Metalation of a thiocatechol-functionalized Zr(IV)-based metal-organic framework for selective C-H functionalization

Article abstract of DOI:10.1021/ja5126885

The incorporation of 2,3-dimercaptoterephthalate (thiocatecholate, tcat) into a highly robust UiO-type metal-organic framework (MOF) has been achieved via postsynthetic exchange (PSE). The anionic, electron-donating thiocatecholato motif provides an excel

Full text of DOI:10.1021/ja5126885

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Communication
Metalation of a Thiocatechol-Functionalized Zr(IV)-based
Metal-Organic Framework for Selective C-H Functionalization
Honghan Fei, and Seth M. Cohen
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 01 Feb 2015
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Journal of the American Chemical Society
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Metalation of a Thiocatechol-Functionalized Zr(IV)-based Met-
al-Organic Framework for Selective C-H Functionalization
Honghan Fei, and Seth M. Cohen*
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Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, 92093, United
States
Supporting Information Placeholder
bridged by linear 1,4ꢀbenzene dicarboxylate (bdc) ligꢀ
ands. UiOꢀ66 has been extensively studied for gas abꢀ
ABSTRACT:
The
incorporation
of
2,3ꢀ
dimercaptoterephthalate (thiocatecholate, tcat) into a
highly robust UiOꢀtype metalꢀorganic framework
(MOF) has been achieved via postsynthetic exchange
(PSE). The anionic, electronꢀdonating thiocatecholato
motif provides an excellent platform to obtain siteꢀ
isolated and coordinatively unsaturated soft metal
sites in a robust MOF architecture. Metalation of the
thiocatechol group with palladium affords unpreceꢀ
dented Pdꢀmono(thiocatecholato) moieties within theꢀ
se MOFs. Importantly, Pdꢀmetalated MOFs are effiꢀ
cient, heterogeneous, and recycable catalysts for regiꢀ
7
8
9
sorption, catalysis, photochemical reactions, and merꢀ
1
0
cury sequestration.
Catechol, a widely studied chelator in coordination
chemistry, has been successfully introduced into a UiOꢀ
8
b
66 topology. Subsequent metalation with highꢀvalent,
firstꢀrow transition metals affords metalꢀ
mono(catecholato) species that act as reusable alcohol
oxidation catalysis. Herein, the hard Lewis base phenol
groups of the catechol were replaced with thiophenols,
thereby presenting a soft thiocatechol metalꢀchelating
motif in a highly robust MOF. Although relatively unꢀ
2
oselective functionalization of sp CꢀH bond. This
material is a rare example of chelationꢀassisted CꢀH
functionalization performed by a MOF catalyst.
11
explored in the literature, the thiocatechol group
should be an excellent ligand for 2nd and 3rdꢀrow transiꢀ
tion metals, giving rise to isolated metalꢀ
mono(thiocatecholato) sites. Additionally, the dianionic,
bidentate thiocatecholato ligands should tightly bind and
stabilize active metal sites; thus, generating a stable, but
highly unsaturated metal site suitable for catalysis.
Metalꢀorganic frameworks (MOFs) are a class of miꢀ
croporous crystalline materials gathering increasing atꢀ
tention due to their tunable functionality and high surꢀ
face area, thus applications in gas storage, separation,
The regioꢀ and chemoselective functionalization of arꢀ
omatic carbonꢀhydrogen bonds is of tremendous value
for the synthesis of natural products and medicinal comꢀ
1
molecular sensing, catalysis, and drug delivery. Imꢀ
1
2
portantly, MOFs provide a versatile platform to achieve
accessible and coordinatively unsaturated metal sites,
and metalation of these free openꢀmetal sites give rise to
siteꢀisolated catalytically active centers. Postsynthetic
approaches have proven to be valuable for preparing
these singleꢀsite solid catalysts, due to their limited acꢀ
pounds.
Carbonꢀoxygen and carbonꢀhalogen bond
formation are two important fundamental reactions in
1
3
organic transformations.
Etherꢀcontaining and haloꢀ
2
,3
genated aromatic compounds are widely employed in
1
3b, 14
the synthesis of pharmaceuticals.
The use of cheꢀ
lateꢀdirected functionalization of CꢀH bonds has attractꢀ
ed widespread attention, thanks to the pioneering work
4
cessibility via direct solvothermal synthesis. Recently,
1
2c, 15
postsynthetic exchange (PSE, also known as SALE =
solventꢀassisted linker exchange) has been developed as
a powerful and facile method to synthesize a variety of
functionalized MOF materials that otherwise would be
inaccessible. In particular, the incorporation of singleꢀ
site catalytic centers into the Zr(IV)ꢀbased UiO (UiO =
University of Oslo) series of MOFs has proven attracꢀ
tive, due in part to their excellent chemical stability.
Among them, UiOꢀ66 consists of 12ꢀcoordinated
Zr(IV)ꢀcarboxylate clusters Zr (ꢁ ꢀO) (ꢁ ꢀOH) (CO )
2 12
of Sanford and coꢀworkers.
Herein, we report the synthesis and metalation of a
thiocatecholꢀfunctionalized UiOꢀ66 material via
postsynthetic methods. Though other thiolꢀcontaining
5
16
MOFs have been reported, this is one of the few MOF
examples with a sulfurꢀcontaining, open metal chelating
site. The metalated Pd(thiocatecholato) sites exhibit
highly efficient, reusable, and selective catalysis for the
oxidative functionalization of aromatic CꢀH bond. To
the best of our knowledge, this is the first example of a
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MOF catalyst that performs chelationꢀassisted CꢀH funcꢀ exhibited a BrunauerꢀEmmettꢀTeller (BET) surface area
2
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tionalization, achieved by a strong metalꢀsulfur coordiꢀ
nation motif.
of 950±5 m /g, measured with dinitrogen absorption at
77 K. This value is close to the BET surface area of
unmodified UiOꢀ66 (1110±105 m /g), suggesting a clean
2
O
OH
SH
ligand exchange process and not simple incluꢀ
H
2
O
sion/encapsulation of tcatꢀH bdc within the MOF pores
2
5 oC, 24 h
8
SH
(which would significantly decrease the surface area).
Indeed, extensive characterization in our previous studꢀ
ies on PSE of UiOꢀ66 materials confirms a ligand meꢀ
tathesis phenomenon for this functionalization
PSE
HO
O
SH
SH
tcat-H
2
bdc
UiO-66
UiO-66-TCAT
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b, 9a, 17
method.
Pd(OAc)
55 oC, 4 h
2
ZrCl
4
Direct
Metalation
20 oC, 24 h Synthesis
X
1
SH
S
solv
SH
S
Pd
solv
UiO-66-TCAT
UiO-66-PdTCAT
Catalytically Acitve
Scheme 1. Synthesis of UiOꢀ66ꢀTCAT and UiOꢀ66ꢀ
PdTCAT.
The ligand precursor, 2,3ꢀdimercaptoterephthalic acid
(
tcatꢀH bdc), was synthesized starting from dimethyl
2
2
,3ꢀdihydroxyterephthalate in three steps and 37% overꢀ
all yield as described in the Supporting Information.
Direct solvothermal synthesis of a DMF solution conꢀ
Figure 1. PXRD of UiOꢀ66 (a, black), UiOꢀ66ꢀTCAT (b,
red), UiOꢀ66ꢀPdTCAT (c, blue), and recovered UiOꢀ66ꢀ
PdTCAT after 1 (d, magenta) and 5 (e, gold) catalytic cyꢀ
cles.
taining anhydrous ZrCl and tcatꢀH bdc did not afford a
4
2
UiOꢀ66 material, presumably due to the presence of the
thiocatechol metalꢀchelating functionality. Given the
high structural analogy of the H bdc and tcatꢀH bdc ligꢀ
Transition metal bis(dithiolene) complexes, especially
group 10 metals with square planar coordination geomeꢀ
tries, have attracted increasing attention in the field of
magnetic and conducting materials because of the strong
πꢀelectron donor ability from the involvement of the
2
2
ands, PSE was employed as a strategy to introduce diꢀ
mercapto functionality into UiOꢀ66. UiOꢀ66, consisting
of Zr(IV)ꢀbased secondary building units [Zr O (OH) ]
6
4
4
and bdc organic linkers, was prepared using solvotherꢀ
mal conditions containing a mixture of ZrCl , H bdc,
18
sulfur donor atoms. Immobilized thiocatechol ligands
4
2
on the UiOꢀ66ꢀTCAT provide an excellent platform to
and acetic acid (as a modulator) at 120 °C in DMF for
4 h, followed by washing with MeOH and activation
under dynamic vacuum. PSE was performed by incuꢀ
achieve
accessible
and
unsaturated
2
19
mono(thiocatecholato) metal centers. The metalation
of 40% thiocatecholꢀfunctionalized UiOꢀ66ꢀTCAT using
Pd(OAc) in CH Cl afforded darkꢀbrown solids. The
bating solid UiOꢀ66 in an aqueous solution of tcatꢀH bdc
2
20
2
2
2
for 24 h at 85 °C. The linkerꢀexchanged material, UiOꢀ
66ꢀTCAT, was isolated as a yellow microcrystalline
powder using centrifugation, followed by extensive
washing with fresh MeOH and activation under vacuum.
The presence of tcatꢀbdc in UiOꢀ66ꢀTCAT was conꢀ
crystallinity of UiOꢀ66ꢀPdTCAT was maintained upon
metalation, as evidenced by PXRD and FEꢀSEM (Figure
1
and S2). Inductively coupled plasmaꢀoptical emission
spectroscopy (ICPꢀOES) confirmed an atomic ratio of
1:0.18:0.85 (Zr:Pd:S) in the metalꢀloaded sample, conꢀ
firming ~42% of thiocatechol sites were metalated. A
slight, but expected decrease of the BET surface area
1
firmed by H NMR of the MOFs digested with dilute HF
in CD OD (Figure S1). An equimolar reaction between
3
bdc in the UiOꢀ66 solid and tcatꢀH bdc in aqueous soluꢀ
2
2
was observed after metalation at 865±90 m /g for UiOꢀ
tion affords 40% dimercaptoꢀfunctionalized UiOꢀ66ꢀ
TCAT. The degree of functionalization was tunable beꢀ
6
6ꢀPdTCAT (N at 77 K).
2
tween 40ꢀ71%, using 2ꢀ5 equivalents of tcatꢀH bdc in
With isolated and coordinatively accessible Pd centers
2
the PSE solution (Figure S1). Powder Xꢀray diffraction
in a robust MOF, we sought to investigate its catalytic
activity in regioselective CꢀH oxidation. Commonly
used methods to convert sp CꢀH bond to CꢀO or CꢀX
(PXRD) patterns and fieldꢀemission scanning electron
2
microscopy (FEꢀSEM) of functionalized UiOꢀ66 conꢀ
firmed retention of crystallinity with high phase purity
(X=Cl, Br, I) require strong acids/bases, e.g. nꢀBuLi,
2
1
(
Figure 1 and S2). In addition, activated UiOꢀ66ꢀTCAT
CF
3
SO
3
H.
Homogeneous Pd(II)ꢀcatalyzed methods
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Nevertheless, the siteꢀisolated Pdꢀthiocatecholato speꢀ
for chelateꢀdirected oxidative activation has been inꢀ
creasingly studied,
1
2c, 22
1
and MOFs can provide a solidꢀ
cies in the UiO platform presented here proved that
MOFs can achieve efficient and recyclable catalysis for
sp CꢀH activation and installation of alkoxy groups.
2
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state platform to prepare analogous catalysts that can
reuse these preciousꢀmetal active sites, achieving recyꢀ
clable catalysis.
2
Table 2. Pdꢀcatalyzed directed CꢀH bond halogenation reacꢀ
tions.
a
a
Table 1. Regioselective alkoxy group installment of 1.
R
R
1
R
R1
PhI(OAc)
R-OH, 60-100 o
-24 h
2
NXS, CH
3
CN
C
85 oC, 24 h
N
N
N
N
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H
O
H
X
R
Enꢀ
try
Pd
(mol %)
MOF
(mol %)
Yield
(%)
Product
Catalyst
b
Enꢀ
try
1
R (prodꢀ
uct/solvent
Pd
(mol %)
MOF
(mol %)
0
Yield
(%)
0
Catalyst
b
c
CH
CH
CH
CH
CH
3
3
3
3
3
blank
0
1
2
3
4
5
6
7
blank
0
0
0
0
c
N
2
UiOꢀ66
0
0
25
25
25
25
75
50
50
0
Cl
c
3
UiOꢀ66ꢀTCAT
0
c
c
d
d
e
4
5
6
7
8
UiOꢀ66ꢀPdTCAT
5
99(1)
99(1)
95(2)
99(1)
21(3)
UiOꢀ66
25
25
25
25
50
50
50
0
N
Pd(OAc)
2
5
Cl
CH
CH
(CH
2
CH
CF
CH
3
UiOꢀ66ꢀPdTCAT
UiOꢀ66ꢀPdTCAT
UiOꢀ66ꢀPdTCAT
15
10
10
UiOꢀ66ꢀ
TCAT
0
0
2
3
N
Cl
2
)
2
3
a
UiOꢀ66ꢀ
PdTCAT
0
2
.21 mmol benzoquinoline, 0.42 mmol PhI(OAc) , 5ꢀ15 mol% Pd in
b 1
5
95(1)
97(1)
50(1)
32(2)
87(1)
N
1
.75 mL alcohol (RꢀOH). Determined by GCꢀMS and H NMR, three
c d e
Cl
independent trials. 6h, 60 °C. 24h, 80 °C. 24h, 100 °C.
UiOꢀ66ꢀ
PdTCAT
The oxidation of benzo[h]quinoline (1) to install
5
N
alkoxy groups on a CꢀH10 single bond using iodobenꢀ
zene diacetate [PhI(OAc) ] as the oxidant was investiꢀ
gated using the metalated MOF.
PdTCAT (5 mol% in Pd) nearly quantitative yield of
Br
2
UiOꢀ66ꢀ
PdTCAT
10
10
10
Using UiOꢀ66ꢀ
N
Cl
methoxyꢀfunctionalized 1 was achieved in 6 h at 60 °C
UiOꢀ66ꢀ
PdTCAT
(Table 1, entry 4). By comparison, both pristine UiOꢀ66
N
Br
and UiOꢀ66ꢀTCAT (before Pd metalation) gave no conꢀ
version (Table 1, entries 2 and 3). In order to confirm
the heterogeneous nature of UiOꢀ66ꢀPdTCAT, a hot filꢀ
tration experiment was performed, removing the catalyst
by filtration after the first hour of the reaction. Timeꢀ
dependent GC yield indicated no additional conversion
to product was observed (up to 5 h) after filtration (Figꢀ
ure S3). No Pd leaching was observed (as evidenced by
ICPꢀOES of the filtrate contained <0.1 ppm Pd), further
confirming the heterogeneity of the MOF catalyst. Altꢀ
hough the homogeneous Pd(II) catalysts [Pd(OAc)2]
completed the reaction in only ~3 h, UiOꢀ66ꢀPdTCAT
exhibited excellent recyclability without a significant
decrease in yields (92~99%) over five catalytic cycles
UiOꢀ66ꢀ
PdTCAT
8
N
I
a
0.21 mmol substrate, 0.252 mmol NXS, 5 mol% Pd in 1.75 mL
b
1
3
CH CN. Determined by GCꢀMS and H NMR, three independent trials.
Chelateꢀdirected oxidation can be extended to haloꢀ
genations using Nꢀhalosuccinimides as both oxidants
and halogenating reagents. Using the same MOF cataꢀ
lyst (5 mol% in Pd) as well as 1.2 eq. of Nꢀ
chlorosuccinimide achieved 95% yield of monoꢀ
chlorinated benzo[h]quinoline product (Table 2, entry 4).
Again, control reactions, such as using UiOꢀ66ꢀTCAT as
catalyst, did not produce the desired product (Table 2,
entry 1ꢀ3). Recyclability tests were carried out with
UiOꢀ66ꢀPdTCAT, showing conversions of 86~95% of 1
to monoꢀchlorinated products over five successive runs
(Table S2). Between each run, the catalyst could be
recovered by centrifugation, washed with MeOH, dried
under vacuum, and then directly used for additional reꢀ
actions. The crystallinity of the MOF was maintained
after each cycle, as confirmed by PXRD and FEꢀSEM
(Table S2). Palladiumꢀcatalyzed direct halogenations
were also extended to bromination using Nꢀ
bromosuccinimide as a terminal oxidant (Table 2, entry
(
Figure 1 and S2). The alkoxy functional group installaꢀ
5
). Though iodination was unsuccessful on 1, perhaps
tion of 1 can be successfully extended to achieve other
alkylꢀaryl ethers (e.g. OEt, OCH CF ) in nearly quantitaꢀ
tive yields, as summarized in Table 1. However, using
1ꢀpropanol as solvent only gave 21% conversion, likely
due to the weak nucleophilicity of the propoxy group.
15c
due to steric constraints of the rigid, planar substrate,
2
3
Nꢀiodosuccinimide could be used to selectively iodinate
ꢀmethylꢀ2ꢀphenylpyridine (2) to give 87% of the monoꢀ
3
iodinated product. Chlorination and bromination of 2
only afforded 50% and 32% yield (Table 2, entry 6, 7),
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.
(a) Kim, M.; Cohen, S. M., CrystEngComm 2012, 14, 4096ꢀ
104; (b) Fei, H.; Cohen, S. M., Chem. Commun. 2014, 50, 4810ꢀ4812.
(a) Wu, H.; Chua, Y. S.; Krungleviciute, V.; Tyagi, M.; Chen,
respectively; however, these catalysis results are compaꢀ
1
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rable to homogeneous Pd catalysts (44~56% yield, Table
.
15c
S3).
The lower yield in these cases may be due to the
P.; Yildirim, T.; Zhou, W., J. Am. Chem. Soc. 2013, 135, 10525ꢀ10532;
b) Lau, C. H.; Babarao, R.; Hill, M. R., Chem. Commun. 2013, 49, 3634ꢀ
3636; (c) Morris, W.; Doonan, C. J.; Yaghi, O. M., Inorg. Chem. 2011, 50,
853ꢀ6855; (d) Cmarik, G. E.; Kim, M.; Cohen, S. M.; Walton, K. S.,
Langmuir 2012, 28, 15606ꢀ15613.
(a) Vermoortele, F.; Bueken, B.; Bars, G. L.; Voorde, B. V.;
(
low reactivity of the relatively electronꢀdeficient arene
substrate.
6
In conclusion, PSE is shown to be a facile and mild
functionalization approach to synthesize a sulfurꢀ
containing thiocatechol site in a robust UiOꢀ66 material.
The robust MOF allows for preparation of unprecedentꢀ
ed metalꢀmono(thiocatecholato) species with coordinaꢀ
tively unsaturated soft metal sites. Pd metalation of the
thiocatechol functionality affords an efficient and recyꢀ
clable MOF catalyst for regioselective CꢀH oxidation.
Aromatic substrates are readily oxidized with this metaꢀ
8
.
Vandichel, M.; Houthoofd, K.; Vimont, A.; Daturi, M.; Waroquier, M.;
Speybroeck, V. V.; Kirschhock, C.; De Vos, D. E., J. Am. Chem. Soc.
2013, 135, 11465ꢀ11468; (b) Fei, H.; Shin, J.; Meng, Y. S.; Adelhardt, M.;
Sutter, J.; Meyer, K.; Cohen, S. M., J. Am. Chem. Soc. 2014, 136, 4965ꢀ
4
9.
Am. Chem. Soc. 2013, 135, 16997ꢀ17003; (b) Fei, H.; Pullen, S.; Wagner,
A.; Ott, S.; Cohen, S. M., Chem. Commun. 2015, 51, 66ꢀ69; (c) Sun, D.;
Fu, Y.; Liu, W.; Ye, L.; Wang, D.; Yang, L.; Fu, X.; Li, Z., Chem. Eur. J.
0
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973.
(a) Pullen, S.; Fei, H.; Orthaber, A.; Cohen, S. M.; Ott, S., J.
2
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1. (a) Ekkehardt Hahn, F.; Offermann, M.; SIsfort, C. S.; Pape,
2
lated MOF converting sp CꢀH bonds to ethers and arylꢀ
1
halides. The strong covalent metalꢀthiocatecholato bindꢀ
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Supporting Information. Experimental details, additional
characterization of MOF catalysts and catalysis reactions.
This material is available free of charge via the Internet at
http://pubs.acs.org.
1
(
1
AUTHOR INFORMATION
4
Corresponding Author
1
Li, J. J.; Johnson, D. S., Modern Drug Synthesis. Wiley:
scohen@ucsd.edu
Funding Sources
2
No competing financial interests have been declared.
Chem. Soc. 2004, 126, 9542ꢀ9543; (c) Kalyani, D.; Dick, A. R.; Anani, W.
Q.; Sanford, M. S., Tetrahedron 2006, 62, 11483ꢀ11498; (d) Zhang, S. Y.;
He, G.; Nack, W. A.; Zhao, Y.; Li, Q.; Chen, G., J. Am. Chem. Soc. 2013,
135, 2124ꢀ2127; (e) Zhang, Q.; Chen, K.; Rao, W.; Zhang, Y.; Chen, F. J.;
Shi, B. F., Angew. Chem., Int. Ed. 2013, 52, 13588ꢀ13592.
ACKNOWLEDGMENT
This work was supported by a grant from the National Sciꢀ
ence Foundation, Division of Chemistry (CHEꢀ1359906).
1
2
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(a) Sun, L.; Miyakai, T.; Seki, S.; Dinca, M., J. Am. Chem. Soc.
013, 135, 8185ꢀ8188; (b) Yee, K. K.; Reimer, N.; Liu, J.; Cheng, S. Y.;
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