An approach to the total synthesis of the marine ascidian metabolite perophoramidine via a halogen-selective tandem Heck/carbonylation strategy.
A halogen-selective tandem intramolecular Heck/carbonylation reaction has been developed for the construction of the C,E,F-ring system and the C20 quaternary center found in perophoramidine (1). This process can be effected in good yields in the presence of both the chlorine and bromine atoms found in the natural product. In addition, it is possible to introduce the quaternary center at C4 in a stereoselective manner by a lactone enolate alkylation, using NaH and allyl bromide. [reaction: see text]
Artman
Gerald D
GD
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA.
Weinreb
Steven M
SM
D000478:Alkylation; D000818:Animals; D003500:Cyclization; D006219:Halogens / Q000737:chemistry; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis*; D006846:Hydrocarbons, Halogenated / Q000138:chemical synthesis*; D007783:Lactones / Q000737:chemistry; D013237:Stereoisomerism; D014561:Urochordata / Q000737:chemistry*
D006219:Halogens; D006576:Heterocyclic Compounds, 4 or More Rings; D006846:Hydrocarbons, Halogenated; D007783:Lactones; C472225:perophoramidine