A symmetry-driven approach toward the total synthesis of dodecahedrane

Tetrahedron. 2022 Nov 5;126:133041. doi: 10.1016/j.tet.2022.133041. Epub 2022 Sep 21.ABSTRACTHerein, we describe our progress toward the total synthesis of dodecahedrane, a complex and highly symmetrical hydrocarbon that bears twelve fused rings arranged in a cage-like architecture. Central to our approach is a late-stage [2+2+2+2+2] polyene cyclization cascade, which is expected to construct five new bonds and ten new rings in a single transformation. Toward this end, we describe efforts to synthesize key monomeric fragments, along with successful dimerization studies using a pinacol coupling approach. Subsequent studies include an attempted olefin metathesis rearrangement cascade in addition to a successful intramolecular photochemical [2+2] reaction. Although attempts to elaborate the photocycloaddition product were unsuccessful, our studies provide access to complex dimeric scaffolds and are expected to help guide our future total synthesis studies.PMID:37663313 | PMC:PMC10470822 | DOI:10.1016/j.tet.2022.133041

Source: Tetrahedron - September 4, 2023 Category: Chemistry Authors: Jason V Chari Luca McDermott Jacob E Dander Bryan J Simmons Neil K Garg Source Type: research