Metal‐Organic Frameworks for Catalytic Construction of C−B Bond and Related Reactions

Abstract

Organoboranes are important reagents in modern synthetic organic chemistry. The CÀ B bonds presented in these derivatives are transformable into a CÀ X (X=C, N, O, and halogen) bonds stereoretentively to provide valuable complex molecules employed in medicinal chemistry, agrochemicals, natural products, and materials science. The homogeneous transition-metalcatalyzed borylation reaction is one of the most effective methodologies to synthesize organoboranes. However, these catalytic systems suffer from the inability to recover the catalysts and metal contamination into products, which limits their application towards chemical and pharmaceutical processes. Recently, the metal-organic frameworks (MOFs)-based heterogeneous catalytic systems have gained prominence to overcome these limitations. This review article surveys the employment of MOFs-based catalysts in the borylation reactions, and the related mechanisms are also discussed.

Heterovalent Metal Pair Sites on Metal–Organic Framework Ordered Macropores for Multimolecular Co-Activation

“…Vinylboronates (VBEs) are a versatile class of intermediates in pharmaceutical and synthetic chemistry, which widely participate in certain cross-coupling reactions for the construction of new carbon–carbon bond, etc . − For now, the hydroboration of alkynes with water-resistant and oxygen-insensitive bis­(pinacolato)­diboron (B 2 Pin 2 ) is an effective method for the synthesis of VBEs, which usually involves transition metal catalysts, especially Cu-based ones. − To date, the reported homogeneous Cu systems not only require ligands and bases but also bear high waste because of difficult recycling (Figure S30). ,,, Despite several heterogeneous Cu catalysts such as Cu-MOFs, − Cu (oxides), − or Cu single atoms have been utilized, the base or high reaction temperature is still necessary (Figure S30).…”

Facile Synthesis of Vinyl Boronate Esters via Dehydrogenative Borylation of Alkenes Enabled by a Co-MOF Catalyst: An Additive-Free Approach

“…Due to the presence of multiple active sites, these heterogeneous catalysts suffer from selectivity issues. Therefore, recyclable and site-selective metal–organic frameworks (MOFs)-catalyzed reactions have attracted a great deal of attention to install boron motifs into organic entities with high regio- and stereoselectivity to achieve organoborane derivatives, which are valuable synthetic intermediates for various organic transformations. − Over the past few decades, the construction of C–B bonds has seen an upsurge due to their high demand in pharmaceuticals and therapeutics and in material chemistry. , However, from an economic and environmental perspective, introduction of boron atoms into hydrocarbon derivatives utilizing recyclable base metal catalyst systems is rare…”

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal–Organic Framework with High Catalytic Activity

“…18 Hydroboration reactions have also attracted the attention of the scientific community using MOFs as Lewis acid catalysts. 45 The addition of boranes (HBR 2 ) to carbonyl bonds leads to the formation of B−O bonds, which, together with hydrolysis, constitutes a two-step process equivalent to a reduction. 46 In this way, derivatized alcohols could be obtained, allowing the synthesis of fine chemicals and natural products.…”