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Full-Text Articles in Physical Sciences and Mathematics
The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry
The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry
Electronic Thesis and Dissertation Repository
Main group Lewis acids have been shown to be viable alternatives to state-of-theart transition metal catalysts. While extensive research into a variety of p-block Lewis acids have been reported, the field of germanium Lewis acid chemistry has been described as “almost non-existent”. A variety of bis(catecholato)germane derivatives have been synthesized. The Lewis acidity of these compounds was analyzed by the Gutmann-Beckett and fluoride ion affinity methods demonstrating the high Lewis acidity of these complexes. The bis(catecholato)germanes were utilized as Lewis acid catalysts for the hydrosilylation of aldehydes, the hydroboration of alkynes, Friedel-Crafts alkylation of alkenes, and the oligomerization of styrene …
Investigations Into The Role Of Conformational Dynamics In Protein Function: Insights From Hydrogen/Deuterium Exchange-Mass Spectrometry, Courtney S. Fast
Investigations Into The Role Of Conformational Dynamics In Protein Function: Insights From Hydrogen/Deuterium Exchange-Mass Spectrometry, Courtney S. Fast
Electronic Thesis and Dissertation Repository
Deciphering protein structure and dynamics is a key prerequisite for understanding biological function. The current work aims to apply HDX-MS to improve the understanding of protein structure and dynamics for systems that remain challenging for other techniques. Following a general overview of the field (Chapter 1), Chapter 2 investigates the relationship between enzyme dynamics and catalysis. By conducting comparative HDX-MS measurements on rM1-PK during substrate turnover and in the resting state, catalytically active rM1-PK undergoes significant rigidification of the active site. However, virtually the same rigidification was seen upon exposing rM1-PK to substrate or product in the …
New Chemistry Of Donor-Acceptor Cycloalkanes And Studies Towards The Synthesis Of Streptorubin B, Naresh Vemula
New Chemistry Of Donor-Acceptor Cycloalkanes And Studies Towards The Synthesis Of Streptorubin B, Naresh Vemula
Electronic Thesis and Dissertation Repository
This dissertation presents two separate chapters within the broad area of synthetic organic chemistry. The first chapter describes the annelation chemistry of donor-acceptor (DA) cyclopropanes and cyclobutanes for the synthesis of heterocycles. The Yb(OTf)3-catalyzed [4+2] cycloaddition between DA cyclobutanes and nitrosoarenes facilitated the synthesis of tetrahydro-1,2-oxazines in good to excellent yields as single diastereomers. Additionally, an unexpected deoxygenation occurred with electron-rich nitrosoarenes under MgI2-catalysis that afforded pyrrolidine products. The GaCl3-catalyzed [4+2] cycloaddition of DA cyclobutanes and cis-diazenes provided hexahydropyridazine derivatives in good to excellent yields as single diastereomers. Furthermore, a procedure to make …
Metal-Ligand Cooperative Catalysis And Methods For Metal Removal From Organic Transformations, John-Paul J. Bow
Metal-Ligand Cooperative Catalysis And Methods For Metal Removal From Organic Transformations, John-Paul J. Bow
Electronic Thesis and Dissertation Repository
Organometallic catalysis has revolutionized the synthesis of complex organic molecules. Methods for C-C, C-X and C-H bond formation and cleavage are exploited throughout the areas of fine chemicals synthesis, with major applications for pharmaceuticals. This situation raises duel challenges: 1) high-performance catalysts for environmentally and economically sustainable synthesis and 2) efficient methods of catalyst (i.e. metal) removal must be identified. This work tackles both of these areas. The highly tunable cooperative PR2NR'2 ligands have been implemented for the first time for catalytic organic transformations. I show that [Ru(Cp)(PtBu2NBn2)(MeCN)][PF6 …