Boronate Ester Bullvalenes

Boronate ester bullvalenes are now accessible in two to four operationally simple steps. This unlocks late-stage diversification through Suzuki cross-coupling reactions to give mono-, di-, and tri-substituted bullvalenes. Moreover, a linchpin strategy enables pre-programmed installation of two different substituents. Analysis of solution phase isomer distributions and single crystal X-ray structures reveals that isomer preference in the crystal lattice is due to general shape selectivity.