Subscribe to RSS
Synthesis of NakiterpiosinContributor(s):Philip Kocienski
The University of Texas Southwestern Medical Center at Dallas, USA
Synthesis and Structure Revision of Nakiterpiosin
J. Am. Chem. Soc. 2009, 131: 1410-1412
22 June 2009 (online)
nakiterpiosin - photo-Nazarov cyclization - carbonylative cross-coupling - Diels-Alder reaction
The synthesis of nakiterpiosin, a cytotoxic sponge metabolite, features a Pd-catalyzed carbonylative cross-coupling (K → L) followed by a photo-Nazarov cyclization (L → M) to create the indanone moiety.
The photo-Nazarov cyclization entails a thermal electrocyclization induced by photoisomerization of the enone L. Lewis acid cataly-zed variants were too harsh. CuCl and DMSO dramatically enhanced the rate of the cross-coupling K → L.