title: Construction of the Tricyclo
abstract: Histrionicotoxin derivatives have long been attractive targets for synthetic chemists as a result of their useful neurophysical properties, low natural abundance, and the unique structural features of the azaspiro[5.5]undecane ring system. Utilizing our tandem pinacol rearrangement-ene strategy and regiospecific Baeyer-Villiger oxidation as key steps, we have successfully synthesized an advanced synthetic intermediate, spiro[5.4]decane 4, which has previously been converted to (+/-)-perhydrohistrionicotoxin (5b). Pinacol rearrangement of simple Diels-Alder derived bicyclo[2.2.2]octene system 2a, followed by an ene reaction, led to the efficient formation of the highly fuctionalized tricyclo[5.3.1.0(1,5)]undecane system 1a. This tricyclic system 1a was selectively transformed into spiro[5. 4]decane system 4 via a regiospecific Baeyer-Villiger oxidation reaction. We also report the results of systematic studies of Baeyer-Villiger oxidation reactions of tricyclo[5.3.1.0(1, 5)]undecanone systems to elucidate the origin of the regioselectivity of this process.
authors.affiliation: Research Institute of Pharmaceutical Sciences, College of Pharmacy, Seoul National University, San 56-1, Shillim-Dong, Kwanak-Ku, Seoul 151-742, Korea.
authors.initials: D
authors.lastname: Kim
authors.initials: PJ
authors.lastname: Shim
authors.initials: J
authors.lastname: Lee
authors.initials: CW
authors.lastname: Park
authors.initials: SW
authors.lastname: Hong
authors.initials: S
authors.lastname: Kim