Chiral β-substituted [3.3.0] bicyclic lactams can be synthesized with stereocontrol by cyclocondensation of substituted ketoacids and chiral amino alcohols. During synthesis, the β-position of the lactam is racemized due to dynamic kinetic resolution (DKR). Based on the proposed mechanism, this in situ epimerization occurs during equilibration of the acyliminium ion and enamine intermediates resulting in a predominantly endo selectivity in the final β-substituted lactam product. Data reported in this thesis from experimental studies reveal that an increase in the size of the amino alcohol substituent led to an increase in the observed endo selectivity at the β-position of the bicyclic lactam. A similar increase in endo selectivity was shown to be dependent on the bridgehead substituent of the bicyclic lactam also. Both of these observed trends can be explained by the steric interactions on the exo face of the [3.3.0] bicyclic lactam and be attributed to dynamic kinetic resolution (DKR).
|School:||California State University, Long Beach|
|School Location:||United States -- California|
|Source:||MAI 50/04M, Masters Abstracts International|
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