3 research outputs found
Rhodium-Catalyzed Carbonylation of 3-Acyloxy-1,4-enynes for the Synthesis of Cyclopentenones
Functionalized cyclopentenones were synthesized by a Rh-catalyzed carbonylation of 3-acyloxy-1,4-enynes, derived from alkynes and α,β-unsaturated aldehydes. The reaction involved a Saucy–Marbet 1,3-acyloxy migration of propargyl esters and a [4 + 1] cycloaddition of the resulting acyloxy substituted vinylallene with CO
Rhodium-Catalyzed Chemo- and Regioselective Cross-Dimerization of Two Terminal Alkynes
Cross-dimerization of terminal arylacetylenes and terminal propargylic alcohols/amides has been achieved in the presence of a rhodium catalyst. This method features high chemo- and regioselectivities rendering convenient and atom economical access to functionalized enynes
Rhodium-Catalyzed Intra- and Intermolecular [5 + 2] Cycloaddition of 3-Acyloxy-1,4-enyne and Alkyne with Concomitant 1,2-Acyloxy Migration
A new type of rhodium-catalyzed [5 + 2] cycloaddition
was developed
for the synthesis of seven-membered rings with diverse functionalities.
The ring formation was accompanied by a 1,2-acyloxy migration event.
The five- and two-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes
(ACEs) and alkynes, respectively. Cationic rhodiumÂ(I) catalysts worked
most efficiently for the intramolecular cycloaddition, while only
neutral rhodiumÂ(I) complexes could facilitate the intermolecular reaction.
In both cases, electron-poor phosphite or phosphine ligands often
improved the efficiency of the cycloadditions. The scope of ACEs and
alkynes was investigated in both the intra- and intermolecular reactions.
The resulting seven-membered-ring products have three double bonds
that could be selectively functionalized