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Title: New methods for the synthesis of [2]rotaxanes : applications as molecular switches and artificial peptide synthesisers
Author: Echavarren, Javier
ISNI:       0000 0005 0290 3809
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2020
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Many biological processes require the intervention of sophisticated molecular machines to orchestrate complex actions. The last few decades have witnessed how the community of synthetic chemists has learnt the lessons from biology to create a wide variety of different artificial molecular machines able to perform all sorts of different tasks. The development of new artificial molecular machines has evolved hand in hand with the synthesis of new molecular structures and topologies. This thesis revolves around the use of [2]rotaxanes (a particular kind of mechanically interlocked structure with an axle threaded across a macrocycle) as privilege scaffolds for their use as molecular machines. In particular, the large amplitude motion of a macrocycle in a rotaxane with respect to its threaded axle can allow for the fine control in the outcome of a reaction. This feature has been explored in this thesis for two different applications. First a [2]rotaxane has been used to assemble a peptide in a sequence specific way via the direct aminolysis of thioesters. This is reminiscent of the way in which the ribosome operates to decode genetic material into proteins. Secondly, a structurally different [2]rotaxane architecture has been employed as a switchable organocatalyst to selectively flip the enantioselectivity in the conjugative addition of aldehydes to activated electrophiles. Finally, due to the importance of rotaxanes as molecular machines, a new method for the synthesis of non-symmetric alkyl [2]rotaxanes is described using a recently reported Ni-catalysed decarboxylative protocol.
Supervisor: Leigh, David ; Greaney, Michael Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: switchable catalyst ; molecular machine ; [2]rotaxane