Inorganic Chemistry
Article
hydrogen bonding of catalyst with the substrate plays a key
role in the reaction.
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CONCLUSION
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A primary amide-decorated Zn(II) coordination network, 1,
has been utilized as an effective HBD heterogeneous catalyst in
the Michael addition of malononitrile to 2-enoylpyridines. Its
uniqueness and efficiency was demonstrated by making an
isostructural coordination network with a fully pyridyl-based
ligand, 2. Based on the results reported in this work, 3 mol % 1
and 2 provided >99% and 7% conversion, respectively. This
clearly established the selective catalytic activity of 1 over 2
due to the presence of the primary amide side arms. Their full
characterization by several analytical techniques, including
single-crystal X-ray diffraction, allowed us to investigate this
catalysis in an elaborative manner. Extending the scope for 1,
six other 2-enoylpyridines with both electron withdrawing and
electron donating groups were successfully converted to the
expected products with quantitative percent conversions for all
except the one with a methyl group. Its heterogeneous nature
and recyclability were established. With the strategic substrate
choice, a mechanism for the action of 1 in this reaction was
also established. Further design of new CN catalysts with
primary amide-based ligands and distinct kinds of carboxylate-
based linkers is ongoing in our laboratory for the organic
reactions requiring activation via hydrogen bond donating
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ASSOCIATED CONTENT
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Hiemstra, H. Asymmetric Organocatalytic Henry Reaction. Angew.
Chem., Int. Ed. 2006, 45, 929−931.
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* Supporting Information
The Supporting Information is available free of charge on the
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Optimization of a Highly Enantioselective Catalyst for the Strecker
Reaction. J. Am. Chem. Soc. 2002, 124, 10012−10014.
Materials and methods, physical measurements, single-
crystal X-ray data collection and refinements, Figures
S1−S24, and Table S1 (PDF)
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Accession Codes
tallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(18) Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H. Mixed-Metal or
Mixed-Linker Metal Organic Frameworks as Heterogeneous Cata-
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AUTHOR INFORMATION
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(19) Chughtai, A. H.; Ahmad, N.; Younus, H. A.; Laypkov, A.;
Verpoort, F. Metal−Organic Frameworks: Versatile Heterogeneous
Catalysts for Efficient Catalytic Organic Transformations. Chem. Soc.
Rev. 2015, 44, 6804−6849.
Corresponding Author
ORCID
̌
(20) Dhakshinamoorthy, A.; Opanasenko, M.; Cejka, J.; Garcia, H.
Notes
Metal Organic Frameworks as Heterogeneous Catalysts for the
Production of Fine Chemicals. Catal. Sci. Technol. 2013, 3, 2509−
2540.
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Linker Strategy for the Construction of Multifunctional Metal−
Organic Frameworks. J. Mater. Chem. A 2017, 5, 4280−4291.
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Frameworks as Catalysts: The Role of Metal Active Sites. Catal. Sci.
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Catalysis to Gas Storage; Wiley-VCH: 2011.
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Functionalized Highly Efficient and Recyclable Hydrogen-Bond-
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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Funding, as well as the instrumentation facility used in this
work, was provided by IISER, Mohali. D.M. is grateful to
UGC, India, for a research fellowship. The central facilities (X-
ray, NMR, and SEM) and other departmental facilities at
IISER Mohali are acknowledged.
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Inorg. Chem. XXXX, XXX, XXX−XXX