Palladium catalyzed C(sp³)–H acetoxylation of aliphatic primary amines to γ-amino alcohol derivatives

Abstract

It still remains a major challenge to apply free primary amino groups as the directing group for aliphatic C–H functionalization.

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[111][112][113][114][115] Therefore,m ajor studies have focused on amine functionalization either by protection or by installing adirecting group on the amino function. This can be attributed to the high reactivity of amines towards various reagents and their strong coordinating ability towards am etal center, which makes them inconvenient for use in ac atalytic reaction.…”

“…This can be attributed to the high reactivity of amines towards various reagents and their strong coordinating ability towards am etal center, which makes them inconvenient for use in ac atalytic reaction. [111][112][113][114][115] Therefore,m ajor studies have focused on amine functionalization either by protection or by installing adirecting group on the amino function. Although the major focus of this Review is on directed CÀHf unctionalization, we also summarize our current knowledge on the CÀHfunctionalization of amines where ad irecting group is installed on the amino function.…”

Rhodiumkatalysierte sp2‐ und sp3‐C‐H‐Funktionalisierungen mit entfernbaren dirigierenden Gruppen

“…Dies kann der hohen Reaktivität von Aminen mit verschiedenen Reagenzien zugeschrieben werden und der starken Koordinationsfähigkeit an Metallzentren. Letzteres erschwert die Verwendung in katalytischen Reaktionen . Daher wurden umfangreiche Untersuchungen zur Aminfunktionalisierung, entweder durch Schützen oder durch Einführen einer dirigierenden Gruppe an der Aminofunktion, vorangetrieben.…”

Palladium‐Catalyzed C(sp3)−H Arylation of Primary Amines Using a Catalytic Alkyl Acetal to Form a Transient Directing Group

“…Notably, Gaunt developed palladium‐catalyzed functionalization of hindered secondary amine substrates, to avoid formation of inactive bis(amine) palladium complexes, including the arylation of tetramethylpiperidine derivatives (Scheme a) . Shi reported acetoxylation of t ‐amylamine in AcOH with diacetoxyiodobenzene as the oxidant, minimizing inactive amine‐Pd complexes by protonation …”

“…[5d] Shi reported acetoxylation of t-amylamine in AcOH with diacetoxyiodobenzene as the oxidant, minimizing inactive amine-Pd complexes by protonation. [6] Very recently,t ransient directing groups (TDGs) have been applied to the functionalization of C(sp 3 )ÀHb onds, [7] particularly arylation of aldehyde andk etones ubstrates via endo-imines formed in situ with amine additives. [8] The use of exo-imine directingg roups for CÀHf unctionalization of primary amines remainsr are, with examples using palladium catalysis.…”