title: Distal-selective hydroformylation using scaffolding catalysis.
abstract: In hydroformylation, phosphorus-based directing groups have been consistently successful at placing the aldehyde on the carbon proximal to the directing group. The design and synthesis of a novel catalytic directing group are reported that promotes aldehyde formation on the carbon distal relative to the directing functionality. This scaffolding ligand, which operates through a reversible covalent bond to the substrate, has been applied to the diastereoselective hydroformylation of homoallylic alcohols to afford δ-lactones selectively. Altering the distance between the alcohol and the olefin revealed that homoallylic alcohols gives the distal lactone with the highest levels of regioselectivity.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
authors.forename: Candice L
authors.initials: CL
authors.lastname: Joe
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Blaisdell
authors.forename: Allison F
authors.initials: AF
authors.lastname: Geoghan
authors.forename: Kian L
authors.initials: KL
authors.lastname: Tan
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol