Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/27885
Title: Alpha-Fluorinated aromatic ketone as nucleophile in asymmetric organocatalytic C-N and C-C bonds formation reactions
Authors: ZHAO YUJUN
Keywords: fluorinated aromatic ketone, nucleophile, organocatalytic
Issue Date: 3-Jan-2011
Source: ZHAO YUJUN (2011-01-03). Alpha-Fluorinated aromatic ketone as nucleophile in asymmetric organocatalytic C-N and C-C bonds formation reactions. ScholarBank@NUS Repository.
Abstract: The development of fluorocarbon as nucleophile in asymmetric organocatalysis is an important approach for the construction of fluorinated quaternary carbon centers. This dissertation focused on asymmetric catalysis of a-fluorinated aromatic ketones. In chapter two, we investigated the asymmetric H/D exchange reaction via deprotonation/deuteration reaction of a-fluorinated aromatic ketones catalyzed by chiral bicyclic guanidine. The best enantioselectivity was obtained with 30% ee. The DFT calculations were also carried out. In chapter three, we have developed a series of a-fluorinated aromatic cyclic ketone nucleophiles in asymmetric a-amination reaction catalyzed by chiral bicyclic guanidine. Under the optimal conditions, the chiral a-hydrozino-a-fluorinated aromatic ketone (up to 96% ee) were achieved with high yields. The modification of racemic amination products was also carried out, but we failed to obtain the desired products. In chapter four, a series of new pentanidines was prepared over 10 steps synthesis. The application of these catalysts in the asymmetric Mannich reaction with a-fluorinated aromatic ketones were examined;moderate enantioselectivities and diastereoselectivities were achieved. We also have developed this kind of nucleophiles in asymmetric Mannich reaction catalyzed by chiral bicyclic guanidine. The syn-adducts were obtained in high yields (70-95%) with excellent enantioselectivities (94-99% ee).
URI: http://scholarbank.nus.edu.sg/handle/10635/27885
Appears in Collections:Ph.D Theses (Open)

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1 Cover.pdf10.77 kBAdobe PDF

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2 title page.pdf13.6 kBAdobe PDF

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3 contents.pdf94.74 kBAdobe PDF

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4 chapter 1 intro.pdf385.42 kBAdobe PDF

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5 chapter 2 Deuteration.pdf268.48 kBAdobe PDF

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6 chapter 3 amination.pdf469.55 kBAdobe PDF

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7 chapter 4 C-C Bond formation.pdf211.94 kBAdobe PDF

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8 chapter 5 expe.pdf300.55 kBAdobe PDF

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9 appendix.pdf4.06 MBAdobe PDF

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