Using Nazarov Electrocyclization to Stage Chemoselective [1,2]-Migrations: Stereoselective Synthesis of Functionalized Cyclopentenones

Authors


  • We thank the National Institutes of Health (NIGMS R01 GM079364, supporting J.H.) and the National Science Foundation (grant no. CHE-0847851, supporting D.L.) for funding this research. We thank R. Eisenberg for useful discussions. We used the computing facility of the CRIHAN (project no. 2006-013).

Abstract

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Highly functionalized cyclopentenones have been prepared stereospecifically through a chemoselective copper(II)-mediated Nazarov/Wagner–Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]-migrations depending upon both migratory ability and steric bulk of the substituents at C1 and C5 (see scheme). The proposed mechanism of the reaction is supported by DFT studies.

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