jo062594f_si_001.pdf (369.06 kB)
On Accounting for the Stereoselective Control of the Metal-Catalyzed Rautenstrauch Cyclopropanation by Computational Methods§
journal contribution
posted on 2007-03-30, 00:00 authored by Elena Soriano, José Marco-ContellesThe mechanism of the intramolecular Pt(II)-catalyzed Rautenstrauch cyclopropanation and the stereochemical implications have been investigated by computational methods. The
reaction takes place through a cyclopropanation step preceding the cleavage of the C−O bond, thus ensuring the transfer
of chiral information from the stereogenic propargylic center.
Our results agree with experimental findings and account
for the origin of the substrate-dependent selectivity on the
basis of subtle electronic effects and steric interactions in
the cyclopropanation transition-state structure.