東華大學圖書館 |

Language: English

Help

回圖書館首頁

手機版館藏查詢

Back

Switch To: Labeled | MARC Mode | ISBD

Method Development and Mechanistic I...

Kozack, Caitlin V.

Linked to FindBook

Google Book

Amazon

博客來

Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes./
Author:	Kozack, Caitlin V.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2021,
Description:	234 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-11, Section: B.
Contained By:	Dissertations Abstracts International82-11B.
Subject:	Organic chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28497058
ISBN:	9798738620928

Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes.
Kozack, Caitlin V.

Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes. - Ann Arbor : ProQuest Dissertations & Theses, 2021 - 234 p.

Source: Dissertations Abstracts International, Volume: 82-11, Section: B.

Thesis (Ph.D.)--The University of Wisconsin - Madison, 2021.

This item must not be sold to any third party vendors.

Palladium-catalyzed allylic C-H acetoxylation has been the subject of significant study in its 60-year history, however several limitations still exist. There are no methods for the allylic acetoxylation of terminal alkenes that exhibit high catalytic turnover. This is of considerable interest in order to establish large scale reactions. Reactions with a broad scope in substrate and coupling partner are also relatively sparse. In order for the field to continue to move forward, it is critical to understand the mechanistic systems so the insights can be applied to develop new methods that are broad in scope and robust in catalytic activity. This thesis will focus on mechanistic investigations to understand the mechanism of 4,5-diazafluoren-one (DAF)/Pd(OAc)2-catalyzed aerobic allylic C-H acetoxylation reactions, as well as develop methods that will expand the scope and increase the catalytic activity of allylic acetoxylation.Chapter 1 analyzes high turnover methods for Pd-catalyzed allylic acetoxylation with a focus on the factors that contribute to the success of existing catalytically robust methods, as well as the challenges with developing high turnover methods for terminal akenes and how recent advances with this substrate class may provide insights into unlocking reactivity. Chapter 2 presents the development of a method for Pd-catalyzed aerobic allylic acyloxylation with a low stoichiometry of carboxylic acid coupling partners. Chapter 3 provides an in-depth mechanistic investigation into 4,5-diazafluoren-9-one (DAF)/Pd(OAc)2-catalyzed aerobic allylic C-H acetoxylation by using operands spectroscopy to elucidate the two distinct rate regimes. Chapter 4 probes the role of benzoquinone additives in DAF/Pd(OAc)2-catalyzed aerobic allylic acetoxylation in the presence and absence of Co(salophen), a transition metal cocatalyst. Chapter 5 presents the development of a method for high turnover DAF/Pd(OAc)2-catalyzed allylic C-H acetoxylation of a terminal alkene as well as preliminary kinetics to probe the mechanism.

ISBN: 9798738620928Subjects--Topical Terms:

523952
Organic chemistry.
Subjects--Index Terms:

Acetoxylation

Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes.
LDR:03176nmm a2200337 4500 001 2285080
005 20211124104346.5
008 220723s2021 ||||||||||||||||| ||eng d
020 $a 9798738620928
035 $a (MiAaPQ)AAI28497058
035 $a AAI28497058
040 $a MiAaPQ $c MiAaPQ
100 1 $a Kozack, Caitlin V. $3 3564344
245 1 0 $a Method Development and Mechanistic Investigation of Palladium-Catalyzed Allylic Oxidation Reactions of Terminal Alkenes.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2021
300 $a 234 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-11, Section: B.
500 $a Advisor: Stahl, Shannon S.
502 $a Thesis (Ph.D.)--The University of Wisconsin - Madison, 2021.
506 $a This item must not be sold to any third party vendors.
520 $a Palladium-catalyzed allylic C-H acetoxylation has been the subject of significant study in its 60-year history, however several limitations still exist. There are no methods for the allylic acetoxylation of terminal alkenes that exhibit high catalytic turnover. This is of considerable interest in order to establish large scale reactions. Reactions with a broad scope in substrate and coupling partner are also relatively sparse. In order for the field to continue to move forward, it is critical to understand the mechanistic systems so the insights can be applied to develop new methods that are broad in scope and robust in catalytic activity. This thesis will focus on mechanistic investigations to understand the mechanism of 4,5-diazafluoren-one (DAF)/Pd(OAc)2-catalyzed aerobic allylic C-H acetoxylation reactions, as well as develop methods that will expand the scope and increase the catalytic activity of allylic acetoxylation.Chapter 1 analyzes high turnover methods for Pd-catalyzed allylic acetoxylation with a focus on the factors that contribute to the success of existing catalytically robust methods, as well as the challenges with developing high turnover methods for terminal akenes and how recent advances with this substrate class may provide insights into unlocking reactivity. Chapter 2 presents the development of a method for Pd-catalyzed aerobic allylic acyloxylation with a low stoichiometry of carboxylic acid coupling partners. Chapter 3 provides an in-depth mechanistic investigation into 4,5-diazafluoren-9-one (DAF)/Pd(OAc)2-catalyzed aerobic allylic C-H acetoxylation by using operands spectroscopy to elucidate the two distinct rate regimes. Chapter 4 probes the role of benzoquinone additives in DAF/Pd(OAc)2-catalyzed aerobic allylic acetoxylation in the presence and absence of Co(salophen), a transition metal cocatalyst. Chapter 5 presents the development of a method for high turnover DAF/Pd(OAc)2-catalyzed allylic C-H acetoxylation of a terminal alkene as well as preliminary kinetics to probe the mechanism.
590 $a School code: 0262.
650 4 $a Organic chemistry. $3 523952
653 $a Acetoxylation
653 $a Catalysis
653 $a Oxidation
653 $a Palladium
690 $a 0490
710 2 $a The University of Wisconsin - Madison. $b Chemistry. $3 2049906
773 0 $t Dissertations Abstracts International $g 82-11B.
790 $a 0262
791 $a Ph.D.
792 $a 2021
793 $a English
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28497058