This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.
Compounds consisting of a carbonyl group and an alkyne group, especially enynals and enynones, are versatile and powerful building blocks for generating structurally diverse polycyclic compounds. In the past decades, the transitionmetal-catalyzed nucleophilic addition of a carbonyl group to an alkyne has attracted great interest for the high reactivity, good selectivity, excellent functional-group tolerance, and mild reaction conditions. Most importantly, versatile intermediates, such as pyrylium-ion, metal-carbene, 1,3-dipole, and metal-vinyl species, make it highly attractive for both the development of synthetic methodologies and applications in the synthesis of bioactive compounds or complex naturally occurring skeletons. This review focuses on the transition-metal-catalyzed nucleophilic addition of carbonyl groups to alkynes with an emphasis on the scope and limitations, the mechanisms, and applications in organic synthesis.
A porous metal–organic cage (MOC-Rh-1) with Rh–Rh bonds has been prepared, which can act as a heterogeneous catalyst and promote the intramolecular C–H amination of azides.
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