Controlled Acceleration and Inhibition of Bergman Cyclization by Metal Chlorides
Benjamin P. Warner 1,
Susan P. Millar 2,
Richard D. Broene 2, and
Stephen L. Buchwald 1
1 Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
2 Department of Chemistry, Bowdoin College, Brunswick, ME 04011, USA.
The Bergman cyclization has been the subject of renewed interest with the discovery of naturally occurring enediyne-based antitumor agents that cleave DNA by means of an aromatic diradical. These natural substrates have a means to trigger this cycloaromatization process. Control of this reaction by substrate modification would allow aromatic diradicals to be generated selectively. In the studies presented here it is disclosed that the Bergman cyclization of 1,2-bis(diphenyl phosphinoethynyl) benzene was accelerated by a factor of >30,000 by the addition of palladium(II) chloride or platinum(II) chloride and was inhibited by the addition of mercury(II) chloride.
Submitted on March 14, 1995
Accepted on June 14, 1995
