A Simple and Broadly Applicable C−N Bond Forming Dearomatization Protocol Enabled by Bifunctional Amino Reagents

Abstract

ACÀNbond forming dearomatization protocol with broad scope is outlined. Specifically,b ifunctional amino reagents are used for sequential nucleophilic and electrophilic C À Nb ond formations,w ith the latter effecting the key dearomatization step.Using this approach, g-arylated alcohols are converted to aw ide range of differentially protected spirocyclic pyrrolidines in just two or three steps.

Chiral Phosphoric Acid-Catalyzed Enantioselective Dearomative Electrophilic Hydrazination: Access to Chiral Aza-Quaternary Carbon Indolenines

“…In sharp contrast, the dearomatization reaction of 2,3-disubstituted indoles with a nitrogen electrophilic reagent for enantioselective synthesis of aza-quaternary carbon indolenines was rarely reported. In 2017, Bower realized the construction of aza-quaternary carbon indolenines by designing 2,3-disubstituted indole substrates with electrophilic nitrogen through Mitsunobu alkylation . Xu achieved a copper-catalyzed dearomatization reaction of indole from 2-methylindole-derived oxime acetates and synthesized aza-quaternary carbon indolenines in the same year .…”

Electrophilic Aminating Agents in Total Synthesis

“…carbamates,s ulfonamides) and offers broad scope with respect to the aromatic nucleophile. [311] Compared to prior approaches,t hese methods are relatively mild and flexible, such that they seem well suited to applications in total synthesis.I ti sa lso important to note that certain types of dearomatizing aminations can be achieved under transitionmetal-catalyzed conditions,a nd these protocols will also likely find use in total synthesis. [312][313][314][315][316] It is pertinent to highlight that arange of powerful metalfree intermolecular CÀNb ond-forming dearomatization processes have been developed recently by Sarlah and coworkers.…”

Electrophilic Aminating Agents in Total Synthesis

“…carbamates,s ulfonamides) and offers broad scope with respect to the aromatic nucleophile. [311] Compared to prior approaches,t hese methods are relatively mild and flexible,…”