Ruthenium-catalyzed oxidation of a carbon–carbon triple bond: facile syntheses of alkenyl 1,2-diketones from alkynes

Abstract

A new oxidation procedure of alkynes catalyzed by Tp(PPh(3))(CH(3)CN)Ru-Cl is presented, which provides an efficient way to obtain alkenyl 1,2-diketones via ruthenium alkenyl 1,2-diketone intermediates. In contrast, the analogous reactions with Tp(PPh(3))(PhCN)Ru-Cl gave rise to the ruthenium metallacycle complexes.

Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of FcCN and FcCCCN

“…In the other cases of alkyne–nitrile coupling to give comparable five‐membered cycles, the established compounds were stabilized to give B1 (Scheme ). The formation of B1 was observed for zirconium,8 tungsten,9 iridium,10 osmium,11 and ruthenium 12. As the first step, the metallacyclopropenes of these elements reacted with nitriles to give 1‐metalla‐2‐aza‐cyclopenta‐2,4‐dienes.…”

“…The formation of B1 was observed for zirconium, [8] tungsten, [9] iridium, [10] osmium, [11] and ruthenium. [12] As the first step, the metallacyclopropenes of these elements reacted with nitriles to give 1-metalla-2-azacyclopenta-2,4-dienes.…”

Synthesis of 1,2‐Dicarbonyl‐3‐enes by Hydroacylation of 1‐Alkynes with Glyoxal Derivatives Using Metal–Organic Framework Cu/MOF‐74 as Heterogeneous Catalyst

“…[10] Lo and co-workers demonstrated ar uthenium-catalyzed oxidation of alkynes to form alkenyl-substituted 1,2-diketones. [11] However,ageneral methodf or the synthesis of alkenyl-substituted 1,2-diketones still remains to be explored. [11] Hashmi and co-workersr ecently reportedt he first example of aA uCl-catalyzed synthesis of 1,2dicarbonyl-3-enes by meanso ft he formal hydroacylation of terminal alkynes with a-ketoaldehydes in the presence of piperidine.…”

“…[11] However,ageneral methodf or the synthesis of alkenyl-substituted 1,2-diketones still remains to be explored. [11] Hashmi and co-workersr ecently reportedt he first example of aA uCl-catalyzed synthesis of 1,2dicarbonyl-3-enes by meanso ft he formal hydroacylation of terminal alkynes with a-ketoaldehydes in the presence of piperidine. [12] Independently,L ia nd co-workersa lso developed aC uBr-promoted approachf or the synthesis of 1,2-dicarbonyl-3-enes based on the formal hydroacylation reaction of terminal alkynes with a-carbonyl aldehydes in the presence of morpholine.…”

Preparation of ruthenium azido complex containing a Tp ligand and ruthenium-catalyzed cycloaddition of organic azides with alkynes in organic and aqueous media: Experimental and computational studies

“…The structures of these ruthenium azido complexes are shown in Scheme 2. Most of the complexes (1, 3 and 4) are known [16]. The catalytic properties of these ruthenium complexes were investigated using the cycloaddition of benzyl azide and phenylacetylene as the prototypical reaction.…”