Allylic stereocontrol of the intramolecular Diels-Alder reaction.
The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituents about a stereogenic center attached to C1. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dienophile. The stereochemical outcomes of these reactions are explained by reference to B3 LYP/6-31G(d) transition structures. New insights into the conformational preferences of allylic alcohol derivatives are reported, results which allow an explanation of the differing levels of pi-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.
Lilly
Michael J
MJ
Institute of Fundamental Sciences, Massey University Private Bag 11222, Palmerston North, New Zealand.
Miller
Natalie A
NA
Edwards
Alison J
AJ
Willis
Anthony C
AC
Turner
Peter
P
Paddon-Row
Michael N
MN
Sherburn
Michael S
MS
D001205:Ascorbic Acid / Q000737:chemistry; D003201:Computers; D019344:Lactic Acid / Q000737:chemistry; D008293:Malates / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D013237:Stereoisomerism
D008293:Malates; D019344:Lactic Acid; C030298:malic acid; D001205:Ascorbic Acid