Mechanistic investigations of the sought-after organic reactions-the Morita Baylis Hilman reaction and halofunctionalization of olefins has led to insightful and critical mechanistic discernments. Tools such as quantum chemical computational analysis, labeling experiments, kinetic isotopic effects, and kinetics studies (RPKA) were employed towards a comprehensive analysis of these reactions. These mechanistic revelations were applied towards development of three novel reactions a.) [4+2] formal cycloaddition towards asymmetric synthesis of dihydropyrans, b.) halenium ion initiated diastereoselective cascade spiroketalization of alkenoic ketones and c.) Iodenium ion initiated cascade towards a diastereoselevtive synthesis of tricyclic molecules with an octahydroquinoline core. This dissertation describes in detail the tools that were involved in probing the mechanistic nuances and a rational approach designed towards reaction discovery and optimization endevors.
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