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Development of the Enantioselective Oxidation of Secondary Alcohols and Natural Products Total Synthesis


Bagdanoff, Jeffrey Thomas (2006) Development of the Enantioselective Oxidation of Secondary Alcohols and Natural Products Total Synthesis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z94F1NQK.


Oxidation is a fundamental process in chemistry and biology. In synthetic chemistry, there are several methods for the asymmetric oxidation of organic substrates. Classically, these methods have focused on the delivery of a heteroatom from a reagent or catalyst to a prochiral substrate. What have historically been underdeveloped are enantioselective oxidation methods that do not involve the transfer of a heteroatom, but rather are defined by the enantioselective dehydrogenation of an organic substrate. This type of oxidative transformation was investigated using a palladium(II) catalyst system.

A palladium-catalyzed oxidative kinetic resolution of secondary alcohols was developed. Key features of the catalytic system include the use of (–)-sparteine as the source of chiral relay, and molecular oxygen as the sole stoicheometric oxidant. Under the described catalytic system, a number of benzylic and allylic alcohols have been oxidized in an enantioselective manner, to provide a ketone and residual alcohol in high enantiomeric excess and excellent yield.

Subsequent to the original system, the systematic investigation of a number of mechanistic hypotheses involving the role of exogenous bases and H-bonding additives prompted the discovery of new reaction conditions displaying greatly enhanced reactivity, selectivity, atom economy, and generality. The net result of these improvements was a catalytic system effective in oxidative desymmetrization of a number of complex meso-diols. Ultimately, these advances have permitted our method to be applied towards a number of synthetic endeavors, including the key step in the total synthesis of the natural product alkaloid (–)-lobeline.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:catalysis; enantioselective; oxidation; palladium
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:Tobacco-Related Disease Research Program (TRDRP) Dissertation Award, 2002
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Stoltz, Brian M.
Thesis Committee:
  • Grubbs, Robert H. (chair)
  • Stoltz, Brian M.
  • Tirrell, David A.
  • Hsieh-Wilson, Linda C.
Defense Date:5 August 2005
Record Number:CaltechETD:etd-08182005-120859
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5248
Deposited By: Imported from ETD-db
Deposited On:18 Aug 2005
Last Modified:08 Nov 2023 00:39

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