Conjugated Microporous Polymer as Heterogeneous Ligand for Highly Selective Oxidative Heck Reaction

Article abstract of DOI:10.1021/jacs.7b00643

A series of pyridine-type ligands containing C C bonds were designed and synthesized for selective oxidative Heck reaction. These ligands were utilized as functional units and integrated into the skeleton of conjugated microporous polymers. 6,6′-diiodo-2,2′-bipyridine and 1,3,5-triethynylbenzene were polycondensed via Sonogashira cross-coupling strategy to afford CMP-1 material. The resultant CMP-1 was used as a heterogeneous catalytic ligand for the Pd^II-catalyzed oxidative Heck reaction with high linear selectivity. The linear selectivity of CMP-1 is about 30 times higher than that of bipyridine-based monomer ligand. This work opens a new front of using CMP as an intriguing platform for developing highly efficient catalysts in controlling the regioselectivity in organic reactions.

Full text of DOI:10.1021/jacs.7b00643

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Communication
Conjugated Microporous Polymer as Heterogeneous
Ligand for Highly Selective Oxidative Heck Reaction
Yun-Bing Zhou, Yu-Qing Wang, Li-Chao Ning, Zong-Cang Ding, Wen-Long Wang,
Cheng-Ke Ding, Ren-Hao Li, Jun-Jia Chen, Xin Lu, Yun-Jie Ding, and Zhuang-Ping Zhan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b00643 • Publication Date (Web): 03 Mar 2017
Downloaded from http://pubs.acs.org on March 3, 2017
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Yun-Bing Zhou, a † Yu-Qing Wang, b † Li-Chao Ning, a Zong-Cang Ding, a Wen-Long Wang,b Cheng-
Ke Ding, a Ren-Hao Li, a Jun-Jia Chen, a Xin Lu, a Yun-Jie Ding,*b and Zhuang-Ping Zhan*a
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aDepartment of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and
Chemical Engineering, Xiamen University, Xiamen 361005, China
bDalian National Laboratory for Clean Energy, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian
Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023, China
†
Authors contributed equally to this work
Supporting Information Placeholder
Scheme 1. Two different products of Heck reaction
ABSTRACT: A series of pyridine-type ligands containing C≡C
bonds were designed and synthesized for selective oxidative Heck
reaction. These ligands were utilized as functional units and
integrated into the skeleton of conjugated microporous polymers.
6,6'-diiodo-2,2'-bipyridine and 1,3,5-triethynylbenzene were
polycondensed via Sonogashira cross-coupling strategy to afford
CMP-1 material. The resultant CMP-1 was used as a heterogeneous
catalytic ligand for the PdII-catalyzed oxidative Heck reaction with
high linear selectivity. The linear selectivity of CMP-1 is about 30
times higher than that of bipyridine-based monomer ligand. This
work opens a new front of using CMP as an intriguing platform for
developing highly efficient catalysts in controlling the
regioselectivity in organic reactions.
The Heck-Mizoroki reaction is one of the most powerful
transformations for the construction of C–C bonds.1 A key issue
remains to be solved is to control the position where aryl groups
insert into olefins. For electronically biased olefins such as styrene,
vinyl ethers and acrylates, high regioselectivity can be achieved
easily. Typically, electron-rich alkenes favor coupling at the
internal site to deliver the branched products,2 while electron-poor
alkenes favor coupling at the terminal site to give the linear
products (Scheme 1).3 However, the development of regioselective
Heck reactions using electronically unbiased alkenes, especially for
aliphatic olefins, as substrates in a catalytic manner is a formidable
challenge.4 In the past few years, several groups have focused on
homogeneous catalyst-controlled highly selective oxidative Heck
reaction of electronically unbiased alkenes. For example, Sigman
and co-workers demonstrated that high linear-selectivity could be
achieved by submitting electronically unbiased alkene substrates to
a catalytic system incorporating a carbene ligand (Figure 1, L1).5
Stahl’s group also demonstrated high regioselectivity in oxidative
Heck synthesis of branched conjugated dienes, using the catalyst
derived from palladium and phenanthroline-type ligand (Figure 1,
L2).6 Meanwhile, the homogeneous catalyst-controlled selective
Heck reaction of electronically unbiased alkenes have been made
some progress. With bulky bisphosphine ligands (Figure 1, L3),
Zhou and co-workers developed Pd0-catalyzed branched-selective
Heck reaction of electronically unbiased alkenes.7 Furthermore,
Jamison and co-workers reported Heck-coupling reactions between
Figure 1. Ligands for selective Heck reaction.
benzyl chlorides and electronically unbiased alkenes using
[Ni(cod)2] and PCy2Ph (Figure 1, L4),8 providing a regioselective
access to branched alkene products. Subsequently, Jamison
expanded the Ni0-catalyzed regioselective Heck-type reaction to
include widely used aryl electrophiles as substrates by using a
bidentate phosphine ligand (Figure 1, L5).9 In all of these
approaches, the ligands play a crucial role in controlling the
regioselectivity for the Heck reaction. Nevertheless, to the best of
our knowledge, there have been no reports of heterogeneous ligand
capable of promoting selective Heck reactions of electronically
unbiased alkenes.
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Over the past decade, conjugated microporous polymers (CMPs)
Table 1. Impact of different ligands on selective oxidative
Hecka
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with extended π-conjugation have attracted much attention as an
important porous organic material platform. Various microporous
CMPs with high surface areas have been synthesized via proper
selection of cross-linking strategies and building blocks. Compared
with materials such as covalent organic frameworks (COFs) and
metal-organic frameworks (MOFs), the CMPs usually have good
thermal and chemical stability. Remarkably, CMPs possess
crosslinked 3D molecular skeletons which can be finely tuned in
many aspects such as specific surface areas and pore size
distributions. Therefore, CMP materials have been applied in many
areas such as energy storage,10 gas adsorption,11 sensing,12 light
emitting13 and light harvesting.14 More importantly, CMPs can
serve as an intriguing platform for incorporating homogeneous
catalytic sites into heterogeneous polymeric systems.15 For
example, an iron(III) porphyrin-based CMP (FeP-CMP) showed
excellent catalytic activity for the oxidation of thiols15b and the
epoxidation of olefins under mild conditions.15g A cyclometalated
Ir(III) complex-contained CMP was found to be highly active for
reductive amination reaction.15c However, CMP catalysts have not
been used for regioselective reactions. We speculated that the rigid
porous structures of CMPs might have a positive effect on
controlling the regioselectivity of organic reactions. Herein, a new
type of organic conjugated microporous polymer (Figure 1, CMP-
1) used as ligand for heterogeneous catalysis was designed and
synthesized, which shows high selectivity for the PdII-catalyzed
linear-selective oxidative Heck reaction.
In order to design rational framework of CMP for selective
oxidative Heck reaction, proper functional units should be firstly
selected. Over the past decades, various bidentate nitrogen ligands
in complex with palladium have been successfully applied to the
Heck coupling reactions.16 On the other hand, several groups have
demonstrated that a PdII center could coordinate with the N atom
and the C≡C bond simultaneously.17 Bearing these knowledge in
mind, several pyridine-type ligands containing C≡C bonds (Figure
2, L6-L10) were designed and employed in selective oxidative
Heck reaction.
In our initial screening experiments, the efficiency of different
nitrogen ligands in promoting the coupling of phenylboronic ester
and 1-octene was investigated (Table 1). To our delight, the
pyridine-type ligands containing acetylene bond (L6-L9) showed
good yields, ln/br selectivities and moderate regioisomeric ratios
(Table 1, entries 1-4). A decrease in ln/br selectivity was observed
with the pyridine-type ligand L10 in which the C≡C bonds are too
far from the N sites to coordinate to the palladium center (Table 1,
entry 5). For comparison, we then screened commercially available
nitrogen ligands. Both bipyridine and phenanthroline led to very
low regioisomeric ratio of the desired product despite high
conversions (Table 1, entries 6-7). These results were similar to
those in the absence of a ligand (Table 1, entry 8). Based on above
results, we selected L9 (a bifunctional ligand consists of C≡C and
pyridine-N sites with proper coordination geometric angle) as a
functional unit and further integrated into the skeleton of CMP to
serve as a heterogeneous catalytic ligand.
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aReaction conditions: 1-octene (0.4 mmol), phenylboronic ester (1.2 mmol),
Pd(OAc)2 (6 mol%), Cu(OTf)2 (20 mol%), L6-L15 (20 mol%), CMP-1,
CMP-2 CMP-3 or POL-1 (35 mg), DMA (4 mL), 40 oC, O2 (1 atm), 48 h.
bIsolated yield. cDetermined by 1H NMR spectroscopy. dRatio of
linear/other isomers, as determined by GC analysis.
Figure 2. Ligands designed or selected for selective Heck reaction.
alkene in 76% yield，excellent ln/br selectivity of 70:1 and high
regioisomeric ratio of 30:1 (Table 1, entry 9). These impressive
experimental results indicated these porous polymer, such as CMP-
1 and CMP-3, outperformed the monomeric pyridine-type ligands
L6 and L10 in controlling the regioselectivity (Table 1, entry 9 vs
entry 1, entry 11 vs entry 5), which can be largely attributed to the
confinement effect of the porous structure of CMP materials.
Scheme 2. Synthesis of porous polymers
CMP-1 was synthesized by Sonogashira coupling of 6,6'-diiodo-
2,2'-bipyridine and 1,3,5-triethynylbenzene in the presence of
PdCl2(PPh3)2 and CuI (Scheme 2, Eq.1). For comparison, other
bipyridine-containing polymers CMP-2, CMP-3, CMP-4 and POL-
1 were also synthesized (Scheme 2, Eq.2-5). In the presence of
CMP-2 or POL-1, good or moderate yield and low regioisomeric
ratios were obtained (Table 1, entries 10 and 13). Compared with
L10 monomer, polymer CMP-3 provided some improvement in
regioisomeric ratios(Table 1, entry 11 vs entry 5). Excitedly, the
use of CMP-1 as a heterogeneous ligand furnished the desired
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Table 2. Substrate scope of oxidative Hecka
To explore the structure-activity relationship, CMP-1 and related
prepared Pd(OAc)2/CMP-1 were characterized by
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thermogravimetry (TG), N2 adsorption-desorption analysis,
scanning electron micrograph (SEM), transmissiron electron
micrograph (TEM) and X-ray photoelectron spectroscopy (XPS).
The TG shows that CMP-1 remains intact at temperatures up to
400oC, even with only about 15% weight loss at 800 oC, indicating
its good thermal stability (see the Supporting Information, Figure
S1). Nitrogen adsorption-desorption analysis (Figure S2a)
demonstrates that CMP-1 possesses hierarchical porosity, which is
further confirmed by SEM (Figure 3A) and TEM images (Figure
S5). The BET surface areas and total pore volumes of CMP-1 are
up to 415 m2/g and 0.71 cm3/g respectively. The pore sizes of CMP-
1 are mainly distributed between 1-4 nm which was calculated from
the method of non-local density functional theory (NLDFT),
indicating that the hierarchical porous CMP-1 mainly consists of
micropores and mesopores. We suggest that the confinement effect
of these porous space plays an important role in controlling the
regioselectivity for the Heck reaction. No obvious change in the
pore size distribution emerged between CMP-1 and
Pd(OAc)2/CMP-1 (Figure 3B). Despite the slight decrease in
specific surface area, Pd(OAc)2/CMP-1 is still significantly
microporous (Table S2). Furthermore, XPS confirmed the
coordination of palladium with pyridyl nitrogen (Figure S3 ).
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Figure 3. A) SEM of CMP-1. B) Pore size distribution curves.
The catalytic efficiency of the Pd(OAc)2/CMP-1 system was
evaluated using a variety of electronically unbiased alkenes and
arylboronic esters (Table 2). This oxidative Heck reaction
favorsformation of the (E)-linear product and was proved to be
tolerant of various functional groups. For example, the olefins
bearing a ketone (Table 2，entry 6), an ester (Table 2，entry 7) or
a silyl ether (Table 2，entry 13) all proceed with good yields and
excellent regio- and E:Z stereoselectivities. Moreover, the catalyst
Pd(OAc)2/CMP-1 promoted the cross-coupling of a doubly
protected allylic amine with a broad range of arylboronic esters to
afford the linear products with excellent yields and selectivity
(Table 2，entries 1-5). It should be pointed out that good yield and
excellent selectivity were observed for an allyl ester, a type of
substrate which is prone to undergo oxidative addition in the
presence of a palladium catalyst (Table 2，entry 8).18 Substrates
containing an acetyl or TBS-protected homoallylic alcohol also
afforded high selectivities and moderate yields with a range of
arylboronic esters (Table 2 ， entries 9-11). Alkenyl epoxides
usually suffered from nucleophilic attack by organoboron
compounds.19 However, the alkene containing a oxirane group was
a suitable substrate for the oxidative Heck reaction in the presence
of Pd(OAc)2/CMP-1, delivering the desired product with good
yield and selectivity (Table 2，entry 12).
aReaction conditions: olefins (0.4 mmol), arylboronic esters (1.2 mmol),
Pd(OAc)2 (6 mol%), Cu(OTf)2 (20 mol%), CMP-1 (35 mg), DMA (4 mL),
40 oC, O2 (1 atm), 48 h. The selectivity (r.r.) for desired product was 10:1.
bIsolated yield. cRecovered starting material. dDetermined by 1H NMR
spectroscopy.
branched-selective Heck reactions of aliphatic olefins have been
made much progress in recent years.6-9 However, less attention has
been paid to linear-selective Heck reactions of aliphatic olefins.
Several methods were developed for Heck-type reactions that
delivered only a maximum selectivity of 10:1 for (E)-linear product
using aliphatic olefin substrate.5,20 Of note, in the presence of CMP-
1, aliphatic olefins were converted smoothly to the (E)-linear
products in good yields with excellent ln/br selectivity (>25:1 ratio
in most cases) (Table 2, entries 15-24), which provided strong
evidence that the selectivity obtained is catalyst-controlled rather
than chelate-controlled.20a
In order to know more mechanistic study about the selectivity in
homogeneous system, DFT calculations have been performed to
explore the pathways of 1-octene inserting into a PdII-phenyl
species chelated by L8 (Figure S8). The coordination of 1-octene
Owing to the lack of chelation and inductive effects, the
heteroatom-free substrates such as aliphatic olefins are usually
challenging substrates for selective Heck reaction. Highly
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to PdII gives rise to two lowest-energy isomers Ipro-R and Ipro-S. They
are followed by the two most favorable alkene insertion transition
states TSlinear(pro-R) and TSbranched(pro-S) that lead correspondingly to
the linear and branched products. Note that TSlinear(pro-R) is lower
than TSbranched(pro-S) by 4 kcal/mol in free energy. Thus, formation
of linear regioisomer is much more preferable than that of branched
isomer both kinetically and thermodynamically, in sharp contrast
to the reversed regioselectivity in the neocuproine-ligated PdII-
catalyzed Heck reaction.6 The heterogeneous system is more
complex, and further study is underway to uncover the detailed
mechanism of the excellent selectivity in heterogeneous system.
In conclusion, we have developed a highly linear-selective
oxidative Heck reaction of simple olefins by employing CMP
materials as a ligand. Because of the beneficial confinement effect
of the porous structure in CMP materials and the bifunctional
ligand feature (consists of C≡C and pyridine-N sites with proper
coordination geometric angle), this heterogeneous ligand displayed
very high selectivity toward a broad range of electronically
unbiased alkenes. The linear selectivity of CMP-1 is about 30 times
higher than that of bipyridine-based monomer ligand. This work
opens a new front of using CMP as an intriguing platform for
developing highly efficient catalysts in controlling the
regioselectivity of organic reactions.
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zpzhan@xmu.edu.cn
dyj@dicp.ac.cn
The authors declare no competing financial interests.
Financial support from National Natural Science Foundation of
China (Nos. 21272190 and 91545105), the Strategic priority
research program of the Chinese Academy of Sciences, Grant No
XDB17020400 and NFFTBS (No. J1310024).
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60
5
ACS Paragon Plus Environment