Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with Möbius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic Möbius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral Möbius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes.

We report density-functional and coupled-cluster calculations on conformation change and degenerate bond shifting in [10]annulene isomers 1-5. At the CCSD(T)/cc-pVDZ//CCSD/6-31G level, conversion of the twist (1) to the heart (2) has a barrier of 10.1 kcal/mol, compared to Ea = 16.2 kcal/mol for degenerate "two-twist" bond shifting in 1. Pseudorotation in the all-cis boat isomer (3) proceeds with a negligible barrier. The naphthalene-like isomer 4 has a 3.9 kcal/mol barrier to degenerate bond shifting. The azulene-like isomer 5 is the only species for which the nature of the bond-equalized form (5-eq) depends on the method. At the CCSD(T)/cc-pVDZ//CCSD/6-31G level, 5-eq is 1.2 kcal/mol more stable than the bond-alternating form 5-alt. Conversion of 5-eq to 4 has a barrier of 12.6 kcal/mol. Despite being significantly nonplanar, both 5-eq and the transition state for bond shifting in 4 are highly aromatic based on magnetic susceptibility exaltations. On the basis of a detailed consideration of these mechanisms and barriers, we can now, with greater confidence, rule out 4 and 5 as candidates to explain the NMR spectra observed by Masamune. Our results support Masamune's original assignments for both isolated isomers.

Dynamics calculations are described for carbocation rearrangements involving product-forming pathways with post-transition-state bifurcations. We show that noncovalent interactions with associated benzene rings (a simple model of aromatic amino acid side chains) can switch inherent dynamical tendencies for competing modes of disrotation, establishing that meaningful changes in dynamically controlled product selectivity can be achieved with few weak noncovalent interactions.

The lifetimes of secondary carbocations proposed to occur along reaction coordinates for terpene-forming carbocation rearrangements were estimated from direct dynamics simulations using density functional theory. Classical secondary carbocations supported by bicyclo[2.2.1] and bicyclo[2.2.2] frameworks have distinct characteristic lifetimes, ca. 40 and 90 fs, respectively. The fusion of additional rings to these frameworks was found to have little effect on these lifetimes, despite altering the potential energy surfaces for rearrangement. Inherent dynamical tendencies of secondary carbocations are shown to be manipulable by alkylation and enforced intermolecular interactions.

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