title: Catalyst-controlled C-O versus C-N allylic functionalization of terminal olefins.
abstract: The divergent synthesis of syn-1,2-aminoalcohol or syn-1,2-diamine precursors from a common terminal olefin has been accomplished using a combination of palladium(II) catalysis with Lewis acid cocatalysis. Palladium(II)/bis-sulfoxide catalysis with a silver triflate cocatalyst leads for the first time to anti-2-aminooxazolines (C-O) in good to excellent yields. Simple removal of the bis-sulfoxide ligand from this reaction results in a complete switch in reactivity to afford anti-imidazolidinone products (C-N) in good yields and excellent diastereoselectivities. Mechanistic studies suggest the divergent C-O versus C-N reactivity from a common ambident nucleophile arises due to a switch in mechanism from allylic C-H cleavage/functionalization to olefin isomerization/oxidative amination.
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Iulia I
authors.initials: II
authors.lastname: Strambeanu
authors.forename: M Christina
authors.initials: MC
authors.lastname: White
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry; D000586:Amination; D000605:Amino Alcohols / Q000138:chemical synthesis*; D002384:Catalysis; D003959:Diamines / Q000138:chemical synthesis*; D058116:Lewis Acids / Q000737:chemistry; D010165:Palladium / Q000737:chemistry
chemical_list: D000475:Alkenes; D000498:Allyl Compounds; D000605:Amino Alcohols; D003959:Diamines; D058116:Lewis Acids; D010165:Palladium