title: Computational elucidation of the origins of reactivity and selectivity in non-aldol aldol rearrangements of cyclic epoxides.
abstract: The non-aldol aldol reaction of the isomeric epoxy silyl ethers is controlled by the conformation of the transition states leading to an internal hydride shift. One isomer rearranges to the β-silyloxy ketone whereas the other isomer gives a β-elimination product. Theoretical calculations show that the substrates with substituents that favor the formation of the chairlike transition state rearrange normally while those that do not undergo elimination instead.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095-1569, USA.
authors.forename: Hao
authors.initials: H
authors.lastname: Wang
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Damian A
authors.initials: DA
authors.lastname: Allen
authors.forename: Michael E
authors.initials: ME
authors.lastname: Jung
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008962:Models, Theoretical; D015394:Molecular Structure; D012821:Silanes / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D004852:Epoxy Compounds; D007659:Ketones; D012821:Silanes; C116609:3-hydroxybutanal