453574-73-7Relevant articles and documents
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.