Author: Michael J. Krische
Publisher:
ISBN:
Category :
Languages : en
Pages : 674
Book Description
Synthetic Access to the Picrotoxane Family of Natural Products Via the Palladium Catalyzed Cycloisomerization of 1,6-enynes and Related Degradation Studies
Author: Michael J. Krische
Publisher:
ISBN:
Category :
Languages : en
Pages : 674
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 674
Book Description
Dissertation Abstracts International
Author:
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 806
Book Description
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 806
Book Description
New Strategies for the Synthesis of Bioactive Natural and Unnatural Products Via Palladium Catalyzed Asymmetric Allylic Alkylation
Author: Weiping Tang
Publisher:
ISBN:
Category :
Languages : en
Pages : 496
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 496
Book Description
Studies on the Scope of the Palladium Catalyzed Reductive Diyne Cyclization
Author: Fred J. Fleitz
Publisher:
ISBN:
Category :
Languages : en
Pages : 618
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 618
Book Description
The Chemoselective Catalytic Oxidation of Alcohols, Diols, and Polyols to Ketones and Hydroxyketones
Author: Ronald Michael Painter
Publisher: Stanford University
ISBN:
Category :
Languages : en
Pages : 110
Book Description
The chemoselective oxidation of vicinal diols to α-hydroxyketones is a challenge in organic syntheses because not only does the diol need to be oxidized selectively to a monocarbonyl compound, but diols are also prone to overoxidation and oxidative cleavage. Employing a cationic palladium complex, [(neocuproine)Pd(OAc)]2(OTf)2, we were able to demonstrate the selective oxidation of glycerol to dihydroxyacetone mediated by either benzoquinone or O2 as the terminal oxidant, an accomplishment that has little precedent in homogeneous catalysis. Mechanistic studies were undertaken to uncover the nature of this remarkable chemoselectivity. Kinetic and deuterium-labeling studies implicate reversible β-hydride elimination from isomeric Pd alkoxides and turnover-limiting displacement of the dihydroxyacetone product by benzoquinone. We successfully extended this methodology to other terminal 1,2-diols and symmetric vicinal 1,2-diols and have carried out aerobic oxidation of these substrates catalyzed by 1. Examination of the reactivity of 1 with conformationally-restricted 1,2-cyclohexanediols suggests that the diol must chelate to the Pd center for effective oxidation to the hydroxyketone product. In a separate project, we have also investigated the electrocatalytic reduction of dioxygen by several dinuclear copper complexes, an important reaction for fuel cell applications.
Publisher: Stanford University
ISBN:
Category :
Languages : en
Pages : 110
Book Description
The chemoselective oxidation of vicinal diols to α-hydroxyketones is a challenge in organic syntheses because not only does the diol need to be oxidized selectively to a monocarbonyl compound, but diols are also prone to overoxidation and oxidative cleavage. Employing a cationic palladium complex, [(neocuproine)Pd(OAc)]2(OTf)2, we were able to demonstrate the selective oxidation of glycerol to dihydroxyacetone mediated by either benzoquinone or O2 as the terminal oxidant, an accomplishment that has little precedent in homogeneous catalysis. Mechanistic studies were undertaken to uncover the nature of this remarkable chemoselectivity. Kinetic and deuterium-labeling studies implicate reversible β-hydride elimination from isomeric Pd alkoxides and turnover-limiting displacement of the dihydroxyacetone product by benzoquinone. We successfully extended this methodology to other terminal 1,2-diols and symmetric vicinal 1,2-diols and have carried out aerobic oxidation of these substrates catalyzed by 1. Examination of the reactivity of 1 with conformationally-restricted 1,2-cyclohexanediols suggests that the diol must chelate to the Pd center for effective oxidation to the hydroxyketone product. In a separate project, we have also investigated the electrocatalytic reduction of dioxygen by several dinuclear copper complexes, an important reaction for fuel cell applications.