Asymmetric Suzuki-Miyaura couplings of acyclic allylic systems

Thesis

The objective of this thesis is to investigate and develop Rh(I)-catalysed Suzuki-Miyaura cross-couplings of acyclic allylic species with arylboronic acids. While our group has achieved an asymmetric Rh-catalyzed Suzuki-Miyaura cross-coupling of cyclic racemic allylic halides and boronic acids, the catalyst-controlled stereoselective coupling of more complex acyclic unsymmetrical molecules has not been explored.

In this thesis, we present our efforts towards the development of a Rh-catalyzed enantioselective Suzuki-Miyaura cross-coupling with racemic acyclic substrates that have few or no symmetry elements. This approach represents an unprecedented advance that significantly broadens the applicability of this reaction.

We discuss the development of an enantioconvergent Suzuki-Miyaura cross-coupling of acyclic allylic systems in Chapter 2, while Chapter 3 explores the asymmetric formation of all-carbon quaternary stereocenters via the developed Suzuki-Miyaura cross-coupling of acyclic allylic systems. Additionally, Chapter 4 focuses on Suzuki-Miyaura couplings using terminal acyclic allylic systems and outlines a modular asymmetric synthesis of 3-aryl-α-tetralones via sequential double arylation.

Overall, the thesis addresses the challenges associated with synthesising acyclic C(sp3)-rich compounds using novel asymmetric Suzuki-Miyaura couplings, with the aim of developing more efficient methods for producing enantioenriched small molecules.

Authors: Stojalnikova, V

• DOI: 10.5287/ora-aoyary4md
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: asymmetric catalysis