Synthesis of shape-persistent macrocycles by a one-pot suzuki-miyaura cross-coupling reaction

Article abstract of DOI:10.1002/chem.201002574

Ring creation: Shape-persistent macrocyclic structures were prepared by a one-pot catalyst-transfer Suzuki-Miyaura cross-coupling (CTSMCC) reaction (see figure). The reaction of 3,6-dibromo-substituted carbazoles and diboronic ester monomers afforded shap

Full text of DOI:10.1002/chem.201002574

DOI: 10.1002/chem.201002574
Synthesis of Shape-Persistent Macrocycles by a One-Pot Suzuki–Miyaura
Cross-Coupling Reaction
Weiguo Huang,[a] Ming Wang,[a] Chun Du,[a] Yulan Chen,[a] Ruiping Qin,[b] Linjie Su,[a]
Chi Zhang,[a] Zhengping Liu,[b] Cuihong Li,[b] and Zhishan Bo*[a, b]
Dedicated to Professor Jiacong Shen on the occasion of his 80th birthday
Shape-persistent macrocycles have attracted considerable
interest as molecular components in the fields of supra-
molecular chemistry and materials science due to their
unique molecular structures and properties.[1–2] These rigid
molecular rings with a nanoscale sized hole in the center
may be tailored with specific chemical constitutions, geomet-
rical shapes, peripheral functional groups, and so on. Recent
advances in the preparation, supramolecular self-assembling,
and practical applications of shape-persistent macrocycles
have verified this class of molecules as promising building
blocks for supramolecular chemistry and nanodevice fabri-
cation. Intense efforts have been devoted to the synthesis of
shape-persistent macrocycles, and they have been well sum-
marized in several excellent reviews.[3] The most successful
methods used in the synthesis of shape-persistent macrocy-
cles include the following approaches: 1) intramolecular ring
closure of a,w-difunctionalized oligomer strategy and the
one-pot intermolecular coupling and intramolecular cycliza-
tion method; 2) the template strategy; 3) thermodynamically
controlled synthetic strategies.[3] Based on these elegant syn-
thetic strategies, a large number of shape-persistent macro-
cycles with well-defined shapes and sizes have been pre-
pared and reported.[1]
Recently, Sherburn and Sinclair found that Suzuki–
Miyaura coupling of diiodoaryls and arylboronic acid in a
feed ratio of 10:1 afforded the product of double coupling in
good yields.[4] Hu and Dong demonstrated that the use of
[Pd2ACHTNUTRGNE(NUG dba)3] and tBu3P as the catalyst precursor for Suzuki–
Miyaura cross-coupling of dibromobenzenes with arylboron-
ic acid (1 equiv) afforded exclusively diaryl-substituted ben-
zenes.[5] Scherf et al. reported the cross-coupling of 2,7-di-
bromofluorene with arylboronic acid (1 equiv) formed pref-
erentially the diaryl-substituted fluorenes.[6] Yokozawa et al.
reported chain-growth Suzuki–Miyaura polymerization of
an AB-type monomer, bromoarylboronic acid, using
[PdBr{PACHTUNGTRNEUNG
(tBu)3}(Ph)] as an arylpalladium halide catalyst.[7]
Kiriy et al. have successfully grafted polyfluorene onto a
functionalized surface by catalyst-transfer chain-growth
Suzuki–Miyaura polycondensation of 7-bromo-9,9-bis(2-
ethyl-hexyl)-9H-fluoren-2-ylboric using [PdACTHUNTRGNE(UNG tBu3P)2] as the
catalyst precursor.[8] Very recently, Yokozawa et al. have
demonstrated that catalyst-transfer Suzuki–Miyaura poly-
condensation can be used to prepare even diblock conjugat-
ed polymers with a narrow molecular weight distribution.[9]
We have recently demonstrated that the catalyst-transfer
Suzuki–Miyaura cross-coupling (CTSMCC) reaction can be
used to prepare hyperbranched polymers with a branching
degree of 100%.[10] We think the unique catalyst-transfer be-
havior can be used to prepare shape-persistent macrocycles.
Herein, we report the application of the CTSMCC reaction
in the preparation of shape-persistent macrocycles. To the
best of our knowledge, this is the first example of the syn-
thesis of macrocycles by the CTSMCC reaction. Four mac-
rocycles were selected as targeted macrocycles to verify our
idea.
[a] W. Huang, M. Wang, C. Du, Dr. Y. Chen, L. Su, C. Zhang,
Prof. Dr. Z. Bo
Institute of Chemistry CAS
Beijing 100190 (P.R. China)
Fax : (+86)10-82618587
E-mail: zsbo@iccas.ac.cn
[b] Dr. R. Qin, Prof. Dr. Z. Liu, C. Li, Prof. Dr. Z. Bo
Institute of Polymer Chemistry and Physics
College of Chemistry, Beijing Normal University
Beijing 100875 (P.R. China)
Due to the competition of linear polymerization, a one-
pot reaction usually affords macrocycles in very low yield.
Therefore, the synthesis of shape-persistent macrocycles nor-
mally requires pseudo high dilution.[1h,11] The reactants are
usually added to the reaction vessel by a syringe pump over
Fax : (+86)10-62206891
E-mail: zsbo@bnu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201002574.
440
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Chem. Eur. J. 2011, 17, 440 – 444

COMMUNICATION
Table 1. Synthesis of macrocycle 1.[a]
several days.[3e,12] Schlꢁter et al. have first reported the syn-
theses of many kinds of phenylene-based shape-persistent
macrocycles by the Suzuki–Miyaura cross-coupling reac-
tion.[11] They have demonstrated that yields of cyclization
dropped from 68–85% for iodotelechelics to 18% for bro-
motelechelics for a one precursor route. For the two precur-
sor route, cyclization yields for iodotelechelics are in the
range of 30 to 50%, whereas for cyclization of bromotele-
chelics the yield is only around 13%.[10] Herein, we will
demonstrate that shape-persistent macrocycles and even
more complicated bimacrocycles can be easily synthesized
in relatively high yield in a one-pot reaction using two and
three precursor routes. One-pot technique has many clear
advantages over the pseudo high dilution one in many as-
pects, such as the ease of preparing macrocycles on a larger
scale, shorter reaction times, a simpler reaction setup. In ad-
dition, the synthesis of macrocycles by the one precursor
route is more time consuming than that of the two precursor
one.
Entry
Concentration
Catalyst
Pd0
[mmol%]
Yield
[%]
[mm]
precursor
ACHTUNGTRENNUNG
1
2
3
4
5
6
7
8
1.25
1.25
1.25
1.25
1.25
1.25
2.50
5.00
N
(dba)3]/P
R
0.5
1.0
2.0
5.0
10.0
2.0
55
56
56
65
67
16
54
37
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
R
N
5.0
5.0
T
[a] Reaction conditions: mixture of A2, B2, [Pd
AHCTUNGTRENNUNG
2ACHTUNGTREN(UNGN dba)3]·CHCl3, and P-
high-dilution technique.[3e,11] For a control experiment, the
use of a traditional catalyst precursor, [Pd(PPh3)4], for the
coupling reaction was also performed. The results are also
summarized in Table 1. Under the exact same conditions,
AHCTUNGTRENNUNG
the use of [PdACHTNUTRGNEUNG(PPh3)4] only afforded the desired macrocycle
As shown in Scheme 1, macrocycle 1 is synthesized by a
one-pot CTSMCC of two precursors. Coupling of 3,6-dibro-
mocarbazole A2 and diboronic pinacol ester monomer B2
1 in a yield of 16% (Table 1, entry 6). The GPC elution
curves of the crude products of macrocycle 1 synthesized by
using [Pd2ACHTUGNTREN(NNUG dba)3]/PACHTNUGTREN(GUNN tBu)3 or [PdACHTNUGTREN(UNGN PPh3)4] as catalyst precur-
sors are shown in Figure 1a. Clearly, for the catalyst-transfer
reaction the higher-molecular-weight side products are sig-
nificantly smaller than those of the normal Suzuki–Miyaura
reaction. The reason for the high yield cyclization of two
precursors to form macrocycle 1 is that when bulky PACHTUNGTRENNUNG(tBu)3
is used as a ligand, the palladium catalyst will transfer from
one bromide to another one through the carbazole unit and
the two coupling reactions will happen successively.[5–10] The
concentration of reactive species is determined by that of
the catalyst not the reactants. Therefore, for the synthesis of
macrocycles, the CTSMCC reaction is intrinsically of a
pseudo-high-dilution nature.
As shown in Scheme 2, the CTSMCC reaction was also
utilized for the synthesis of larger macrocycle 2. The synthe-
sis and characterization of precursor D2 are described in the
Supporting Information. The CTSMCC of diboronic esters
(D2) and 2,7-dibromo-9,9-dioctylfluoene (C2) with [Pd2-
Scheme 1. Synthesis of macrocycle 1 by catalyst-transfer Suzuki–Miyaura
coupling reaction.
was carried out in a biphasic mixture of THF and aqueous
NaHCO3 with [Pd
(dba)3] and P
E
N
ACHTUNGRTENUN(NG tBu)3 as catalyst precursors afforded macrocy-
The catalyst Pd0 loads varied from 0.5 to 10 mol%. The re-
action mixture was stirred at reflux under a nitrogen atmos-
phere for 5 days. Macrocycle 1 can be easily purified by
chromatography on a silica gel column or by preparative gel
permeation chromatography (GPC). The structure of carba-
zole-containing macrocycle 1 is characterized unambiguous-
AHCTUNGTRENNUNG
tion afforded macrocycle 2 in a yield of 9%. The yield of
macrocycle 2 cannot be estimated by the GPC elution
curves of the crude product, since the macrocycle and some
linear oligomers eluted simultaneously. Nevertheless, pure
macrocycle 2 can be obtained by silica gel column chroma-
tography. Macrocycle 2 is fully characterized by 1H and
13C NMR spectroscopy and MALDI-TOF mass spectrosco-
py.
It is also possible to synthesize more complicated shape-
persistent macrocyclic structures by using the CTSMCC re-
action. As a demonstration of its potential use, we have suc-
cessfully prepared dodecylene spacer linked bimacrocycle 3
and spiro-bridged bimacrocycles 4 using the CTSMCC reac-
tion, as shown in Scheme 3. The synthesis of bimacrocycles
3 and 4 involves three precursors, that is, four coupling reac-
1
ly by H and 13C NMR spectroscopy, element analysis, and
MALDI-TOF mass spectroscopy. The coupling reaction con-
ditions were screened by varying the amount of catalyst and
the concentration of monomers. The crude coupling prod-
ucts were characterized by GPC analysis to estimate the
yields of macrocycle 1. The concentrations of monomers, the
amounts of catalyst, and the yields of macrocycle 1 are
listed in Table 1. Under the conditions tested, the yields of
macrocycle 1 by the one-pot CTSMCC reaction are in the
range of 37 to 67%. The yields are comparable with the syn-
thesis of macrocycles from a one precursor route using the
Chem. Eur. J. 2011, 17, 440 – 444
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www.chemeurj.org
441

Z. Bo et al.
Scheme 2. Synthesis of macrocycle 2 by catalyst-transfer Suzuki–Miyaura
coupling reaction.
led to no desired product being separated. The structures of
bimacrocycles 3 and 4 were also confirmed by MALDI-TOF
mass spectroscopy, as shown in Figure 2, and 1H and
13C NMR spectroscopy. The molecular ion of bimacrocycle 3
is at m/z 1216.7 (calcd: 1216.7). The MALDI-TOF mass
spectrum of bimacrocycle 4 has two signals at m/z 2516.0
(calcd: 2515.6 [M+]) and 2539.1 (calcd: 2538.6 [M++Na]).
In conclusion, shape-persistent macrocyclic structures
were successfully synthesized in yields of 21 to 67% by a
one-pot CTSMCC reaction. The reaction was carried out
with [Pd
(tBu)3 as the bulky ligand. In comparison, the control ex-
periment using traditional conditions with [Pd(PPh3)4] as the
catalyst precursor only afforded the desired macrocycles in
yields of about 0 to 16%. Our results have clearly demon-
strated that the CTSMCC reaction can be a very useful
method for the synthesis of shape-persistent macrocycles,
the synthetic routes of which are usually tedious.
2ACHTUNGTRENUN(NG dba)3] as the zero-valent palladium source and P-
AHCTUNGTRENNUNG
Figure 1. a) The GPC curves of crude product of macrocycle 1 catalyzed
by 1.0% [Pd2A(dba)3]+4.0% P(tBu)3 (c) and 2.0% [Pd(PPh3)4] (a).
b) The GPC curves of crude product of macrocycle 3 catalyzed by 1.0%
[Pd2A(dba)3]+4.0% (tBu)3 (c) and 2.0% [Pd(PPh3)4] (a). The
AHCTUNGTRENNUNG
G
U
ACHTUNGTRENNUNG
G
P
E
ACHTUNGTRENNUNG
sharp peaks marked with arrows represent target macrocycles.
tions. The reaction of diboronic ester B2 and tetrabromide
A4 under the CTSMCC reaction conditions using [Pd2-
A
ACHTUNGTRENNUNG(tBu)3 as catalyst precursors afforded bimacrocycle
AHCTUNGTRENNUNG
Experimental Section
precursor only afforded a trace amount of 3, which cannot
be separated. The GPC elution curves of crude macrocycle
3 synthesized by using [Pd2ACTHUNGTREN(UNNG dba)3]/PACHTNURGTEG(NNNU tBu)3 and [PACTHUNGTRENN(NGU PPh3)4] as
General procedure for four macrocycles: Arylbromide and arylboronic
ester were carefully dissolved in neat THF, then water and NaHCO3
were added to the solution. After carefully degassing the mixture, [Pd2-
catalyst precursors are shown in Figure 1b. It is noticeable
that the formation of undesired oligomer side products is
markedly suppressed under the CTSMCC reaction condi-
tions. Similarly, three-dimensional spiro-bridged shape-per-
sistent bimacrocycle 4 was also prepared by the CTSMCC
reaction. The coupling of tetraboronic ester D4 and dibro-
mide C2 under similar conditions afforded the desired spiro-
bridged bimacrocycle 4 in a yield of 21%, which was puri-
fied by preparative TLC on silica gel plates. For the control
AHCUTNGERTN(GNUN dba)3]·CHCl3 and PACHTUNREGTGN(NNU tBu)3 or [PdCATHNUGTREN(NNGU PPh3)4] were added. The mixture was
stirred and heated at reflux under nitrogen for five days. After cooling,
water was added, the mixture was extracted with CH2Cl2 (ꢂ3), and the
combined organic layers were dried over anhydrous Na2SO4 and evapo-
rated to dryness. The residue was purified by preparative GPC and then
silica gel column chromatography; for macrocycle 4, it was purified by
preparative TLC.
GPC analysis: After the reactions were cooled, a 1.0 mL aliquot of the
reaction mixture was dried over anhydrous Na2SO4 and filtered through
a membrane (polytetrafluoroethylene (PTFE), 0.2 mm pore size), then
the samples were subject to GPC analysis using THF as an eluent. All of
experiment, the use of [PdACHTNUGTRNEUG(N PPh3)4] as the catalyst precursor
442
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Chem. Eur. J. 2011, 17, 440 – 444

Synthesis of Shape-Persistent Macrocycles
COMMUNICATION
3H); 13C NMR (100 MHz, CDCl3): d=
142.0, 141.6, 141.5, 140.1, 139.8, 138.8,
138.7, 133.1, 127.5, 127.2, 126.0, 125.1,
124.6, 124.1, 123.7, 122.3, 122.1, 109.5,
43.9, 31.6, 29.3, 27.0, 22.6, 22.0, 21.8,
14.0; MALDI-TOF MS: m/z: 609.6
[M+]; HRMS (ESI+): m/z: calcd for
C46H43N: 609.33955; found: 609.33854;
elemental analysis calcd (%) for
C46H43N:
C 90.60, H 7.11, N 2.30;
Found: C 90.24, H 7.15, N 2.41.
Synthesis and characterization of mac-
rocycle 2: A mixture of D2 (146.3 mg,
0.1 mmol),
9H-fluorene
2,7-dibromo-9,9-dioctyl-
(54.8 mg, 0.1 mmol),
NaHCO3 (1.0 g, 0.012 mol), H2O
(10 mL), and THF (100 mL) was care-
fully degassed before [Pd
(2.3 mg, 2 mmol) or [Pd2A(dba)3]·CHCl3
(1.0 mg, 1 mmol) and P(tBu)3 (0.81 mg,
ACHTUNGTRENNUNG(PPh3)4]
CTHUNGTRENNUNG
AHCTUNGTRENNUNG
4 mmol) was added. The mixture was
stirred and heated at reflux for 5 days
under nitrogen. Water and CH2Cl2
were added and then the organic layer
was separated, dried over Na2SO4, and
evaporated to dryness. The residue
was first purified by preparative GPC
and then by column chromatography
on silica gel using hexane/CH2Cl2 (5:2,
v/v) as the eluent to afford macrocycle
2
N
as
(dba)3]·CHCl3 and
67.1 mg, 42%; for [PdAHCTUNGTRENNUNG
a
colorless solid (for [Pd2-
(tBu)3, yield:
(PPh3)4], yield:
PACHTUNGTRENNUNG
14.4 mg, 9%). 1H NMR (400 MHz,
CDCl3): d=7.84–7.74 (m, 10H), 7.68–
7.60 (m, 8H), 7.53 (s, 2H), 7.23–7.16
(m, 12H), 4.20–4.06 (m, 12H), 2.12 (t,
J=6.0 Hz, 4H), 1.98–1.76 (m, 12H),
1.63–1.46 (m, 12H), 1.46–1.32 (m,
24H), 1.29–1.18 (m, 4H), 1.08–0.82
(m, 38H), 0.62 ppm (t, J=5.7 Hz,
6H); 13C NMR (100 MHz, CDCl3): d=
160.1, 160.0, 159.9, 151.5, 143.8, 143.2,
143.0, 142.4, 142.1, 140.3, 140.2, 140.1,
139.8, 127.6, 127.5, 127.4, 126.9, 121.4,
120.1, 119.4, 118.7, 118.6, 113.0, 112.7,
112.5, 112.1, 111.9, 111.7, 68.4, 68.3,
68.2, 55.8, 40.5, 31.7, 31.6, 30.0, 29.4,
29.1, 25.8, 25.6, 23.9, 22.6, 22.5, 14.1,
13.9, 1.0 ppm; MALDI-TOF MS: m/z:
1598.2 [M+]; elemental analysis calcd
(%) for C113H144O6: C 84.91, H 9.08;
found: C 84.93, H 8.91.
Scheme 3. Synthesis of bimacrocycles 3 and 4.
the GPC measurements were carried out under conditions as identical as
possible.
Synthesis and characterization of bimacrocycle 3:
A mixture of B2
(92.1 mg, 0.15 mmol), compound A4 (61.2 mg, 0.075 mmol), NaHCO3
(1.0 g, 0.012 mol), H2O (10 mL), and THF (120 mL) was carefully de-
Synthesis and characterization of macrocycle 1:
(92.1 mg, 0.15 mmol), 3,6-dibromo-9-hexyl-9H-carbazole (61.4 mg,
0.15 mmol), NaHCO3 (1.0 g, 0.012 mol), H2O (10 mL), and THF
A mixture of B2
gassed before [Pd
CAHUTNGTRENNU(G PPh3)4] (3.5 mg, 3 mmol) or [Pd2AHCTUNGTRNE(NUGN dba)3]·CHCl3 (1.5 mg,
1.5 mmol) and P(tBu)3 (1.22 mg, 6 mmol) was added. The mixture was
AHCTUNGTRENNUNG
(120 mL) was carefully degassed before [Pd
CAHUTGTNERN(NGU PPh3)4] or [Pd2ACHTUGNTERN(NUGN dba)3]·CHCl3
stirred and heated at reflux for 5 days under nitrogen. Water and CH2Cl2
were added and then the organic layer was separated, dried over Na2SO4,
and evaporated to dryness. The residue was first purified by preparative
GPC and then by column chromatography on silica gel using hexane/
CH2Cl2 (5:2, v/v) as the eluent to afford macrocycle 3 as a colorless solid
and P(tBu)3 was added. The mixture was stirred and heated at reflux for
ACHTUNGTRENNUNG
5 days under nitrogen. Water and CH2Cl2 were added and then the or-
ganic layer was separated, dried over Na2SO4, and evaporated to dryness.
The residue was purified by column chromatography on silica gel using
hexane/CH2Cl2 (5:2, v/v) as the eluent to afford macrocycle 1 as a color-
(for [Pd2ACHTUNGTNER(NUNG dba)3]·CHCl3 and PACHTNUTREGGNN(UN tBu)3, yield: 36.5 mg, 40%; for [PdACHTUNGTRENNUNG(PPh3)4],
1
less solid (for Pd2ACHTUNGTRENNUNG(dba)3 and PACHTNURTEGG(NNUN tBu)3, yield: 61 mg, 67%; for PdACHTUNGTREN(NNGU PPh3)4,
yield: 4.5 mg, 5%). H NMR (400 MHz, CDCl3): d=8.76 (s, 4H), 8.15 (s,
4H), 8.07 (s, 4H), 7.67 (d, J=8.3 Hz, 4H), 7.60 (s, 8H), 7.56 (s, 4H), 7.51
(s, 4H), 7.37 (d, J=8.4 Hz, 4H), 4.24 (t, J=6.9 Hz, 4H), 2.55 (s, 12H),
2.51 (s, 12H), 1.92 (m, 4H), 1.35 (brs, 12H), 0.86 ppm (t, J=4.3 Hz, 4H);
13C NMR (100 MHz, CDCl3): d=142.0, 141.6, 141.5, 140.1, 139.7, 138.8,
1
yield: 15 mg, 16%). H NMR (400 MHz, CDCl3): d=8.79 (s, 2H), 8.17 (s,
2H), 8.09 (s, 2H), 7.69 (d, J=8.2 Hz, 2H), 7.62 (s, 4H), 7.58 (s, 2H), 7.52
(s, 2H), 7.39 (d, J=8.3 Hz, 2H), 4.26 (t, J=7.1 Hz, 2H), 2.57 (s, 6H),
2.53 (s, 6H), 1.97–1.93 (m, 2H), 1.35 (brs, 6H), 0.89 ppm (t, J=6.9 Hz,
Chem. Eur. J. 2011, 17, 440 – 444
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443

Z. Bo et al.
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Synthesis and characterization of spiro-bridged bimacrocycle 4: A mix-
ture of D4 (224.6 mg, 0.1 mmol), 2,7-dibromo-9,9-dioctyl-9H-fluorene
(109.6 mg, 0.2 mmol), NaHCO3 (1.0 g, 0.012 mol), H2O (10 mL), and
´
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4 mmol) or [Pd2A(dba)3]·CHCl3 (2.0 mg, 2 mmol) and PCAHTUNGRTENNUGN
G
8 mmol) was added. The mixture was stirred and heated at reflux for
5 days under nitrogen. Water and CH2Cl2 were added and then the or-
ganic layer was separated, dried over Na2SO4, and evaporated to dryness.
The residue was purified by preparative TLC using hexane/CH2Cl2 (5:2,
v/v) as the eluent to afford macrocycle 4 as a colorless solid (for [Pd2-
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4H), 7.82 (d, J=8.1 Hz, 4H), 7.72 (d, J=7.8 Hz, 4H), 7.60–7.52 (m,
20H), 7.48 (s, 4H), 7.25 (s, 4H), 7.17 (m, 8H), 7.14 (s, 4H), 6.98 (s, 4H),
4.04 (t, J=6.4 Hz, 8H), 2.53 (s, 12H), 2.33 (s, 12H), 1.94 (t, J=6.0 Hz,
8H), 1.79 (m, 8H), 1.46 (m, 8H), 1.36–1.26 (m, 24H), 0.89–0.55 ppm (m,
64H); 13C NMR (100 MHz, CDCl3): d=159.7, 152.0, 149.8, 144.2, 142.5,
142.2, 142.1, 141.0, 140.9, 140.5, 140.3, 140.2, 139.9, 138.9, 138.3, 127.6,
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119.3, 112.8, 112.0, 68.2, 54.8, 40.3, 31.6, 31.4, 29.8, 29.7, 29.3, 28.8, 28.7,
25.7, 23.7, 22.6, 22.4, 21.8, 21.4, 14.0, 13.9 ppm; MALDI-TOF MS: m/z:
2516.0 [M+].
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Acknowledgements
Financial support by the NSF of China (20834006 and 20774099) and the
National Basic Research Program of China (2009CB623601) is gratefully
acknowledged. We thank Professors A. D. Schlꢁter, A. Kiriy, and Zhao-
hui Wang for helpful discussions.
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Keywords: cross-coupling
·
homogeneous catalysis
·
Received: September 5, 2010
macrocycles · palladium · Suzuki–Miyaura coupling
Published online: November 29, 2010
444
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