title: Asymmetric total synthesis of (+)-didemniserinolipid B via Achmatowicz rearrangement/bicycloketalization.
abstract: A new synthetic strategy was developed for the asymmetric total synthesis of (+)-didemniserinolipid B in 19 linear steps, featuring a highly efficient and enantioselective construction of 6,8-dioxabicyclo[3.2.1]octane (6,8-DOBCO) framework via a rarely explored Achmatowicz rearrangement/bicycloketalization strategy. In addition, the first total synthesis of the proposed (+)-didemniserinolipid C was accomplished with 41.6% yield in 4 steps from a common advanced intermediate 18, and a possible revised structure of (+)-didemniserinolipid C was proposed. The new convergent synthetic strategy greatly expedites the entry to the didemniserinolipids and their analogues for biological activity evaluation.
authors.affiliation: Department of Chemistry, The Hong Kong University of Science and Technology , Clearwater Bay, Kowloon, Hong Kong, China.
authors.forename: Jingyun
authors.initials: J
authors.lastname: Ren
authors.forename: Rongbiao
authors.initials: R
authors.lastname: Tong
mesh_terms: D001669:Biochemical Phenomena; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D003500:Cyclization; D015394:Molecular Structure; D011409:Propylene Glycols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C000595010:6,8-dioxabicyclo(3.2.1)octane; D001643:Bridged Bicyclo Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D011409:Propylene Glycols; C467921:didemniserinolipid B