title: Fate of the intermediate diradicals in the caldera: stereochemistry of thermal stereomutations, (2 + 2) cycloreversions, and (2 + 4) ring-enlargements of cis- and trans-1-cyano-2-(E and Z)-propenyl-cis-3,4-dideuteriocyclobutanes.
abstract: This paper addresses the decades-old problem of gaining a measure of intellectual control over the fate of the diradical intermediate in not-obviously-concerted thermal rearrangements. It focuses mainly on the stereochemistry of the thermal rearrangement of cis- and trans-1-cyano-2-trans-propenylcyclobutane to the related ring-enlarged products, 4-cyano-3-methylcyclohexenes. The complete stereochemical profile is revealed by the incorporation of a pair of cis deuterons to serve as a stereochemical lighthouse. The striking result (besides providing a further example of the inapplicability of the orbital symmetry rules of Woodward and Hoffmann to not-obviously-concerted reactions) is the predominance of the same stereoisomer regardless whether starting from the cis or trans educt. This preference is rationalized by a simple conceptual scheme based on two premises of the behavior of the diradical as intermediate: removal of the diradical from the caldera of rotationally labile conformations occurs whenever the two radical centers come within bonding distance in an appropriate orientation of orbitals; relative internal rotational rates are in the order, cyanomethyl faster than methallyl, faster than internal rotation about the backbone.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138-2902, USA. doering@chemistry.harvard.edu
authors.forename: W von E
authors.initials: Wv
authors.lastname: Doering
authors.forename: Xueheng
authors.initials: X
authors.lastname: Cheng
authors.forename: Kyuwang
authors.initials: K
authors.lastname: Lee
authors.forename: Zisen
authors.initials: Z
authors.lastname: Lin
mesh_terms: D003503:Cyclobutanes / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D006361:Heating; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D003503:Cyclobutanes; D005609:Free Radicals; D003903:Deuterium