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Chiral hypervalent iodine mediated enantioselective oxidative dearomatization of naphthols

University of British Columbia

This dissertation investigates and describes the hypervalent iodine mediated dearomatization of naphthols, thereby yielding diversity of spiro-heterocyclic compounds in both racemic and chiral form. The first part of this thesis discloses the synthesis of racemic spiropyrrolidines and spirolactams via oxidative amidation of corresponding naphtholic sulfonamides, employing DIB as the oxidant. Enantioselective variant of the same have been demonstrated by using in situ generated chiral hypervalent iodine to provide chiral spiropyrrolidines. A noteworthy side reaction discovered in the course of these studies is the asymmetric oxidative addition of meta-chlorobenzoic acid to the naphtholic sulfonamides. The resulting acyloxylated adducts were formed with a greater degree of asymmetric induction compared to spiropyrrolidines in the same reaction mixture. Based on the results obtained from optimization study and substrate scope, plausible mechanistic insights of both cyclization and acyloxylation reactions have been provided. The second part of this thesis unravels the spiroetherification of naphtholic alcohols, thereby yielding spiroethers both in racemic and chiral form. Chiral hypervalent iodine reagents generated in situ provided a range of spiroethers with excellent ee’s and high yields. These chiral oxidants have been evaluated for kinetic resolution of naphtholic primary alcohols bearing stereogenic center at β-position in the side chain.

Text

2017-08-08

Attribution-NonCommercial-NoDerivatives 4.0 International

http://hdl.handle.net/2429/62521

Chemistry

University of British Columbia

UBCV

http://creativecommons.org/licenses/by-nc-nd/4.0/