Studies of the chemistry of Tröger's base, cyclopentadienones, and 2,1-benzothiazines

Abstract

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] The sequential alkylation of Tröger's base was developed for the synthesis of symmetric dialkylation analogs. The products from this reaction were obtained in reasonable yields with regio- and stereoselectivity. The transformation of the products into chiral amines including the metal ion interaction studies of the new chiral ligands was investigated. A novel intramolecular cycloaddition of cyclopentadienone was developed by using molecules that had two cyclopentadienone units. It was demonstrated that the reaction occurs at room temperature or below to produce the dimer adducts in endo-selectivity. A variety of different substituted dimers containing an angular triquinane unit were prepared in relatively low yields. The coupling reaction of compounds incorporating an aryl ring processing a bromide ortho to an electron efficient alkene with methyl phenylsulfoximine was examined. This reaction provided the corresponding sulfoximines in high yields and also gave 2,1- benzothiazines in some cases. The intramolecular, stereoselective Micheal addition reaction of sulfoximine carbanions to compounds containing electron deficient alkenes was studied.