title: Synthetic efforts toward the Lycopodium alkaloids inspires a hydrogen iodide mediated method for the hydroamination and hydroetherification of olefins.
abstract: Progress toward the total syntheses of a diverse set of fawcettimine-type Lycopodium alkaloids via a "Heathcock-type" 6-5-9 tricycle is disclosed. This route features an intermolecular Diels-Alder cycloaddition to rapidly furnish the 6-5-fused bicycle and a highly chemoselective directed hydrogenation to build the azonane fragment. While conducting these synthetic studies, trimethylsilyl iodide was found to effect a hydroamination reaction to furnish the tetracyclic core of serratine and related natural products. This observation has been expanded into a general method for the room temperature hydroamination of unactivated olefins with tosylamides utilizing catalytic "anhydrous" HI (generated in situ from trimethylsilyl iodide and water). The presence of the iodide anion is critical to the success of this Brønsted acid catalyzed protocol, possibly due to its function as a weakly coordinating anion. These conditions also effect the analogous hydroetherification reaction of alcohols with unactivated olefins.
authors: Department of Chemistry, University of California, Berkeley, Latimer Hall, Berkeley, CA 94720 (USA), Fax: (+1) 510-642-9675.
authors: Paul R
authors: PR
authors: Leger
authors: Rebecca A
authors: RA
authors: Murphy
authors: Eugenia
authors: E
authors: Pushkarskaya
authors: Richmond
authors: R
authors: Sarpong
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D007454:Iodides; D006859:Hydrogen
keywords: Brønsted acid catalysis; Lycopodium alkaloids; hydroamination; total synthesis; trimethylsilyl iodide