A stereoselective intramolecular cyclopropanation via a de novo class of push-pull carbenes derived from DMDO-epoxidations of chiral ynamidesCCDC reference numbers 680316, 680317, 763759-763761. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c0nj00063a

This work describes the first examples of diastereoselective intramolecular cyclopropanations of a de novo class of push-pull carbenes derived from DMDO-epoxidations of chiral ynamides. This reaction sequence essentially constitutes a tandem epoxidation-cyclopropanation that effectively gives rise to a series of structurally unique amido-cyclopropanes. A plausible mechanistic model is proposed revealing insights into this novel cyclopropanation process. This work describes the first examples of diastereoselective intramolecular cyclopropanations of a de novo class of push-pull carbenes derived from DMDO-epoxidations of chiral ynamides.