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Design and Synthesis of New Sulfonat...

Kramer, Morgan Jacob.

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Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications./
Author:	Kramer, Morgan Jacob.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2023,
Description:	498 p.
Notes:	Source: Dissertations Abstracts International, Volume: 85-01, Section: B.
Contained By:	Dissertations Abstracts International85-01B.
Subject:	Organic chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30315161
ISBN:	9798379761455

Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications.
Kramer, Morgan Jacob.

Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications. - Ann Arbor : ProQuest Dissertations & Theses, 2023 - 498 p.

Source: Dissertations Abstracts International, Volume: 85-01, Section: B.

Thesis (Ph.D.)--University of Maryland, College Park, 2023.

The use of platinum group metals for the activation and functionalization of C-H bonds has been a topic of substantial interest over the past 60 years. Specifically, platinum-based complexes represent a particularly promising avenue due to their ability to form air-and water-stable species that are capable of reacting with some of the most inert C-H bonds within organic substrates. Over the decades of research contributing to this field, platinum complexes have frequently been angled towards fundamental mechanistic analysis of homogeneous C-H bond activation. In turn, the development of homogenous PtII -based catalytic systems has remained underdeveloped for the practical applications in C-H bond functionalization and, in particular, deuteration of complex organic molecules, including pharmaceuticals. The latter direction is now attracting a significant interest by the pharmaceutical industry. In this work the kinetic and thermodynamic selectivity of our new catalyst, a PtII sulfonated CNN-pincer complex 1.5, in the H/D exchange reaction between aromatic substrates and wet TFE-d1 was screened across thirty-four aromatic substrates with the catalysts TON up to 300 (Chapter 2). A kinetic preference of 1.5 for electron-rich C-H bonds and substrates were firmly established and a novel scale of Hammett-like σXM constants was introduced to characterize the reactivity of the substrates' C(sp2 )-H bonds in transition-metal-mediated C-H activation. To greatly enhance our PtII catalysts' useful life, we used their rigid covalent immobilization to mesoporous silica nanoparticles (immobilized complex 3.5). The resulting robust material served as an efficient H/D exchange catalyst utilizing cheaper sources of exchangeable deuterium, AcOD-d4, and D2O, with the catalyst's TON up to 1600 (Chapter 3). To understand our novel catalyst's structure - activity relationship, a series of benzene fragment - R-substituted analogs of 1.5 (R = MeO, tBu, iPr, F, Cl, CF3) were synthesized and explored in the H/D exchange of a series of aromatic compounds (Chapter 4). Surprisingly, the complex 4.1-tBu (R = tBu) stood out as a most robust homogeneous catalyst compatible with AcOD-d4 and D2O at 120 oC as deuterium sources that can work under air. Thanks to this finding, the substrates scope for the H/D exchange with AcOD-d4 catalyzed by 4.1-tBu was expanded to include eight pharmaceuticals, some alkenes, with signs of engagement of some C(sp3 )-H bond donors. A novel photo-induced (violet light) room temperature H/D exchange catalyzed by 4.1-OMe was discovered with a substantially different substrate selectivity, as compared to the thermal reaction at 80 oC. These observations may provide some important insight into the mechanism of PtII -mediated C-H activation. Finally, Chapter 5 summarizes the results of this work and suggests some future directions for this area of research.

ISBN: 9798379761455Subjects--Topical Terms:

523952
Organic chemistry.
Subjects--Index Terms:

Catalysis

Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications.
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245 1 0 $a Design and Synthesis of New Sulfonated CNN Ligand Scaffolds for Platinum Catalyzed H/D Exchange Applications.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2023
300 $a 498 p.
500 $a Source: Dissertations Abstracts International, Volume: 85-01, Section: B.
500 $a Advisor: Vedernikov, Andrei N.
502 $a Thesis (Ph.D.)--University of Maryland, College Park, 2023.
520 $a The use of platinum group metals for the activation and functionalization of C-H bonds has been a topic of substantial interest over the past 60 years. Specifically, platinum-based complexes represent a particularly promising avenue due to their ability to form air-and water-stable species that are capable of reacting with some of the most inert C-H bonds within organic substrates. Over the decades of research contributing to this field, platinum complexes have frequently been angled towards fundamental mechanistic analysis of homogeneous C-H bond activation. In turn, the development of homogenous PtII -based catalytic systems has remained underdeveloped for the practical applications in C-H bond functionalization and, in particular, deuteration of complex organic molecules, including pharmaceuticals. The latter direction is now attracting a significant interest by the pharmaceutical industry. In this work the kinetic and thermodynamic selectivity of our new catalyst, a PtII sulfonated CNN-pincer complex 1.5, in the H/D exchange reaction between aromatic substrates and wet TFE-d1 was screened across thirty-four aromatic substrates with the catalysts TON up to 300 (Chapter 2). A kinetic preference of 1.5 for electron-rich C-H bonds and substrates were firmly established and a novel scale of Hammett-like σXM constants was introduced to characterize the reactivity of the substrates' C(sp2 )-H bonds in transition-metal-mediated C-H activation. To greatly enhance our PtII catalysts' useful life, we used their rigid covalent immobilization to mesoporous silica nanoparticles (immobilized complex 3.5). The resulting robust material served as an efficient H/D exchange catalyst utilizing cheaper sources of exchangeable deuterium, AcOD-d4, and D2O, with the catalyst's TON up to 1600 (Chapter 3). To understand our novel catalyst's structure - activity relationship, a series of benzene fragment - R-substituted analogs of 1.5 (R = MeO, tBu, iPr, F, Cl, CF3) were synthesized and explored in the H/D exchange of a series of aromatic compounds (Chapter 4). Surprisingly, the complex 4.1-tBu (R = tBu) stood out as a most robust homogeneous catalyst compatible with AcOD-d4 and D2O at 120 oC as deuterium sources that can work under air. Thanks to this finding, the substrates scope for the H/D exchange with AcOD-d4 catalyzed by 4.1-tBu was expanded to include eight pharmaceuticals, some alkenes, with signs of engagement of some C(sp3 )-H bond donors. A novel photo-induced (violet light) room temperature H/D exchange catalyzed by 4.1-OMe was discovered with a substantially different substrate selectivity, as compared to the thermal reaction at 80 oC. These observations may provide some important insight into the mechanism of PtII -mediated C-H activation. Finally, Chapter 5 summarizes the results of this work and suggests some future directions for this area of research.
590 $a School code: 0117.
650 4 $a Organic chemistry. $3 523952
650 4 $a Thermodynamics. $3 517304
650 4 $a Physical chemistry. $3 1981412
650 4 $a Pharmaceutical sciences. $3 3173021
653 $a Catalysis
653 $a H/D exchange
653 $a Homogenous catalysis
653 $a Isotope labeling
653 $a Pharmaceuticals
653 $a Platinum
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792 $a 2023
793 $a English
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30315161