title: The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.
abstract: The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.
authors.affiliation: Faculty of Mathematics and Natural Science, The Jan Kochanowski University in Kielce , Świętokrzyska 15, 25-406 Kielce, Poland.
authors.forename: Karolina
authors.initials: K
authors.lastname: Stefańska
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences , Kasprzaka 44/52, 01-224 Warsaw, Poland.
authors.forename: Hanna
authors.initials: H
authors.lastname: Jędrzejewska
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences , Kasprzaka 44/52, 01-224 Warsaw, Poland.
authors.forename: Michał
authors.initials: M
authors.lastname: Wierzbicki
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences , Kasprzaka 44/52, 01-224 Warsaw, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Szumna
authors.affiliation: Faculty of Mathematics and Natural Science, The Jan Kochanowski University in Kielce , Świętokrzyska 15, 25-406 Kielce, Poland.
authors.forename: Waldemar
authors.initials: W
authors.lastname: Iwanek