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001 on1506074803;

003 OCoLC;

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006 m o d ;

007 cr unu||||||||;

008 250310s2024 ncua obm 000 0 eng d;

035 a| (OCoLC)1506074803;

090 a| QD505.5;

049 a| EREE;

100 1 a| Lares, Cristian Guadalupe,e| author.?| UNAUTHORIZED;

245 10 a| Investigation into the ortho-functionalization of 2-aryloxypyridines using [alpha]-keto amides via platinum-assisted C-H activation /c| by Cristian Guadalupe Lares.;

264 1 a| [Greenville, N.C.] :b| [East Carolina University],c| 2024.;

300 a| 1 online resource (112 pages) :b| illustrations (some color);

336 a| textb| txt2| rdacontent;

337 a| computerb| c2| rdamedia;

338 a| online resourceb| cr2| rdacarrier;

347 a| text fileb| application/pdfc| 2.34 MB2| rda;

538 a| System requirements: Adobe Reader.;

538 a| Mode of access: World Wide Web.;

502 b| M.S.c| East Carolina Universityd| 2024.;

500 a| Presented to the Faculty of the Department of Chemistry.;

500 a| Advisor: Shouquan Huo;

500 a| Title from PDF t.p. (viewed April 9, 2026).;

520 3 a| Transition metals are commonly used to catalyze thermodynamically unfavorable reactions, decreasing the activation energy required to break stable bonds and reform new bonds. Activation of a C-H bond can lead to the formation of more reactive C-X bonds, where X=N, O, Cl, Br, I, and Si, allowing for further reactivity or synthesis. Platinum was used as a catalyst as it serves as a soft Lewis acid, in an organic soluble cis-bis(benzonitrile)dichloroplatinate(II), cis-Pt(PhCN)2Cl2, in order to facilitate in C-H activation. Aryloxypyridines have been used as the scaffolding in several bioactive compounds, from insecticides to human enzyme inhibitors. [alpha]-keto amides have shown to have anti-inflammatory and anti-cancer properties, rendering them great candidates for study. The [alpha]-keto amides were introduced to the reaction as 2-(dialkylamino)-2-oxoacetyl chloride, as chlorine serves a good leaving group. By utilizing the pyridyl nitrogen as a directing group, the platinum catalyst can undergo rapid ligand exchange and bind itself to the aryloxypyridine. The platinum facilitated C-H activation by the interaction with the 2-(dialkylamino)-2-oxoacetyl chloride, functionalizing an ortho-position on the aryl ring. An array of different 2-aryloxypyridines was tested, with different functional groups at the ortho-, meta-, and para-positions, in order to determine the effects of resonance, induction, and steric hindrance had on the overall reaction. Three different [alpha]-keto amide containing acylating agents were tested to see how the size of the dialkyl groups performed in reactivity, where alkyl=methyl, ethyl, and isopropyl. A range of 14% to 88% was found for products using 2-(diethylamino)-2-oxoacetyl chloride, a range of 13% to 57% was found for products using 2-(dimethylamino)-2-oxoacetyl chloride, and a range of 19% to 84% was found for products using 2-(diisopropylamino)-2-oxoacetyl chloride. Due to the wide range of product yields from these reactions, a series of thermal degradations studies were conducted to determine how fragile the different 2-(dialkylamino)-2-oxoacetyl chloride were at the reaction temperature of 155°C. While the 2-(dialkylamino)-2-oxoacetyl chlorides were stable by themselves at 155°C, they underwent rapid degradation under the presence of cis-Pt(PhCN)2Cl2, as the acylating agents underwent decarbonylation.;

504 a| Includes bibliographical references.;

650 0 a| Metal activation.=| ^A1488901;

650 0 a| Organic reaction mechanisms.=| ^A404361;

650 0 a| Catalyst supports.=| ^A217070;

650 0 a| Platinum catalysts.=| ^A1345129;

653 a| C-H Functionalization;

653 a| C-H Activation;

653 a| C-H Acylation;

653 a| Aryloxypyridine;

653 a| Alpha-keto amides;

653 a| No oxidizers;

653 a| No additives;

653 a| cis-bis(benzonitrile)dichloroplatinate(II);

653 a| organometallic;

653 a| organoplatinate;

700 1 a| Huo, Shouquan,e| degree supervisor.?| UNAUTHORIZED;

710 2 a| East Carolina University.b| Department of Chemistry.?| UNAUTHORIZED;

856 40 z| Access via ScholarShipu| http://hdl.handle.net/10342/13864;

994 a| C0b| ERE;

596 a| 1 4;

998 a| 6560826;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 6560826-1001l| JNETm| JOYNERr| Ys| Yt| JNE3ETDu| 3/10/2025x| ETDz| JERESOURCE;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 6560826-2001l| HSLELECm| HSLr| Ys| Yt| HEETDu| 3/10/2025x| ETDz| HERESOURCE;

Investigation into the ortho-functionalization of 2-aryloxypyridines using [alpha]-keto amides via platinum-assisted C-H activation / by Cristian Guadalupe Lares.

Author/creator	Lares, Cristian Guadalupe author.
Other author	Huo, Shouquan, degree supervisor.
Other author	East Carolina University. Department of Chemistry.
Format	Theses and dissertations
Publication	[Greenville, N.C.] : [East Carolina University], 2024.
Description	1 online resource (112 pages) : illustrations (some color)
Supplemental Content	Access via ScholarShip
Subjects	Metal activation. Organic reaction mechanisms. Catalyst supports. Platinum catalysts.

Summary	Transition metals are commonly used to catalyze thermodynamically unfavorable reactions, decreasing the activation energy required to break stable bonds and reform new bonds. Activation of a C-H bond can lead to the formation of more reactive C-X bonds, where X=N, O, Cl, Br, I, and Si, allowing for further reactivity or synthesis. Platinum was used as a catalyst as it serves as a soft Lewis acid, in an organic soluble cis-bis(benzonitrile)dichloroplatinate(II), cis-Pt(PhCN)2Cl2, in order to facilitate in C-H activation. Aryloxypyridines have been used as the scaffolding in several bioactive compounds, from insecticides to human enzyme inhibitors. [alpha]-keto amides have shown to have anti-inflammatory and anti-cancer properties, rendering them great candidates for study. The [alpha]-keto amides were introduced to the reaction as 2-(dialkylamino)-2-oxoacetyl chloride, as chlorine serves a good leaving group. By utilizing the pyridyl nitrogen as a directing group, the platinum catalyst can undergo rapid ligand exchange and bind itself to the aryloxypyridine. The platinum facilitated C-H activation by the interaction with the 2-(dialkylamino)-2-oxoacetyl chloride, functionalizing an ortho-position on the aryl ring. An array of different 2-aryloxypyridines was tested, with different functional groups at the ortho-, meta-, and para-positions, in order to determine the effects of resonance, induction, and steric hindrance had on the overall reaction. Three different [alpha]-keto amide containing acylating agents were tested to see how the size of the dialkyl groups performed in reactivity, where alkyl=methyl, ethyl, and isopropyl. A range of 14% to 88% was found for products using 2-(diethylamino)-2-oxoacetyl chloride, a range of 13% to 57% was found for products using 2-(dimethylamino)-2-oxoacetyl chloride, and a range of 19% to 84% was found for products using 2-(diisopropylamino)-2-oxoacetyl chloride. Due to the wide range of product yields from these reactions, a series of thermal degradations studies were conducted to determine how fragile the different 2-(dialkylamino)-2-oxoacetyl chloride were at the reaction temperature of 155°C. While the 2-(dialkylamino)-2-oxoacetyl chlorides were stable by themselves at 155°C, they underwent rapid degradation under the presence of cis-Pt(PhCN)2Cl2, as the acylating agents underwent decarbonylation.
General note	Presented to the Faculty of the Department of Chemistry.
General note	Advisor: Shouquan Huo
General note	Title from PDF t.p. (viewed April 9, 2026).
Dissertation note	M.S. East Carolina University 2024.
Bibliography note	Includes bibliographical references.
Technical details	System requirements: Adobe Reader.
Technical details	Mode of access: World Wide Web.

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Investigation into the ortho-functionalization of 2-aryloxypyridines using [alpha]-keto amides via platinum-assisted C-H activation / by Cristian Guadalupe Lares.

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