Stereoselective total syntheses of (−)-histrionicotoxin and (−)-histrionicotoxin 235A are described. The 1-azaspiro[5.5]undecane skeleton was constructed diastereoselectively by a radical translocation–cyclization reaction involving a chiral cyclic acetal; the use of tris(trimethylsilyl)silane was crucial for the high diastereoselectivity. The cyclization product was converted into (−)-histrionicotoxin 235A through a one-pot partial-reduction–allylation reaction of a derivative containing an unprotected lactam. Finally, two terminal alkenes were transformed into enynes with the 1,3-amino alcohol protected as an oxathiazolidine oxide to complete the total synthesis of (−)-histrionicotoxin.
|Number of pages||5|
|Journal||Angewandte Chemie - International Edition|
|Publication status||Published - 2017 Jan 19|
- radical cyclization
- spiro compounds
- total synthesis
ASJC Scopus subject areas