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      A “one-step” approach to the highly efficient synthesis of lactide through the confinement catalysis of covalent organic frameworks

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          Abstract

          The precision confinement effect of the highly ordered channels with functional moieties in the designed 2D COFs realizes the highly efficient conversion from the lactide acid to the cyclic dimer lactide directly and avoids oligomerization.

          Abstract

          The efficient synthesis of lactide with high purity is the key to poly-lactic acid (PLA) production. Here, we demonstrated a 2D COFs-based catalyst, which could convert l-lactic acid into l-lactide directly in an excellent yield (80%) under mild conditions. Similar to enzymatic catalysis in which the product selectivity is controlled by the enzyme pocket, the precision confinement effect of the highly ordered channels and adjustable structures with functional moieties of the COFs play key roles in converting the monomer to the cyclic dimer directly and avoiding oligomerization. This strategy is sharply different from the current two-stage process for synthesizing lactide. The reactions are carried out at a lower temperature and under atmospheric pressure, which reduces the energy consumption significantly. In addition, this newly developed method avoids the use of metal catalysts and meets the demands of the environmental friendly trend in chemical synthesis. Last, the functions of the emerging COFs materials as excellent heterogeneous catalysts with a confinement effect were further explored.

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          Most cited references70

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          Porous, crystalline, covalent organic frameworks.

          Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
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            Covalent Organic Frameworks: Design, Synthesis, and Functions

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              Construction of covalent organic framework for catalysis: Pd/COF-LZU1 in Suzuki-Miyaura coupling reaction.

              Covalent organic frameworks (COFs) are crystalline porous solids with well-defined two- or three-dimensional molecular structures. Although the structural regularity provides this new type of porous material with high potentials in catalysis, no example has been presented so far. Herein, we report the first application of a new COF material, COF-LZU1, for highly efficient catalysis. The easily prepared imine-linked COF-LZU1 possesses a two-dimensional eclipsed layered-sheet structure, making its incorporation with metal ions feasible. Via a simple post-treatment, a Pd(II)-containing COF, Pd/COF-LZU1, was accordingly synthesized, which showed excellent catalytic activity in catalyzing the Suzuki-Miyaura coupling reaction. The superior utility of Pd/COF-LZU1 in catalysis was elucidated by the broad scope of the reactants and the excellent yields (96-98%) of the reaction products, together with the high stability and easy recyclability of the catalyst. We expect that our approach will further boost research on designing and employing functional COF materials for catalysis. © 2011 American Chemical Society
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                Author and article information

                Contributors
                Journal
                GRCHFJ
                Green Chemistry
                Green Chem.
                Royal Society of Chemistry (RSC)
                1463-9262
                1463-9270
                April 24 2023
                2023
                : 25
                : 8
                : 3103-3110
                Affiliations
                [1 ]College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
                Article
                10.1039/D2GC04771C
                185eb45e-45f4-45e2-be07-5f1540cbf29a
                © 2023

                http://rsc.li/journals-terms-of-use

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