Construction of epidithiodioxopiperazines by directed oxidation of hydroxyproline-derived dioxopiperazines.
Functionalization of the angular methine carbon of hydroxyproline-derived dioxopiperazines by a radical-promoted C-H bond oxidation, which is directed by a proximal (bromomethyl)silyl group, is described. This regioselective oxidation is the key step in a new synthesis of epidithiodioxopiperazines.
Overman
Larry E
LE
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92687-2025, USA. leoverma@uci.edu
Sato
Takaaki
T
D001688:Biological Products / Q000737:chemistry; D018360:Crystallography, X-Ray; D004986:Ether / Q000737:chemistry; D006909:Hydroxyproline / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010879:Piperazines / Q000138:chemical synthesis* / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014364:Tryptophan / Q000737:chemistry
D001688:Biological Products; D010879:Piperazines; D013438:Sulfhydryl Compounds; D004986:Ether; D014364:Tryptophan; D006909:Hydroxyproline; D010100:Oxygen