title: A Bioinspired Cyclization Sequence Enables the Asymmetric Total Synthesis of Dictyoxetane.
abstract: We have developed the first synthesis of the unique oxetane containing diterpene (+)-dictyoxetane. Our retrosynthetic planning was guided by the putative biosynthesis of the unprecedented 2,7-dioxatricyclo[4.2.1.0(3,8)]nonane ring system. A bioinspired 4-exo-tet, 5-exo-trig cyclization sequence enabled the construction of the synthetically challenging dioxatricyclic framework. The overall synthesis proceeds in 15 linear steps from a known and readily available trans-hydrindane fragment. In addition, we were able to realize the first dyotropic rearrangement of an epoxide-oxetane substrate.
authors.affiliation: Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich , Butenandtstrasse 5-13, 81377, Munich, Germany.
authors.forename: Cedric L
authors.initials: CL
authors.lastname: Hugelshofer
authors.affiliation: Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich , Butenandtstrasse 5-13, 81377, Munich, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Magauer