乙炔 环丙烯化.pdfVIP

Synthesis of Stable Derivatives of SCHEME 1. Synthesis of Cycloprop-2-ene Carboxylic Acid 3-(Cycloprop-2-en-1-oyl)oxazolidinones Ni Yan, Xiaozhong Liu, Mahesh K. Pallerla, and Joseph M. Fox* Brown Laboratories, Department of Chemistry and Biochemistry, Uni Versity of Delaware, Newark, Delaware 19716 jmfox@ Recei Ved January 8, 2008 Large-scale syntheses of 3-(cycloprop-2-en-1-oyl)oxazoli- dinones from acetylene and ethyl diazoacetate are described. Unlike other cyclopropenes that bear a single substitutent at C-3, these compounds are stable to long-term storage. Although the cyclopropene derivatives are unusually stable, they are reactive toward cyclic and acyclic dienes in stereoselective Diels-Alder reactions. propenes with a single substituent at their sp3 centers has been limited by their instability. Thus, 3-methylcyclopropene is The Rh-catalyzed reaction of R-diazo esters with alkynes is extremely unstable, whereas 3,3-dimethylcyclopropene is quite an exceptionally useful and operationally simple method for the stable at room temperature.4 Although cycloprop-2-ene car- preparation of cycloprop-2-ene carboxylates1ssubstances that boxylates (1) are more stable than 3-alkylcyclopropenes, their are useful building blocks for a number of strain-assisted long-term storage is also not practical.3a Herein, we describe transformations.2 I