This highlight discusses developments in transition metal-catalysed alkene and alkyne hydroacylation reactions over the past three years. The discussion summarizes the development of new catalyst systems for alkene and alkyne hydroacylation and applications to the synthesis of important ketone building blocks. The highlight captures transition metal-catalysed alkene and alkyne hydroacylation at...

In this work, the SBA-15-supported dithizone-copper(I) [SBA-15-dtz–Cu(I)] complex as a new heterogeneous catalyst is prepared for the first time. The catalyst prepared is characterized by the FT-IR spectroscopy, SEM, and ICP techniques. This reusable heterogeneous catalyst can be used in the click reactions for the green and facile synthesis of 1,4-disubstituted 1,2,3-triazolesvia a on...

Here we describe the metathesis reactions of a strained eight-membered ring that contains both alkene and alkyne functionality. We find that the alkyne metathesis catalyst produces polymer through a ring-opening alkyne metathesis reaction that is driven by the strain release from the monomer. The strained monomer provides unusual reactivity with ruthenium-based alkene metathesis catalysts. We i...

Platinum(II) complexes bearing various alkyne-pyrene, alkyne-4'-terpyridine and alkyne-dibutoxyphenylacetylide-terpyridine units were constructed in a step-by-step procedure based on copper-promoted cross-coupling reactions with preconstructed modules; formation of bis(ligand) complexes of Fe(II) and Zn(II) by binding of the pendent terpyridine units provided heterotrinuclear derivatives, all o...

Aromatic ynamines or N-alkynylheteroarenes are highly reactive alkyne components in Cu-catalyzed Huisgen [3 + 2] cycloaddition ("click") reactions. This enhanced reactivity enables the chemoselective formation of 1,4-triazoles using the representative aromatic ynamine N-ethynylbenzimidazole in the presence of a competing aliphatic alkyne substrate. The unique chemoselectivity profile of N-ethyn...

The reaction pathway for the addition of alkynes to tetramesityldigermene was examined using a cyclopropyl alkyne mechanistic probe. The results obtained indicate that the reaction is stepwise and involves biradical intermediates.

The benzannulation reaction of Fischer carbene complexes is investigated under conditions where the reaction of the carbene complex is occurring in the presence of two different alkynes. A series of competition experiments are examined where the effects of various structural factors are explored by pitting 10 different carbene complexes with 11 different alkynes. Terminal alkynes will react sel...

We report a novel solid phase method for the sequential coupling of heterobifunctional macromonomers to form a new class of polymeric materials that we refer to as polymacromers. Starting from an azide functional substrate, αazido, ω-protected-alkyne macromonomers are added sequentially by thermally initiated click reactions to form polymacromer brushes wherein macromonomers are linked via tria...

Alkyne metathesis is increasingly explored as a reliable method to close macrocyclic rings, but there are no prior examples of an alkyne-metathesis-based homodimerization approach to natural products. In this approach to the cytotoxic C2-symmetric marine-derived bis(lactone) disorazole C1, a highly convergent, modular strategy is employed featuring cyclization through an ambitious one-pot alkyn...