Use this URL to cite or link to this record in EThOS:
Title: Radical cyclisation cascades triggered by electron-transfer to amide derivatives
Author: Huang, Huanming
ISNI:       0000 0004 7429 6799
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2017
Availability of Full Text:
Access from EThOS:
Access from Institution:
Radical cyclisation and cyclisation cascades are a powerful synthetic approach for the formation of multiple carbon-carbon bonds to generate complex carbo and heterocyclic architectures in synthetic chemistry. Radical cyclisation and cyclisation cascades triggered by electron transfer reduction to amide-type carbonyls have been demonstrated for the first time. In one step, simple achiral barbiturates can be converted to hemiaminal or enamine-containing tricyclic scaffolds or unprecedented spirotetracyclic architectures containing up to five contiguous stereocentres (including quaternary stereocentres) with high diastereocontrol. Electron transfer reduction to amide-type carbonyls triggers radical heterocyclisation and heterocyclisation cascades that deliver complex cyclic compounds containing bridgehead nitrogen atoms with up to five contiguous stereocentres with complete diastereocontrol. We have also demonstrated the first example of radical cyclisation triggered by reductive electron transfer to urea carbonyls. A variety of bicyclic products could be constructed in good to excellent yields with complete diastereocontrol. Furthermore, the radical cyclisation of urea carbonyls could be exploited in radical cyclisation cascades. The cyclisation cascades involve the generation of unusual radical anions from urea carbonyls followed by the trapping of aminal radical intermediates.
Supervisor: Flitsch, Sabine ; Procter, David Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available