453574-74-8Relevant academic research and scientific papers
Cyclocarbonylation of silicon tethered enynes derived from propargylic alcohols and vinylsilanes: A new reductive Pauson-Khand reaction with a traceless tether
Reichwein, John F.,Iacono, Scott T.,Patel, Mittun C.,Pagenkopf, Brian L.
, p. 3739 - 3741 (2002)
In nitrile solvents vinylsilyl ethers of propargylic alcohols undergo Pauson-Khand reaction with polysiloxane extrusion and concomitant reduction of the propargylic C-O bond. The product enones are formally the result of an intermolecular PKR reaction with ethylene.
On the mechanism of the silicon-tethered reductive Pauson-Khand reaction
Reichwein, John F,Iacono, Scott T,Pagenkopf, Brian L
, p. 3813 - 3822 (2007/10/03)
The reductive Pauson-Khand reaction (PKR) of tethered vinyl silanes likely proceeds as usual to the bicyclopentenones 2, but rapid loss of the allylic silane initiates a fragmentation process culminating in propargylic carbon reduction. Damp nitrile solvents are crucial for efficient reaction, and under dry conditions additional products are obtained including dimerized cyclopentadienones and 5-(1-amino-alkylidine) cyclopentenes. Solvent incorporated enones likely arise from enolate attack on a cobalt coordinated nitrile. A unified reaction mechanism is proposed. The first example of a PKR with an allyloxy ethynylsilane is also reported.
