Asymmetric ring-opening reaction of <i>meso</i>-epoxides with aromatic amines using homochiral metal–organic frameworks as recyclable heterogeneous catalysts

Tanaka, Kōichi; Kinoshita, Maya; Kayahara, Jun; Uebayashi, Yutaro; Nakaji, Kazusada; Morawiak, Maja; Urbańczyk‐Lipkowska, Zofia

doi:10.1039/c8ra05163a

Cited by 14 publications

(6 citation statements)

References 46 publications

(28 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Metal–organic frameworks (MOFs), also known as porous coordination polymers (PCPs), have been at the forefront of research during the past decade as a new type of porous material for storage, separation, and catalytic applications. Because MOFs provide tunable, three-dimensional architectures that are ideal for controlling the environment of a catalyst, a significant amount of work has been done in the area of enantioselective catalytic reactions using chiral MOFs. − However, the identity of the reaction sites in MOF-based catalysts is still under debate.…”

Section: Introductionmentioning

confidence: 99%

Identification of Reaction Sites on Metal–Organic Framework-Based Asymmetric Catalysts for Carbonyl–Ene Reactions

et al. 2019

View full text Add to dashboard Cite

The characteristics of catalytic sites in metal− organic framework (MOF)-based catalysts could be approximately classified by their location, i.e., the inside of the pore and/or on the surface of the crystal. This classification of catalytic sites in a single-MOF crystal has been widely overlooked. In particular, in a chiral MOF, the environment of any specific reaction site will vary depending on its location. Thus, pin-pointing the reaction site for a MOF-based heterogeneous catalyst is an intriguing issue. In this study, the active site of a MOF-based catalyst is revealed after a thorough investigation comparing substrate size versus reaction rate for two distinct mechanisms of carbonyl−ene reactions. Both Zn-mediated stoichiometric carbonyl−ene reactions and Ti-catalyzed carbonyl−ene reactions were performed separately and compared using homogeneous and heterogeneous media. These results could provide a clear answer to the question of locating the reaction sites within the MOF. Through this work, it became evident that the entire MOF crystal is effective; however, the inside of the pore is an important contributor to having chirality control in the stoichiometric reaction. In addition, for a catalytic reaction, our findings suggest that the substrate size is mostly irrelevant as catalysis can simply take place on the surface of the crystals. Thus, comparison of the reaction rate and substrate size may not be a valid method to ascertain whether a reaction occurs inside the MOF or on its surface. This conclusion is further supported by the effect of particle size on the reaction efficiency and the enantioselectivity along with visualization of the guest-accessible space using two-photon fluorescence microscopy.

show abstract

Section: Introductionmentioning

confidence: 99%

Identification of Reaction Sites on Metal–Organic Framework-Based Asymmetric Catalysts for Carbonyl–Ene Reactions

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Homochiral porous metal–organic frameworks (HPMOFs) as a class of chiral crystalline porous materials combining chirality and porosity have emerged highly promising for the enantioselective resolution of racemic mixtures, enantioselective catalysis and recognition, etc. − Therefore, the HPMOFs have been actively developed in recent decades, due to their high stability, large surface area, and adjustable functionality, which benefits from varying organic building blocks. Those advantages surpass traditional inorganic and organic chiral porous materials.…”

Section: Introductionmentioning

confidence: 99%

Homochiral Porous Metal–Organic Frameworks Constructed from a V-Shaped Alanine Derivative Based on Pyridyl-Dicarboxylate

Guo

Wang

et al. 2019

Crystal Growth & Design

View full text Add to dashboard Cite

Three novel, homochiral, porous metal–organic frameworks based on the H2PDBAla ligand and different divalent cations (Co(II)) and Cu(II)), namely, [M(PDBAla)(bipy)(H2O)2]·3H2O (M = Co 1 and Cu 2), [Cu(PDBAla)(bpea)]·7H2O (3) (H2PDBAla = pyridine-2,6-dicarbonyl-bis(l-alanine), bipy = 4,4′-bipyridine, bpea = 1,2-bis(4-pyridyl)ethane), have been synthesized and characterized with the assistance of N-donor ligands. The distinctive H2PDBAla ligands are coordinated to divalent metal ions by the different coordination modes, forming various helixes in compounds 1–3. Compounds 1 and 2 are isostructural and feature a 2-fold interpenetrating three-dimensional (3D) framework with the cds topological net built by the combination right-handed helical chains and bipy ligands, whereas a 3D framework with the tcj topological net is observed in compound 3, wherein bpea ligands reinforce the 3D framework constructed by right-handed helical chains. Compounds 1 and 3 display high CO2 absorption capability and superior sorption enthalpies, reflecting the strong affinity of the frameworks for CO2. Moreover, compound 3 exhibits a small enantioselective separation performance for racemic alcohol.

show abstract

“…Chiral MOFs can also be used to perform catalytic asymmetric reactions. One of the very recent example uses homochiral MOFs as recyclable heterogeneous catalysts for an asymmetric ring-opening reaction of meso-epoxides with aromatic amines [210]. For instance, a homochiral MOF was obtained by treating (R)-2,2 -dihydroxyl-1,1 -binaphthalene-5,5 -dicarboxylic acid (a ligand) with Cu(NO 3 ) 2 (a metal precursor) and gave excellent results in the asymmetric ring-opening of cyclohexene oxide with several aromatic amines (N-methyl aniline, N-methyl-p-toluidine, N-methyl-p-anisidine, and N-methyl-p-chloroaniline).…”

Section: Discrete and Infinite Porous Metal-organic Networkmentioning

confidence: 99%

Supramolecular Chemistry and Self-Organization: A Veritable Playground for Catalysis

2019

View full text Add to dashboard Cite

The directed assembly of molecular building blocks into discrete supermolecules or extended supramolecular networks through noncovalent intermolecular interactions is an ongoing challenge in chemistry. This challenge may be overcome by establishing a hierarchy of intermolecular interactions that, in turn, may facilitate the edification of supramolecular assemblies. As noncovalent interactions can be used to accelerate the reaction rates and/or to increase their selectivity, the development of efficient and practical catalytic systems, using supramolecular chemistry, has been achieved during the last few decades. However, between discrete and extended supramolecular assemblies, the newly developed “colloidal tectonics” concept allows us to link the molecular and macroscopic scales through the structured engineering of colloidal structures that can be applied to the design of predictable, versatile, and switchable catalytic systems. The main cutting-edge strategies involving supramolecular chemistry and self-organization in catalysis will be discussed and compared in this review.

show abstract

Asymmetric ring-opening reaction of meso-epoxides with aromatic amines using homochiral metal–organic frameworks as recyclable heterogeneous catalysts

Abstract: Asymmetric ring-opening reactions of meso-epoxides by aromatic amines were achieved by using some chiral metal–organic frameworks. The corresponding β-amino alcohols were obtained with good yields and enantioselectivities (up to 97% ee).

Cited by 14 publications

References 46 publications

Identification of Reaction Sites on Metal–Organic Framework-Based Asymmetric Catalysts for Carbonyl–Ene Reactions

Identification of Reaction Sites on Metal–Organic Framework-Based Asymmetric Catalysts for Carbonyl–Ene Reactions

Homochiral Porous Metal–Organic Frameworks Constructed from a V-Shaped Alanine Derivative Based on Pyridyl-Dicarboxylate

Supramolecular Chemistry and Self-Organization: A Veritable Playground for Catalysis

Contact Info

Product

Resources

About