Stereocontrol of intramolecular Diels-Alder reactions by an allylic diphenylcyclopropyl group.
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.
Tripoli
Regis
R
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Cayzer
Tory N
TN
Willis
Anthony C
AC
Sherburn
Michael S
MS
Paddon-Row
Michael N
MN
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
D000498:Allyl Compounds; D002264:Carboxylic Acids; D003521:Cyclopropanes; D004952:Esters; C047607:diphenylcyclopropane