Atom and step economical synthesis of acyclic quaternary centers iridium-catalyzed hydroarylative cross-coupling of 1,1-disubstituted alkenes.

Quaternary benzylic centers are accessed with high atom and step economy by Ir-catalyzed alkene hydroarylation. These studies provide unique examples of the use of non-polarized 1,1-disubstituted alkenes in branch selective Murai-type hydro(hetero)arylations. Detailed mechanistic studies have been undertaken, and these indicate that the first irreversible step is the demanding alkene carbometallation process.

Branch-Selective and Enantioselective Iridium-Catalyzed Alkene Hydroarylation via Anilide-Directed C-H Oxidative Addition.

Tertiary benzylic stereocenters are accessed in high enantioselectivity by Ir-catalyzed branch selective addition of anilide ortho-C-H bonds across styrenes and α-olefins. Mechanistic studies indicate that the stereocenter generating step is reversible.

Stereocontrolled (Me3Si)3SiH-Mediated Radical and Ionic Hydride Transfer in Synthesis of 2,3,5-Trisubstituted THF.

2,3,5-Trisubstituted tetrahydrofurans were prepared stereoselectively through a two-step process involving the addition of an acyl radical to a β-silyloxy acrylic ester followed by an acid-catalyzed desilylation-ketalization sequence and a final oxocarbenium reduction step. High levels of 1,2- and 1,3-stereocontrol were attained when (Me3Si)3SiH was used as a radical followed by a ionic hydrogen transfer agent.