A general catalytic β-C–H carbonylation of aliphatic amines to β-lactams

Abstract

Methods for the synthesis and functionalization of amines are intrinsically important to a variety of chemical applications. We present a general carbon-hydrogen bond activation process that combines readily available aliphatic amines and the feedstock gas carbon monoxide to form synthetically versatile value-added amide products. The operationally straightforward palladium-catalyzed process exploits a distinct reaction pathway, wherein a sterically hindered carboxylate ligand orchestrates an amine attack on a palladium anhydride to transform aliphatic amines into β-lactams. The reaction is successful with a wide range of secondary amines and can be used as a late-stage functionalization tactic to deliver advanced, highly functionalized amine products of utility for pharmaceutical research and other areas.

Amination of isopropanol to isopropylamine over a highly basic and active Ni/LaAlSiO catalyst

“…Thus, the synthesis of aliphatic amines has always attracted considerable attention [1][2][3][4][5]. According to literature, the aliphatic amines were mainly produced through the reduction and ammonolysis processes.…”

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

“…[41] Subsequent studies showed that even non-bulky secondary amines can be used as substrates to synthesize b-lactams if AdCO 2 Ha nd benzoquinone are used as additives. [42] Thep utative fourmembered palladacycle can also be intercepted by aryl boronic acids,t hereby resulting in net arylation of the C À H bonds. [43] Arylated product 85 can be accessed from amine 84.…”

Cobalt-catalysed C–H carbonylative cyclisation of aliphatic amides

“…Prompted by our interest in catalytic oxidative C–H carbonylation reactions, 10–12 we reasoned that its merger with cobalt catalysis, guided by a pyridyl-derived auxiliary, would provide a distinct platform for C(sp 3 )–H activation using earth abundant metals. Herein, we report the development of an oxidative Co-catalysed carbonylative cyclisation procedure of aliphatic quinolinamides to yield a range of substituted succinimide products (Scheme 1C).…”