Design and Development of Chiral Iodoarenes and a Novel Iodine(III)-Mediated Carbamate Cyclisation

  • Mirdyul Das

Student thesis: Doctoral Thesis


This thesis covers the design and development of a range of chiral iodoarenes and their investigation into the asymmetric cyclisation of N-allylbenzamide, N-allycarbamates and N-allyl-1H-pyrrole-2-carboxamide derivatives, or diacetoxylation of styrene.

The first part, describes the development of enantiomerically pure chiral iodo-diarylmethylamine(I) catalyst, oxidised to give the corresponding conformationally rigid iodine(III)-diarylmethylamine species, evaluated in the catalytic enantioselective cyclisation of N-allylbenzamide (Scheme 1a) and the diacetoxylation of styrene (Scheme 1b).

In the second part, illustrates the design and development of chiral monoiodo and diiodoarene lactate and lactamide precatalysts and their study into the catalytic asymmetric cyclisation of N-allylbenzamide using two sets of reaction conditions (Scheme 2a&b).

In the third part of the thesis, there is a report of attempts to cyclise N-allyl-1H-pyrrole-2-carboxamide derivatives (Scheme 3a&b) and modification of the substrate and reaction conditions to bring about cyclisation.

The final part elaborates on the comprehensive development of the cyclisation of carbamates. It depicts solvent screening, preparation and screening of a range of Koser’s Reagent derivatives and carbamate substrates and cyclised product scope (Scheme 4a). The development of a one-step preparation of the novel Koser’s Reagent derivative is illustrated and attempts to make the reaction catalytic or microwave-assisted are described. The development of a one-pot in situ generation of the hypervalent iodine(III) species followed by the cyclisation reaction is shown. It reports a chiral Koser’s derivative could bring about asymmetric cyclisation with moderate enantioselectivity (Scheme 4b) and that an oxazolidinone drug analogue could be synthesised using the reaction.
Date of Award28 Sep 2022
Original languageEnglish
SupervisorWesley Moran (Main Supervisor) & Laura Waters (Co-Supervisor)

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