylation proceeded in high yields
and selectivities for both electron-withdrawing
and electron-donating substituents on the aryl
iodide with the micelle-supported ligand and
palladium.[38] The selectivity can be highlighted
in products 2a1 and 2e1 (as seen in Table 3).
These two coupling partners have second
substitutions ortho- to the active iodo group,
imparting an increase in selectivity. Notably, the
same selectivity is not seen with the para-
substituted compounds 2a3 and 2e3 that are
increase the amount of diarylated product 3 [13]
,
supporting the benefit of a spatially constrained
catalytic pocket for improved selectivity by
elimination of bulkier products. To this end, it
appears the micelle core provided a valuable
steric limitation for the prevention of the
formation of the diarylated product. Previously,
an optimal balance of sterics and electronics for
the ligand-controlled C(sp3)–H arylation was
demonstrated through the evaluation of multiple
ligands,
varying
both
sterics
or
electronically
similar.
Interestingly,
this
electronics.[13,15,36,37] This particular C(sp3)–H
arylation was exceptionally sensitive to the ligand
present, as seen in the homogeneous case, so the
decreased yield for non-optimal ligands was not
entirely unexpected.[13,24]
selectivity pattern has not been observed with
other Pd-catalyzed monoarylation reactions; in
fact, conversely, the yield is typically decreased
with ortho- substitutions due to steric
hindrance.[39] Both 2a3 and 2e3 had excellent
yields of 99% and similarly decreased
selectivities of 77 and 74%. The high reactivity of
both the para- and meta-substituted aryl iodides
contributed to the decreased selectivity toward
monoarylation. This selectivity at the ortho-
position is hypothesized to be an electronically-
influenced steric effect within the micelle core. A
previously reported heterogeneous polymer
Having identified a suitable micelle catalyst
structure with (i) two alkyl tails and a core size
large enough to accommodate both starting
material and product, and (ii) the proper ligand to
promote
monoarylation,
which
produced
encouraging activity with the model substrate,
further investigation of substrate substituent
effects was conducted. The catalytic micelle
showed excellent activity and selectivity with
both electron donating and withdrawing
substituents present on the iodobenzene partner at
the ortho-, meta-, and para-positions, as
presented below in Table 3.
support[24] incorporated
a
polar, hydrogen-
bonding amide backbone to increase the
concentration of polar substrates in the nonpolar
solvent, and we can extrapolate similar activity
trends within the polar, cross-linked micelle core.
The reduced freedom of movement for the
ligands within the micelle core is hypothesized to
create an active catalytic pocket, filled with
Table 3. Substrate scope of the Pd-catalyzed C(sp3)–H
potential
hydrogen-bonding
partners.
arylation using DML-5[a,b]
Hypothesized within the active pocket, the
coordinated palladium complex is sterically
encouraged to interact with the starting materials
and coupling partners. The substrates that
participate in hydrogen-bonding within the core,
such as 2a and 2e, have increased selectivity for
ortho-substituted aryl halides, presumably due to
hydrogen-bonding capability near the active
substitution, drawing the starting material toward
the Pd active site. These substitutions are
electronically favored at the ortho-/para-
positions because of the electron donating
behavior of the methoxy, as well as slight
electron withdrawing but ortho-/para- activation
for the fluoro-substituted starting material, such
that we speculate facilitation of reactivity near the
active site of substitution. Alternatively
hypothesized, the micelle core concentration is
high and the ortho- substitution encumber the
[a]
Reaction conditions: substrate (0.05 mmol) Pd(TFA)2
[palladium(II) trifluoroacetate] (0.01 mmol), DML-5 (10
mg), Ag2CO3 (0.075 mmol), TFA (0.01 mmol),
4
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
stacking of molecules more so compared to the
handles similar to the homogeneous reaction,
recycled micelle was explored for catalytic activity as
one way to enhance the total TON. The micelle-
support alone (without added ligand L), showed
activity, reaching 68% yield of monoarylated product,
which is expected due to the potential for Pd
coordination with the amide groups of the cross-
linked core. Next, the micelle with immobilized
ligand (DML-5) was run under standard reaction
conditions (Table 4, entry 3), and subsequently
recycled as seen in Table 4, entries 5 and 7. The
para-
substituted
aryl
iodides,
thus
accommodating the smaller space and increased
diarylated product. Similar activity is not
observed for 2b compounds, because the
carbonyl group can weakly coordinate to Pd(II),
which promotes the second C–H insertion to give
more diarylated product. Therefore, similar
selectivity trends are not seen with methyl ester
aryl iodides. Generally, stronger electron-
withdrawing functionality added to the substrate
decreased the yield slightly; however the
1
micelle catalyst was successfully reused from H
selectivity remains high, as seen in compound 2f
.
NMR (Figure S5) in its as-recovered form, as well as
with fresh palladium added, which yielded
dramatically different results. Recycled micelle with
no added palladium showed drastically reduced
activity, producing 11 % of product 2, while with
fresh Pd added it yielded 77% (Table 4, entries 4 and
5). This demonstrated that the supported ligand was
successfully recycled, albeit not robustly after
multiple runs (Table 4, entries 6 and 7). Elemental
analysis of the recycled micelle (Table S5) showed
residual palladium, and the UV/vis spectrum of used
DML-5 has characteristics of both the micelle and
palladium present[30] (Figure S1), but only at a 1.5
mol% loading, which explains its very low
productivity in its as-recovered form. Also from
elemental analysis (Table S5), there was a decrease in
nitrogen content over multiple cycles, which was
likely due to the displacement of the initial bromide
counter ions in the amide cross-linked core with free
iodide ions from excess aryl iodide in solution,
causing the micelle core to become more crowded
with larger counter ions present. The recycle of the
micelle demonstrates the ability to reuse the ligand,
without the metal, which is not unexpected with a
weakly coordinated monodentate ligand and fixed
micelle core. For entry 5 in Table 4, there is a notable
decrease of yield, giving similar performance to entry
1 in Table 4. A possible explanation for this
observation is the spatial constraints and limited
mobility of the ligand within the micelle core could
reduce the capability for bidentate coordination of Pd
with two ligands, thus forcing the Pd to coordinate
weakly with the amide cross-linkages, thereby
reducing the probability for metal recycle. Another
possible explanation is that the monodentate ligand
allows for coordination of other species in reaction
solution with the ligand, and as the reaction
progresses and starting materials are consumed, other
reactants take the place of the previously coordinated
starting material or metal.[41]
This tolerance for many functional handles on the
starting materials, paired with excellent yields,
has the potential to be exploited in the future with
C–H activation. Overall, this micelle-supported
palladium catalyst showed high tolerance for both
electron withdrawing and donating groups, as
well as selectivity toward monoarylated products
in all cases.[40]
Table 4. Recycling DML-5 in Pd-catalyzed C(sp3)–H
arylation [a,b,c]
Pd(TFA)2
(mol%)
Yield
(%)[b]
Selectivity
(%)[b]
Entry
Micelle
1
2
3
DM-5
DML-5
DML-5
20
0
20
68
N.R.[c]
93
>99
N.D.[d]
>99
Recycled
DML-5 from
entry 3
Recycled
DML-5 from
entry 3
Recycled
DML-5 from
entry 4
Recycled
DML-5 from
entry 5
4
5
6
0
20
0
11
77
>99
>99
N.D.
>99
N.R.
52
7
20
[a]
Reaction conditions: substrate (0.4 mmol) Pd(TFA)2
[palladium(II) trifluoroacetate] (0.08 mmol), DML-5 (80
mg), Ag2CO3 (0.6 mmol), TFA (0.08 mmol), 2-iodoanisole
(1.2 mmol), and cyclohexane (2.4 mL) were added. The
reaction vessel was sealed and the mixture was stirred at
o
room temperature for 10 min and then heated to 100 C for
20 h with vigorous stirring.
selectivity in brackets were determined by H NMR using
CH2Br2 as the internal standard. [c] NR = no reaction. [d] ND =
not determined.
[b]
The yield percentage and
Conclusions
1
The present work demonstrated a micelle-
supported ligand used for Pd-catalyzed C(sp3)–H
monoarylation. The micelle was designed and
synthesized with tunable properties that can be
further enhanced for future use with C–H
activation, as well as other reactions that benefit
Realizing the micelle-supported Pd has a high
compatibility and selectivity with multiple functional
5
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
analyzed by 1H NMR, and dried overnight for further
experiments.
from spatial constraints of a catalytic pocket.
Specifically, one can imagine creation of active
pockets with multiple functional sites operating
congruently. The micelle-supported ligand
imparted a selectivity unseen by previous
Acknowledgements
polymer-supported
Pd-catalyzed
C(sp3)–H
We would like to thank the NSF under the Center for selective C
– H functionalization (CCHF) (No. CHE-1205646) for funding of
this research. Special thanks given to Andrew Gorman, Paul
Balding, and Dr. Paul Russo for assistance with dynamic light
scattering of micellar supports.
arylation reactions, and was reused a second time.
Enhanced recyclability is expected using systems
that exploit multidentate ligands, reducing loss of
metal from the designed microenvironments.
References
Experimental Section
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8775-8806.
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surfactant A (10.3 mg, 0.012 mmol) and surfactant B (50.0
mg, 0.06 mmol) in heptane (3.0 mL) and CHCl3 (0.1 mL).
The mixture was hand shaken and sonicated at room
temperature to give an optically clear solution. After
addition of 2,2-Dimethoxy-2-phenylacetophenone ( 5
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(Scheme S4).
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0
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was washed by cold methanol to remove unreacted 4-
amino-2-methylpyridine. The final light brown powder
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General arylation procedure
Substrate (0.05 mmol), Pd(TFA)2 (0.01 mmol), ligand
(0.02 mmol), and Ag2CO3 (0.075 mmol) were weighed out
open to air and placed in a pressure tube (5 mL) with a
magnetic stir bar. The aryl iodide (0.15 mmol), TFA (0.01
mmol), and solvent (0.3 mL) were added. The reaction
vessel was sealed and the mixture was first stirred at room
temperature for 10 min and then heated to 100 °C for 20 h
with vigorous stirring. Upon completion, the reaction
mixture was cooled to room temperature. All yields were
determined by analysis of the crude 1H NMR (CDCl3)
spectrum using CH2Br2 as the internal standard after
filtration of the reaction mixture through a pad of silica gel.
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6
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
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7
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10.1002/adsc.201700707
Advanced Synthesis & Catalysis
FULL PAPER
Selective C(sp3)–H Monoarylation Catalyzed by a
Covalently Cross-linked Reverse Micelle-
Supported Pd Catalyst
Adv. Synth. Catal. Year, Volume, Page – Page
Caroline B. Hoyt, Li-Chen Lee, Jian He, Jin-Quan
Yu, Christopher W. Jones*
8
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