kulinkovich reaction jaa反应.pdfVIP

Published on Web 01/27/2004 Stereochemistry of Cyclopropane Formation Involving Group IV Organometallic Complexes Charles P. Casey* and Neil A. Strotman Contribution from the Department of Chemistry, Uniersity of Wisconsin, Madison, Wisconsin 53706 Received July 18, 2003; E-mail: casey@chem.wisc.edu Abstract: The reaction of (Z)-HDCCHCH(OCH )C H (1) with Cp Zr(D)Cl followed by BF OEt gave 3 6 5 2 3 2 phenylcyclopropanes 3a and 3b, both having cis deuterium. This stereochemical outcome requires inversion of configuration at the carbon bound to zirconium and is consistent with a “W-shaped” transition state structure for cyclopropane formation. In a Kulinkovich hydroxycyclopropanation, trans-3-deutero-1-methyl- cis-2-phenyl-1-cyclopropanol (5) was formed stereospecifically from Ti(O-i-Pr) , ethyl acetate, EtMgBr, and 4 trans--deuterostyrene. This stereochemistry requires retention of configuration at the carbon bound to titanium and is consistent with frontside attack of the carbontitanium bond on a carbonyl group coordinated to titanium. In a de Meijere cyclopropylamine synthesis, a 3:1 mixture of N,N-dimethyl-N-(trans-3-deutero- trans-2-phenylcyclopropyl)amine (