Recent Advances in Catalytic Alkyne Transformation via Copper Carbene Intermediates

Abstract

As one of the abundant and inexpensive metals on the earth, copper has demonstrated broad applications in synthetic chemistry and catalysis. Among these copper-catalyzed advances, copper carbenes are versatile and reactive intermediates that can mediate a variety of transformations, which have attracted much attention in the past decades. The present review summarizes two different reaction models that take place between a copper carbene intermediate and alkyne species, including the cross-coupling reaction of copper carbene intermediate with terminal alkyne, and the addition of copper carbene intermediate onto the C–C triple bond. This article will cover the profile from 2010 to 2021 by placing emphasis on the detailed catalytic models and highlighting the synthetic applications offered by these practical and mild methods.

Transition metal catalysed cascade C–C and C–O bond forming events of alkynes

“…The domino functionalization of alkynes mainly involves simultaneous C-C and C-X bond-forming events. [11][12][13][14][15][16][17][18] In this context, the vicinal/geminal cascade functionalization of alkynes involving the C-C and C-O bond formation reaction has been thoroughly studied and numerous elegant approaches have been described in the literature. Different modes of cascades are described in Fig.…”

Metal-Catalysed A3 Coupling Methodologies: Classification and Visualisation

“…Several reviews discuss the role of the metal salts and organic ligands [73][74][75][76][77][78][79] and address catalyst design parameters. These include operational stability and a partially saturated coordination environment fulfilled by ligands bearing two or three heteroatoms.…”

Mechanochemical Cu(ii) complexes and propargylamine synthetic adventures

“…16 The A 3 coupling reaction is a popular organic pathway for synthesizing PAs in the presence of late (Cu, Pd, or Au) transition metals. [17][18][19][20][21][22][23][24][25][26][27][28][29] This process involves three substrates, amine-alkyne-aldehyde and the in situ formation of a p complex (metal-alkyne), which weakens the C-H sp bond with subsequent proton elimination by a weak base, resulting in s activation and formation of the acetylide, which can be subsequently added to the imine (product of the amine-aldehyde condensation), yielding the PA. 14 The A 3 coupling reaction has been a desirable target for mechanochemical synthesis, as it allows for the rapid and efficient construction of complex molecules with high structural diversity. In 2015, Su et al demonstrated a solvent-free enantioselective PAs synthesis via a Cu(OTf) 2 /Phpybox system by ball-milling within 60 minutes.…”