title: Unified Synthesis of 10-Oxygenated Lycopodium Alkaloids: Impact of C10-Stereochemistry on Reactivity.
abstract: The pronounced impact of the C10 stereochemistry on the successful construction of a polycyclic Lycopodium alkaloid scaffold has been explored. A wide range of reaction conditions and functionality were investigated to control a keto sulfone Michael addition to construct the C7-C12 linkage. An unexpected, overriding impact of the C10 stereochemistry in stereoselectivity and reaction rate in the Michael addition was observed. Furthermore, divergent reactivity of a conformationally accelerated, intramolecular Mannich cyclization based on the C10 stereochemistry was discovered. The successful execution of this synthetic route resulted in the total synthesis of all three known 10-oxygenated Lycopodium alkaloids: 10-hydroxylycopodine, paniculine, and deacetylpaniculine.
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Mrinmoy
authors.initials: M
authors.lastname: Saha
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Xin
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Nathan D
authors.initials: ND
authors.lastname: Collett
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Rich G
authors.initials: RG
authors.lastname: Carter
mesh_terms: D000470:Alkaloids / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D007659:Ketones / Q000737:chemistry; D032502:Lycopodium / Q000737:chemistry*; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D011807:Quinolizines / Q000737:chemistry; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry
chemical_list: C581765:10-hydroxylycopodine; D000470:Alkaloids; D007659:Ketones; D011807:Quinolizines; D013450:Sulfones; C581766:deacetylpaniculine; C480481:himeradine A; C581767:paniculine; D010100:Oxygen