ChemInform Abstract: Bipyridine‐ and Phenanthroline‐Based Metal—Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C—H Activation.

Abstract

Activation. -A series of robust and porous bipyridyl-and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology is prepared and metalated with [Ir(cod)(OMe)] 2 to provide Ir-MOF complexes which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation as well as C-H boration of arenes. The Ir(OMe)(cod)(mPT-MOF) system shown in the scheme is also active in catalyzing tandem dehydrosilylation/ dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. MOF-Ir catalysts are up to 95 times more active and stable than their homogeneous counterparts for all three reactions, supporting the beneficial effects of active site isolation within MOFs. -(MANNA, K.; ZHANG, T.; GREENE, F. X.; LIN*, W.; J. Am. Chem. Soc. 137 (2015) 7, 2665-2673, http://dx.doi.org/10.1021/ja512478y ; Dep. Chem., Univ. Chicago, Chicago, IL 60637, USA; Eng.) -Nuesgen 29-026