Transition-metal-catalyzed cleavage of carbon-selenium bond and addition to alkynes and allenes

Abstract

This account summarizes our recent results on transition-metal-catalyzed cleavage of C-Se bond and addition to unsaturated hydrocarbons such as alkynes and allenes. Pd(0)-catalyzed intramolecular carbamoselenation of alkynes forms four- to eight-membered α-alkylidenelactams. Interestingly, four-membered ring formation is faster than five- and sixmembered ring formation. Intramolecular vinylselenation of suitably structured alkynes offers pathways to conjugated α-lactam frameworks. Electron-withdrawing groups on the vinyl moiety are essential to promote this reaction. Intermolecular 1,2-addition of selenol esters onto allenes proceeds with excellent regioselectivity and high stereoselectivity in the presence of a Pd(0) catalyst, producing functionalized allyl selenides. In addition, Pd(0)-catalyzed intramolecular selenocarbamoylation of allenes gives α,β-unsaturated γ- and δ-lactams with perfect regioselectivity. The scope and limitations, as well as reaction pathways, are discussed. © 2010 IUPAC.