Density functional theory computations were used to model the formation and rearrangement of the barbaralyl cation (C9H+ 9). Two highly delocalized minima were located for C9H+ 9, one of C s symmetry and the other of D 3h symmetry, with the former having lower energy. Quantum chemistry-based NMR predictions affirm that the lower energy structure is the best match with experimental spectra. Partial scrambling was found to proceed through a C 2 symmetric transition structure associated with a barrier of only 2.3 kcal mol-1. The full scrambling was found to involve a C 2v symmetric transition structure associated with a 5.0 kcal mol-1 barrier. Ab initio molecular dynamics simulations initiated from the D 3h C9H+ 9 structure revealed its connection to six minima, due to the six-fold symmetry of the potential energy surface. The effects of tunneling and boron substitution on this complex reaction network were also examined.

We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.

Selectivity in radical chain oligomerizations involving [1.1.1]propellane - i.e., to make [n]staffanes - has been notoriously challenging to control when n > 1 is desired. Herein, we report selective syntheses of SF5- and CF3SF4-containing [2]staffanes from SF5Cl and CF3SF4Cl, demonstrating cases whereby oligomerization is preferentially truncated after incorporation of two bicyclopentane (BCP) units. Synthetic and computational studies suggest this phenomenon can be attributed to alternating radical polarity matching. In addition, single-crystal X-ray diffraction (SC-XRD) data reveal structurally interesting features of the CF3SF4-containing [2]staffane in the solid state.