Highly Strained Tertiary sp3 Scaffolds: Synthesis of Functionalized Cubanes and Exploration of Their Reactivity under Pd(II) Catalysis

Abstract

A series of chemically distinct, highly strained, activated cubane scaffolds was synthesized through optimization of the metal-halogen exchange reactions of iodinated cubane derivatives. This included the first reported successful attachment of both boron and phosphorous; key elements in potential transition metal-catalyzed cross coupling reactions; on the cubane scaffold. Additionally, Zn, Sn, Si, S and various C-based systems were also attached in a high-yielding, one-pot reaction from readily available precursors. A comprehensive program investigating the reactivity of these tertiary cubane nucleophiles towards Suzuki-Miyaura, Negishi and Stille cross-coupling methods, never previously reported with the cubane scaffold; is also described, but proved unsuccessful.