Litcius/Paper detail

Ligand‐Enabled β‐Methylene C(sp <sup>3</sup> )−H Arylation of Masked Aliphatic Alcohols

Guoqin Xia, Zhe Zhuang, Luo‐Yan Liu, Stuart L. Schreiber, Bruno Melillo, Jin‐Quan Yu

2020Angewandte Chemie International Edition61 citationsDOIOpen Access PDF

Abstract

Abstract Despite recent advances, reactivity and site‐selectivity remain significant obstacles for the practical application of C(sp 3 )−H bond functionalization methods. Here, we describe a system that combines a salicylic‐aldehyde‐derived L,X‐type directing group with an electron‐deficient 2‐pyridone ligand to enable the β‐methylene C(sp 3 )−H arylation of aliphatic alcohols, which has not been possible previously. Notably, this protocol is compatible with heterocycles embedded in both alcohol substrates and aryl coupling partners. A site‐ and stereo‐specific annulation of dihydrocholesterol and the synthesis of a key intermediate of englitazone illustrate the practicality of this method.

Topics & Concepts

ChemistryAldehydeMethyleneLigand (biochemistry)Reactivity (psychology)AnnulationCombinatorial chemistryAlcoholArylStereochemistrySelectivitySurface modificationMedicinal chemistryOrganic chemistryCatalysisPathologyBiochemistryMedicineReceptorAlternative medicineAlkylPhysical chemistryCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsCyclopropane Reaction Mechanisms