Development of new methodology in environmentally benign solvents: 1. Direct formation of tetrahydropyranol derivatives in both water and ionic liquid. 2. carbon-X activation in aqueous media.

摘要

This work involves the development of novel organic methodology utilizing the principles of green chemistry and exclusively in environmentally benign solvents. The methodologies are developed in two different areas, namely the direct formation of tetrahydropryanols in both ionic liquid and water and C-X activation in aqueous media.; The development of methodologies for direct tetrahydropyranol derivatives synthesis was completed in both ionic liquid and water. In the method that utilized ionic liquid as the solvent, the ionic liquid used was butylmethylimidazolium hexafluorophosphate, [bmim][PF6], in which a simple homoallyl alcohol and an aldehyde reacted in the presence of a catalytic amount of cerium triflate hydrate to yield the exclusive formation of tetrahydropyranol derivatives. In the method that utilized water as the solvent, the acid source used was Amberlite IR-120RTM Plus resin, which has a sulfonic acid moiety. In the presence of the resin and under sonication in water, a simple homoallyl alcohol and an aldehyde yields the direct formation of tetrahydropyranol derivatives in water.; Various factors have limited the extension of the aqueous methodology onto nonactivated C-X bonds and have been limited to activated C-X bonds such as allyl halides. Therefore, the overall goal of the C-X activation project was to develop an environmentally friendly, aqueous solvent based novel methodology that would allow for the addition of nonactivated simple alkyl halides onto the appropriate electrophilic system. We started from the relatively facile addition of an unactivated alkyl halide to a 1,4-unsaturated system, using electron-deficient alpha-phthalimidoacrylate derivates, to form alpha-amino acid derivatives. The next stage involved the addition of unactivated alkyl halides to alpha-imino esters to form alpha-amino acid derivatives, followed by the addition to an imine to form amine derivatives. The culmination of the project was also the most difficult and resulted in the first report of a high yield Barbier-Grignard type carbonyl alkylation with non-activated halides in water.