Pd⁰ -Catalyzed Asymmetric Carbonitratation Reaction Featuring an H-Bonding-Driven Alkyl-Pd^II -ONO₂ Reductive...

Reductive elimination of alkyl-Pd^II -O is a synthetically useful yet underdeveloped elementary reaction. Here we report that the combination of an H-bonding donor [PyH][BF₄ ] and AgNO₃ additive under toluene/H₂ O biphasic system can enable such elementary step to form alkyl nitrate. This results in the Pd⁰ -catalyzed asymmetric carbonitratations of (Z)-1-iodo-1,6-dienes with (R)-BINAP as the chiral ligand, affording alkyl nitrates up to 96 % ee. Mechanistic studies disclose that the reaction consists of oxidative addition of Pd⁰ catalyst to vinyl iodide, anion ligand exchange between I^- and NO₃ ^- , alkene insertion and S_N 2-type alkyl-Pd^II -ONO₂ reductive elimination. Evidences suggest that H-bonding interaction of PyH⋅⋅⋅ONO₂ can facilitate dissociation of O₂ NO^- ligand from the alkyl-Pd^II -ONO₂ species, thus enabling the challenging alkyl-Pd^II -ONO₂ reductive elimination to be feasible.