Transition metal catalyzed hydrogenations are among the most powerful and direct approaches for the synthesis of organic molecules. During the past half century, chiral ligands have been extensively studied in transition metal catalyzed transformations. Development of new chiral ligands, efficient catalyst systems and their applications in the reduction of various prochiral unsaturated substrates are the focus of this dissertation. In chapter 1, novel chiral tridentate f-amphox ligands were designed and synthesized. Two chiral wings in the ligands form a chiral pocket which introduces the chirality in the asymmetric hydrogenation. Tridentate f-amphox ligand has formed a highly enantioselective Iridium catalyst for direct hydrogenation of β-aryl β-ketoesters (up to 99% ee) and 3-oxo-3-arylpropionic acid ethyl esters (up to 99% ee) with high turnover number (up to 1,000,000). In chapter 2, I focus on the highly enantioselective direct reductive amination of aromatic ketone. With phenylhydrazide as the nitrogen source, various chiral hydrazides were synthesized in excellent enantioselectivities and yields. In chapter 3, a highly efficient enantioselective hydrogenation of N-alkyl-2-arylpyridinium salts was discussed. This work provides the unique example of using a chiral phosphole-based ligand for highly efficient asymmetric catalysis. The mechanism of this transformation was studied and a mechanistic cycle was proposed.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
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TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_7481
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xvi, 131 p. : ill.)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Subject (authority = ETD-LCSH)
Topic
Hydrogenation
Note (type = statement of responsibility)
by Shaodong Liu
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TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
Rutgers University. Graduate School - New Brunswick
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License
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Author Agreement License
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