Exploiting the sp2 character of bicyclo[1.1.1]pentyl radicals in the transition-metal-free multi-component difunctionalization of [1.1.1]propellane

Photochemical Intermolecular [3σ + 2σ]-Cycloaddition for the Construction of Aminobicyclo[3.1.1]heptanes

“…Because of these enhanced properties, these bioisosteric scaffolds have received considerable attention in drug molecular design . One of the most studied among small-ring cage hydrocarbons are bicyclo[1.1.1]­pentanes (BCPs), which serve as a bioisosteric replacement of ortho- and para-substituted phenyl rings as well as the tert -butyl group . Synthetic organic chemists have also made great progress in the development of new synthetic methods that provide geometrically complementary meta-substituted arene bioisosteres.…”

Visible-light-induced direct perfluoroalkylation/heteroarylation of [1.1.1]propellane to diverse bicyclo[1.1.1]pentanes (BCPs) under metal and photocatalyst-free conditions

“…To meet the demands of step and atom economy, considerable effort has recently been devoted to developing multi-component reactions that enable one-step access to complex bicyclo[1.1.1]pentane (BCP) products. 6 In 2017, Uchiyama and coworkers reported iron-catalyzed radical multi-component carboamination of [1.1.1]propellane for the synthesis of 1-aminobicyclo[1.1.1]pentane. 6 a Later, MacMillan et al demonstrated a one-step three-component radical coupling of [1.1.1]propellane to give diverse bifunctionalized bicyclo[1.1.1]pentanes (BCPs) using a metallaphotoredox catalysis method.…”

Accelerated Synthesis of Bicyclo[1.1.1]pentylamines: A High-Throughput Approach

“…In the context of BCPs, recently disclosed synthetic manifolds provide rapid access to such versatile and bench-stable building blocks from [1.1.1]­propellane. State-of-the-art examples include BCPs functionalized with carboxylic acid, boronate, and iodine handles . We recognized that in addition to their utility in forming C–C bonds, these reactive functional groups have potential in transition-metal-catalyzed cross-coupling reactions to form C–N linkages as well, including those found in BCPAs .…”