Leveraging Cubenes to Access Highly Functionalized Fused Cubes

Abstract

Abstract Since 1913, cubane has fascinated chemists owing to its remarkable structure. More recently, however, cubanes have emerged as attractive bioisosteres for aromatic rings. Although substituted derivatives are relatively common, ring-fused cubanes (a.k.a. “fused cubes”) are rare and can be difficult to access. Here, we report a strategy for the synthesis of fused cubes leveraging cubenes, unusual fleeting intermediates possessing hyperpyramidalized alkenes, in strain-promoted trapping reactions. Further, experimental and computational studies for the generation and reactivity of unsubstituted cubene and new substituted cubenes are disclosed. These studies not only push the limits of strained intermediate chemistry but also provide an entryway to highly functionalized fused cubes, including new three-dimensional hybrid structures and other unprecedented chemical space.