Exploiting sulfinate coupling partners for the preparation of diversely functionalised heterocycles

Thesis

In the following thesis, sulfinates have been exploited for the formation of di(hetero)arylmethanes and bi(hetero)aryls, either by being formed in situ or through a straightforward synthetic sequence.

Chapter 1 discusses previously developed desulfinative cross-coupling methodologies, an overview of the application of sulfinate salts in synthetic chemistry, and cross-coupling reactions to construct C(sp²)- C(sp³) bonds.

Chapter 2 details the route development for the synthesis of benzyl sulfinate starting materials.

Chapter 3 presents a palladium catalysed C(sp²)- C(sp³) desulfinative cross-coupling to form di(hetero)arylmethanes from benzyl sulfinates and heteroaryl halides.

Chapter 4 demonstrates further developments to the palladium catalysed C(sp²)- C(sp³) desulfinative cross-coupling to form di(hetero)arylmethanes, through a one-pot protocol. The benzyl sulfinate is formed in situ before entering the cross-coupling step. This methodology avoids problematic preparation and storage of unstable benzyl sulfinates, allowing a wider variety of di(hetero)arylmethanes to be accessed.

Chapter 5 describes practical and safety improvements made to the palladium catalysed C(sp²)- C(sp²) desulfinative cross-coupling process, to form bi(hetero)aryls on large scale.

Chapter 6 concludes the work and evaluates potential avenues for future research.

Chapter 7 details the experimental procedures and data.

Authors: McKnight, J

• DOI: 10.5287/ora-gjepa8bke
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: desulfinative; sulfinate; cross-coupling; catalysis; diarylmethane; reductive coupling; palladium
• Subjects: Chemistry, Organic; Catalysis; Synthesis