EXPLORATION INTO THE SCOPE AND MECHANISM OF THE PLATINUM-CATALYZED ACYLATION OF 2-(ARYLOXY)PYRIDINES

ECU Author/Contributor (non-ECU co-authors, if there are any, appear on document)

Jacob D Guthrie (Creator)

Institution

East Carolina University (ECU )

Web Site: http://www.ecu.edu/lib/

Abstract: Transition metal catalysts have played a key role in direct C-H bond functionalization. However , one main drawback of these reactions is that oxidants and additives are often required to regenerate the active catalyst , oxidize the substrates , or promote the reaction. These needed reagents can often add significant cost and safety concerns to the synthesis. Recently the Huo group has discovered a unique platinum catalyzed acylation reaction to produce alpha-keto esters via C-H functionalization using ethyl chorooxoacetate , a cheap and readily accessible reagent. This reaction eliminated the need for any oxidants or additives and , more importantly , was free of any decarbonylation side reactions (see below). Further reaction optimization was performed to lower the catalyst loading. It was found that with the addition of potassium carbonate , strong acids that were produced during the C-H activation step (B) were neutralized thus allowing the catalyst to coordinate to the 1a more readily. The range of the overall synthesis was explored using different acylating agents. Finally , Hammett analysis was used to study the substituent effects of this reaction. Experimental results will be reported , and the significance of these findings will be discussed.

Additional Information

Publication

Thesis

Language: English

Date: 2019

Keywords

C-H Activation, Hammett Analysis

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