SYNTHETIC METHODS .36. UTILIZATION OF ETHYL 2-((PHENYLSULFONYL)METHYL)ACRYLATE FOR THE SYNTHESIS OF ALPHA-METHYLENEVALEROLACTONES

A two-step sequence is described for conversion of cyclic and acyclic ketone enolates into α-methylenevalerolactones. The first step involves Michael addition to ethyl α-((phenylsulfonyl)methyl)acrylate 1 with concomitant elimination of PhS02 and formation of unsaturated keto esters 2–7. In the next sequence che-moselective ketone reduction is usually followed by spontaneous lactonization of acidification. Contrary to the five- and six-membered ring systems, the cis-fused isomer predominates in the seven- and eight-membered ring compounds 12 and 13. Spiro a-methylenevalerolactones 17a,b are as well obtainable by a short sequence of steps from 2-oxocyclohexanecarboxylate and 1. © 1990, American Chemical Society. All rights reserved.