RESUMO
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. Structure-reactivity studies show that the efficiency of this is critically dependent on key structural features of the ligand. Computational studies have been undertaken to rationalize this experimental data, showing how more sterically demanding ligands reduce the reaction barrier via predistortion of the reacting intermediate. The key insight disclosed here will underpin the ongoing development of increasingly sophisticated branch selective Murai hydroarylations.
RESUMO
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.
RESUMO
2,3,5-Trisubstituted tetrahydrofurans were prepared stereoselectively through a two-step process involving the addition of an acyl radical to a ß-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.