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Development of Phase Transfer Catalysed Cyclopropanation and Related Processes

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posted on 22.11.2019 by Claudia Del Fiandra

The aim of this research is to develop new Phase-Transfer catalysed Michael and Michael tandem reactions including bifunctional catalysed Michael reactions. We have brought our own contribution to this field by establishing a few highly enantioselective procedures that used the Michael reaction of enolisable starting materials.

We describe a Michael-initiated ring closure (MIRC) reaction o f 2,3-disubstituted-1,1- cyclopropanediesters, obtained with good enantioselectivities, under operationally simple conditions and mild PTC catalysis. The study delivers a class of novel enantiopure Michael adducts which could serve as valuable building blocks and as template of high potential synthetic utility.

We have also developed a good enantioselective Michael-initiated ring closure (MIRC) reaction, starting from 3-substituted-2-(4-pyridyl)acrylonitrile compound. The study furnishes a new generation of olefins that can be used as Michael’s substrate and densely functionalized enantiopure cyclopropanes.

We describe as well a novel high enantioselective Michael addition under phase-transfer catalysis between (Z)-3-substituted-2-(4-pyridyl)acrylonitrile olefins and isocyanoacetates leading to densely functionalized cycloadducts in excellent enantiomeric excesses.

We describe in addition the tandem intermolecular [4 + 2] / intermolecular [3 + 2] cycloaddition of nitroalkenes, vinyl ethers and acrylates under homogeneous and biphasic conditions.

We finally describe the enantioselective addition of bisulfite to a,P-unsaturated ketones for the preparation of sulfonic acids in a preparative scale to afford multigram quantities of sulfonic acids in high yields and enantioselectivities.

History

First Supervisor

Professor Mauro FA Adamo

Second Supervisor

Dr Maria Moccia

Comments

A thesis submitted for the degree of Doctor of Philosophy from the Royal College of Surgeons in Ireland in 2014.

Published Citation

Del Fiandra C. Development of Phase Transfer Catalysed Cyclopropanation and Related Processes [PhD Thesis]. Dublin: Royal College of Surgeons in Ireland; 2014.

Degree Name

Doctor of Philosophy (PhD)

Date of award

30/06/2014

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