Abstract
Alkylidenecyclopropanes containing a chelation assistant at the terminal carbon atom of the olefinic moiety undergo an Os- or Ru-promoted ring expansion reaction to afford metal cyclobutylidene derivatives. The process occurs through a novel mechanism that implies a 1,2-migration of a CH(2) group of the three-membered ring from an olefinic carbon atom to the other one. It takes place, without direct participation of the metal, on a metallaheterocyclopentene intermediate which is generated from an eta(2)-methylenecyclopropane species stabilized by coordination of the chelation assistant.
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