Biosynthesis and chemical synthesis of presilphiperfolanol natural products.
Presilphiperfolanols constitute a family of biosynthetically important sesquiterpenes which can rearrange to diverse sesquiterpenoid skeletons. While the origin of these natural products can be traced to simple linear terpene precursors, the details of the enzymatic cyclization mechanism that forms the stereochemically dense tricyclic skeleton has required extensive biochemical, computational, and synthetic investigation. Parallel efforts to prepare the unique and intriguing structures of these compounds by total synthesis have also inspired novel strategies, thus resulting in four synthetic approaches and two completed syntheses. While the biosynthesis and chemical synthesis studies performed to date have provided much insight into the role and properties of these molecules, emerging questions regarding the biosynthesis of newer members of the family and subtle details of rearrangement mechanisms have yet to be explored.
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, CA 91125 (USA).
Allen Y
AY
Hong
Brian M
BM
Stoltz
D001688:Biological Products / Q000138:chemical synthesis / Q000378:metabolism / Q000494:pharmacology; D003500:Cyclization; D004798:Enzymes / Q000378:metabolism; D005658:Fungi / Q000187:drug effects; D000081223:Polycyclic Sesquiterpenes; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism* / Q000494:pharmacology; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry
D001688:Biological Products; D004798:Enzymes; D000081223:Polycyclic Sesquiterpenes; D012717:Sesquiterpenes; D013729:Terpenes; C533354:presilphiperfolanol; C024714:caryophyllene
biosynthesis; natural products; structure elucidation; terpenoids; total synthesis