The development of strain-release-driven transformations
: 1,2-metallate and semipinacol rearrangement reactions

Student thesis: Doctoral ThesisDoctor of Philosophy (PhD)

Abstract

Modern approaches to organic synthesis often look to break down target molecules into key molecular fragments. These fragments, or “building blocks”, require reactive functional groups that enable the target molecule to be assembled efficiently and selectively through the formation of new C–C or C–heteroatom bonds. This thesis outlines investigations into novel coupling reactions, which harness the inherent strain energy of small-ring cyclic building blocks. The key reaction mechanisms explored are strain-release-driven 1,2-rearrangement reactions.
Firstly, investigations into the 1,2-metallate rearrangement of boronate complexes with an activated cyclopropane α to boron are described. In addition, the strain-release of azabicyclo[1.1.0]butane was explored as the driving force for the 1,2-metallate rearrangement reaction. Finally, investigations into a novel strain-release semipinacol rearrangement reaction were undertaken.
All three reaction mechanisms facilitated the formation of a new C–C bond and provide access to novel molecules with interesting sp3-rich scaffolds and diverse functionality.
Date of Award28 Sep 2021
Original languageEnglish
Awarding Institution
  • The University of Bristol
SupervisorVarinder K Aggarwal (Supervisor)

Keywords

  • Strain release
  • Boronic esters
  • Azetidines
  • Cyclopropanes
  • Rearrangement reaction
  • Boronate complex
  • Azabicyclo[1.1.0]butane
  • Semipinacol rearrangement

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