CASSCF Computational Study of Pseudopericyclic Character in Electrocyclic Rearrangements Involving Heteroatoms.

The Complete Active Space Self-Consistent Field (CASSCF) computational method, with the 6-31G* basis set, was used to examine six electrocyclic rearrangements, each involving a 1,2,4,6-heptatetraene skeleton with two variously located oxygen and/or nitrogen heteroatoms, as a way to determine which, if any, are pseudopericyclic as opposed to pericyclic. Primarily through the close examination of the active space orbitals, but also considering transition structure geometries and activation energies, it was concluded that rearrangements 3 → 4, 5 → 6, 7 → 8, and 9 → 10 are pseudopericyclic with two orbital disconnections each, whereas the 13 → 14 and 15 → 16 rearrangements are pericyclic. Our conclusions agreed with those of others in two of the four cases that had been studied previously by density functional theory (3 → 4 and 7 → 8) but ran contrary to the previous conclusions that the 5 → 6 rearrangement is pericyclic and that the 15 → 16 rearrangement is pseudopericyclic.

CASSCF molecular orbital calculations reveal a purely pseudopericyclic mechanism for a [3,3] sigmatropic rearrangement.

A comparative CASSCF/6-31G*-level computational study of the concerted [3,3] sigmatropic rearrangements of cis-1-iminyl-2-ketenylcyclopropane (15), cis-1-iminyl-2-propadienylcyclopropane (17), and cis-1-iminyl-2-keteniminylcyclopropane (19) to give products 16, 18, and 20, respectively, was conducted. Analysis of the active space MOs of TS(15-->16), TS(17-->18), and TS(19-->20) suggests that the 17 --> 18 and 19 --> 20 rearrangements are classically pericyclic, whereas the 15 --> 16 rearrangement is pseudopericyclic with two orbital disconnections-one involving the nitrogen lone-pair orbital and the other the carbonyl carbon of the ketene moiety. The novel TS(15-->16) was also found to have a highly planar, tight, geometry, whereas TS(17-->18) and TS(19-->20) were both shown to have the boat-shaped geometry expected for classically pericyclic [3,3] sigmatropic rearrangements.