New organocatalytic strategies for the selective synthesis of centrally and axially chiral molecules / Nicola Di Iorio.

Intro; Supervisor's Foreword; Preface; Parts of this thesis have been published in the following articles:; Acknowledgements; Contents; Abbreviations; 1 Introduction; 1.1 Chirality and its Forms: Central, Axial and UnconventionalID=""Fn1""For further reading on chirality see: Eliel and Wilen [1].; 1.1.1 Central Chirality; 1.1.2 Axial Chirality; 1.1.3 Helical Chirality; 1.1.4 Planar Chirality; 1.2 Pursuing Enantiopure Chiral Molecules: Asymmetric Organocatalysis; 1.2.1 Aminocatalysis: Enamine and Iminium Ion; 1.2.2 Nucleophilic Catalysis

1.2.3 Brønsted Acid and Base CatalysisID=""Fn12""(a) For an exhaustive reading on Brønsted acid/base catalysis see: Rueping et al. [51] (b) Science of synthesis "Asymmetric organocatalysis 2
Brønsted base and acid catalysis, and additional topics", Thieme, 2012.; 1.2.4 Asymmetric Counterion-Directed and Phase-Transfer Catalysis; 1.2.5 Hydrogen-Bonding CatalysisID=""Fn16""For reviews see: (a) Doyle and Jacobsen [65]; (b) Knowles and Jacobsen [66].; 1.2.6 Dual Catalysis: Bifunctional and Cooperative; References

2 The Vinylogous Reactivity of Oxindoles Bearing Non-symmetric 3-Alkylidene Groups2.1 Vinylogy; 2.2 Results and Discussion; 2.3 Conclusions; 2.4 Experimental Section; 2.4.1 General Information; 2.4.2 Preparation of Deuterated Substrates; 2.4.3 General Procedure for the Preparation of Alkylidenoxindoles; 2.4.4 General Procedure for the Vinylogous Michael Addition of Non-symmetric 3-Alkylidene Oxindoles to Nitroalkenes; References; 3 Targeting the Remote Control of Axial Chirality in N-(2-tert-butylphenyl)Succinimides via a Desymmetrization Strategy

3.1 Desymmetrization as a Tool for Asymmetric Synthesis3.2 Results and Discussion; 3.3 Conclusions; 3.4 Experimental Section; 3.4.1 General Information; 3.4.2 Determination of the Barrier to Racemization of the Chiral Axis for Compound 137a; 3.4.3 General Procedure for the Vinylogous Michael Addition of Cyclic Enones to N-Arylmaleimmides; 3.4.4 General Procedure for the Desymmetrization of Maleimides with Different Nucleophiles; 3.4.5 General Procedure for the Desymmetrization of Maleimides with 3-Aryl Oxindoles; References

4 Direct Catalytic Synthesis of C(Sp2)-C(Sp3) Atropisomers with Simultaneous Control of Central and Axial Chirality4.1 Forging a Stereogenic Axis; 4.2 Results and Discussion; 4.3 Conclusions; 4.4 Experimental Section; 4.4.1 General Information; 4.4.2 General Procedure for the Synthesis of 4-Substituted Indenones; 4.4.3 Synthesis of Naphthol Derivatives; 4.4.4 General Procedure for the Synthesys of 8-Arylnaphthalen-2-Ol; 4.4.5 Determination of the Barrier to Racemization Relative to the Naphthol-Phenantrene Stereogenic Axis for Compound 244