Pd⁰‐Catalyzed Asymmetric Carbonitratation Reaction Featuring an H‐Bonding‐Driven Alkyl−Pd^II−ONO₂ Reductive Elimination

Abstract

Reductive elimination of alkylÀ Pd II À O is a synthetically useful yet underdeveloped elementary reaction. Here we report that the combination of an Hbonding donor [PyH][BF 4 ] and AgNO 3 additive under toluene/H 2 O biphasic system can enable such elementary step to form alkyl nitrate. This results in the Pd 0catalyzed 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 Pd 0 catalyst to vinyl iodide, anion ligand exchange between I À and NO 3 À ,

Cobalt-Catalyzed Enantioselective Cross-Electrophile Couplings: Stereoselective Syntheses of 5–7-Membered Azacycles

“…The reactions enable stereoselective construction of partially saturated azacycles of 5–7 ring sizes, carrying new quaternary stereocenters (see Figure ). Pyrrolidines and piperidines are among the most frequently used rings in small-molecule drugs and drug candidates (for example, nifeviroc, paroxetine, and cisapride) . Azepine derivatives are also core structures in some medicines .…”