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"High" Temperature Lithiation-trapping of Nitrogen and Oxygen Heterocycles

Kwong, Wai Sze Alice (2016) "High" Temperature Lithiation-trapping of Nitrogen and Oxygen Heterocycles. PhD thesis, University of York.

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Abstract

This thesis describes some novel aspects of the lithiation-trapping of nitrogen and oxygen heterocycles, including a systematic study of new methodologies at temperature above ‒78 °C and the use of the sustainable solvent, 2-MeTHF, as an alternative to Et2O and THF. Chapter 2 describes a detailed exploration of the s-BuLi-mediated lithiation-trapping of N-Boc heterocycles (pyrrolidine, piperidine, piperazine and azepane) using different conditions (diamine, solvent, temperature and time). For N-Boc pyrrolidine, two new high temperature lithiation conditions were optimised: (i) 0 °C for 5 sec is best for flow system; (ii) ‒20 ° C for 2 min is best for batch conditions. The stability of the lithiated N-Boc pyrrolidine at 0 °C was also investigated. In Chapter 3, the development of novel methodology for the lithiation-trapping of oxygen heterocycles (THF and THP) is presented. Different conditions were optimised for THF and THP lithiation to give trapped products in 20-32% yield. The newly developed methodology was extended to the lithiation-trapping of N-substituted morpholines. A full study of the reaction conditions and scope of the methodology was carried out for three different N-alkyl groups. The best substrate was the N-methyl morpholine and the optimised conditions were s-BuLi/TMEDA in hexane at 0 °C for 1 h, giving yields of trapped products in 75-90%. A procedure that is catalytic in TMEDA was also discovered.

Item Type: Thesis (PhD)
Academic Units: The University of York > Chemistry (York)
Identification Number/EthosID: uk.bl.ethos.703382
Depositing User: Miss Wai Sze Alice Kwong
Date Deposited: 14 Feb 2017 11:30
Last Modified: 24 Jul 2018 15:21
URI: http://etheses.whiterose.ac.uk/id/eprint/16229

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