Synthesis and reactions of [(((η6)-2-acylaryl)-C,O)tetracarbonylmanganese]-tricarbonylchromium complexes: enhancement of diastereoselection during cyclopentaannulation
摘要:
Cyclomanganation reactions of [(eta(6))-acylaryl]tricarbonylchromium complexes have been investigated, Three novel heterobimetallic complexes have been synthesised in moderate to good yield, with one being characterised by X-ray crystallography. Several modes of activating these bimetallic complexes towards coupling reactions with substituted alkenes and alkynes were investigated, including oxidative decarbonylation at room temperature, and thermal promotion. The stereochemistry of one of the cyclopentaannulated adducts has been established by X-ray crystallography. Thermal displacement of one of the CO ligands of the bimetallic complex 27 in the presence of PPh(3) afforded a single adduct, the structure of which was established by X-ray crystallography. The chemistry of this novel bimetallic system was investigated.
Ketones and alkynes join together: The catalytic title reaction proceeds rapidly at 120 °C and requires only 1 hour for completion (see scheme). The reaction mechanism likely involves chelation‐assisted ortho CHactivation, insertion of the alkyne moiety, carbocyclization, and protonation. Cp*=pentamethylcyclopentadienyl.