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Title: Cation-controlled diastereo- and enantioselective synthesis of indolines : an autocatalytic process
Author: Sharma, Krishna
ISNI:       0000 0004 5366 0926
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2014
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Asymmetric phase-transfer catalysis is a powerful technique that enables a wide range of transformations under mild conditions, often using inexpensive and environmentally benign reagents. By extending the applications of phase-transfer catalysis we have developed a highly diastereo- and enantioselective synthesis of functionalized indolines bearing two contiguous stereocentres, one of which is quaternary and all carbon, in a single synthetic step. The reaction proceeds with complete diastereoselectivity and with high levels of enantioselectivity (up to 99% ee). Despite the development of phase-transfer catalysis as a primary synthetic tool in organic synthesis, the mechanistic understanding of these reactions still remains a challenge, due mainly to the difficulty of studying the complex multi-phase systems. Therefore, a further aim of this project was to understand the reaction mechanism of our phase-transfer catalysed transformation. Investigations into the mechanism of our phase-transfer catalysed reaction have been carried out by studying the reaction kinetics. These have shown that the reaction follows a sigmoidal curve with an induction period present. A detailed kinetic investigation was carried out which demonstrated that an autocatalytic mechanism is operational.
Supervisor: Smith, Martin D. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Physical Sciences ; Chemistry & allied sciences ; Organic chemistry ; Organic synthesis ; Catalysis ; Asymmetric catalysis ; Chemical kinetics