title: Stereocontrol of intramolecular Diels-Alder reactions by an allylic diphenylcyclopropyl group.
abstract: Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes carrying a diphenylcyclopropyl substituent attached to C1 proceed with high levels of stereoselectivity. The stereochemical outcomes of these reactions are explained by reference to B3LYP/6-31G(d) transition structures. Experimentally, the diphenylcyclopropane rings remain intact through these IMDA reactions, notwithstanding their predicted extremely high degree of asynchronicity (the B3LYP-computed lengths in the IMDA transition structures differ by as much as 1.1 angstroms), providing support to the notion that these reactions are concerted processes.
authors.affiliation: Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
authors.forename: Regis
authors.initials: R
authors.lastname: Tripoli
authors.forename: Tory N
authors.initials: TN
authors.lastname: Cayzer
authors.forename: Anthony C
authors.initials: AC
authors.lastname: Willis
authors.forename: Michael S
authors.initials: MS
authors.lastname: Sherburn
authors.forename: Michael N
authors.initials: MN
authors.lastname: Paddon-Row
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D002264:Carboxylic Acids; D003521:Cyclopropanes; D004952:Esters; C047607:diphenylcyclopropane