Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones

Abstract

The highly efficient addition of phosphorus and carbon pronucleophiles to α-methylene-γ-butyrolactones (tulipalin A and arglabin) under n-Bu₃P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s-cis geometry of the 1-oxa-1,3-butadiene moiety that favors generation of zwitterionic intermediate stabilized by interaction between the phosphonium center and adjacent carbonyl oxygen. The presented strategy offers an economical and practical method for functionalization of natural biologically active α-methylene-γ-butyrolactones with high levels of chemo- and stereoselectivity.