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035 a| (Sirsi) o1381680645;

035 a| (OCoLC)1381680645;

049 a| EREE;

090 a| QD505;

100 1 a| English, Hunter Wade,e| author.?| UNAUTHORIZED;

245 12 a| A catalytic approach to cyclopentenones :b| unexpected challenges in synthesizing pent-2,4-dienals /c| by Hunter Wade English.;

264 1 a| [Greenville, N.C.] :b| [East Carolina University],c| 2023.;

300 a| 1 online resource (64 pages) :b| illustrations;

336 a| textb| txt2| rdacontent;

337 a| computerb| c2| rdamedia;

338 a| online resourceb| cr2| rdacarrier;

347 a| text fileb| PDFc| 917.2 KB2| rda;

538 a| System requirements: Adobe Reader.;

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

502 b| M.S.c| East Carolina Universityd| 2023.;

502 a| Presented to the Faculty of the Department of Chemistry;

500 a| Advisor: Andrew T. Morehead, Jr.;

500 a| Title from PDF t.p. (viewed August 13, 2024).;

520 3 a| Transition metal catalysis has long been utilized to facilitate a number of chemical reactions outside the scope of traditional organic chemistry. Because of this, there has been a growing interest in the community in utilizing C-H bonds over C-X bonds as synthetic alternatives with better thermodynamic conditions (lower temperatures, pressures, energies, etc.) and forming C-C bonds. For example, rhodium-catalyzed hydroacylation can be used in the conversion of 4-pentenals to cyclopentanones. The mechanistic foundation of this reaction was applied to the synthesis of chiral 3-substituted indanones, unlocking a whole series of transformations towards the construction of biologically active molecules. The Morehead group recently proposed an alternate synthesis of cyclopentenones via a rhodium-catalyzed intramolecular hydroacylation reaction of penta-2,4-dienals by the following reaction sequence: 1. Vilsmeier-Haack Formylation to form 3-bromo-2-enals, 2. Suzuki Cross-Coupling with vinylboronates, and 3. Hydroacylation. Indeed, all reaction steps were performed successfully starting from acetophenone and allylboronic acid pinacol ester, resulting in 4-methyl-3-phenyl-2-cyclopenten-1-one. However, some surprising results were obtained along the way. It was found that when 3-bromo-3-phenyl-2-propenal underwent Suzuki Cross-Coupling, an unexpected mixture of pent-2,4-dienal isomers was obtained. To investigate this matter, a number of reaction conditions were examined in hopes of finding one with optimal yields and little to no isomerized pent-2,4-dienal product. In addition, a variety of cyclopentenones were synthesized to explore the steric effect in influencing the isomerization process. Some potential mechanistic details of this strange isomerization phenomenon along with results obtained from the synthesis will be reported and discussed.;

504 a| Includes bibliographical references.;

650 0 a| Transition metal catalysts.=| ^A419294;

650 0 a| Organic compoundsx| Synthesis.=| ^A1214;

653 a| cyclopentenones;

653 a| hydroacylation;

700 1 a| Morehead, Andrew T.,e| degree supervisor.=| ^A1472993;

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

856 40 z| Access via ScholarShipu| http://hdl.handle.net/10342/12882;

949 o| wjh;

994 a| C0b| ERE;

596 a| 1 4;

998 a| 6143747;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 6143747-1001l| JNETm| JOYNERr| Ys| Yt| JNE3ETDu| 6/9/2023x| ETDz| JERESOURCE;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 6143747-2001l| HSLELECm| HSLr| Ys| Yt| HEETDu| 6/9/2023x| ETDz| HERESOURCE;

A catalytic approach to cyclopentenones : unexpected challenges in synthesizing pent-2,4-dienals / by Hunter Wade English.

Author/creator	English, Hunter Wade author.
Other author	Morehead, Andrew T., degree supervisor.
Other author	East Carolina University. Department of Chemistry.
Format	Theses and dissertations
Publication	[Greenville, N.C.] : [East Carolina University], 2023.
Description	1 online resource (64 pages) : illustrations
Supplemental Content	Access via ScholarShip
Subjects	Transition metal catalysts. Organic compounds--Synthesis.

Summary	Transition metal catalysis has long been utilized to facilitate a number of chemical reactions outside the scope of traditional organic chemistry. Because of this, there has been a growing interest in the community in utilizing C-H bonds over C-X bonds as synthetic alternatives with better thermodynamic conditions (lower temperatures, pressures, energies, etc.) and forming C-C bonds. For example, rhodium-catalyzed hydroacylation can be used in the conversion of 4-pentenals to cyclopentanones. The mechanistic foundation of this reaction was applied to the synthesis of chiral 3-substituted indanones, unlocking a whole series of transformations towards the construction of biologically active molecules. The Morehead group recently proposed an alternate synthesis of cyclopentenones via a rhodium-catalyzed intramolecular hydroacylation reaction of penta-2,4-dienals by the following reaction sequence: 1. Vilsmeier-Haack Formylation to form 3-bromo-2-enals, 2. Suzuki Cross-Coupling with vinylboronates, and 3. Hydroacylation. Indeed, all reaction steps were performed successfully starting from acetophenone and allylboronic acid pinacol ester, resulting in 4-methyl-3-phenyl-2-cyclopenten-1-one. However, some surprising results were obtained along the way. It was found that when 3-bromo-3-phenyl-2-propenal underwent Suzuki Cross-Coupling, an unexpected mixture of pent-2,4-dienal isomers was obtained. To investigate this matter, a number of reaction conditions were examined in hopes of finding one with optimal yields and little to no isomerized pent-2,4-dienal product. In addition, a variety of cyclopentenones were synthesized to explore the steric effect in influencing the isomerization process. Some potential mechanistic details of this strange isomerization phenomenon along with results obtained from the synthesis will be reported and discussed.
General note	Advisor: Andrew T. Morehead, Jr.
General note	Title from PDF t.p. (viewed August 13, 2024).
Dissertation note	M.S. East Carolina University 2023.
Dissertation note	Presented to the Faculty of the Department of Chemistry
Bibliography note	Includes bibliographical references.
Technical details	System requirements: Adobe Reader.
Technical details	Mode of access: World Wide Web.

A catalytic approach to cyclopentenones : unexpected challenges in synthesizing pent-2,4-dienals / by Hunter Wade English.

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