A symmetry-driven approach toward the total synthesis of dodecahedrane. (5th November 2022)

• Record Type: Journal Article
• Authors: Chari, Jason V.; McDermott, Luca; Dander, Jacob E.; Simmons, Bryan J.; Garg, Neil K.
• Is Part Of: Tetrahedron. Volume 126(2022)
• Publication Date: 2022-11-05
• Subjects: Total synthesis -- Polyene cyclization -- Platonic hydrocarbon -- Metathesis; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2022.133041
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: Herein, 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. Graphical abstract: Image 1