title: Catalytic functionalization of unactivated sp3 C-H bonds via exo-directing groups: synthesis of chemically differentiated 1,2-diols.
abstract: We describe a Pd-catalyzed site-selective functionalization of unactivated aliphatic C-H bonds, providing chemically differentiated 1,2-diols from monoalcohol derivatives. The oxime was employed as both a directing group (DG) and an alcohol surrogate for this transformation. As demonstrated in a range of substrates, the C-H bonds β to the oxime group are selectively oxidized. Besides activation of the methyl groups, methylene groups (CH(2)) in cyclic substrates and methine groups (CH) at bridge-head positions can also be functionalized. In addition, an intriguing oxidative skeleton rearrangement was observed using the menthol-derived substrate. The use of exo-directing groups in C-H activation, as illustrated in this work, would potentially open doors for the discovery of new transformations and new cleavable DGs.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: Zhi
authors.initials: Z
authors.lastname: Ren
authors.forename: Fanyang
authors.initials: F
authors.lastname: Mo
authors.forename: Guangbin
authors.initials: G
authors.lastname: Dong
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
chemical_list: D000438:Alcohols; D009942:Organometallic Compounds; D010165:Palladium