Organoboron Reagents and Recent Strategies in Rhodium Catalysed Additions

Hannah Joy Edwards

Research output: ThesisDoctoral Thesis

Abstract

The research presented herein is concerned with the exploration of the rhodium catalysed addition of organoboron reagents.
Chapter 1 firstly introduces the area of organoboron reagents, focussing on the applications of potassium alkenyl trifluoroborate reagents. Secondly, an extensive discussion of the rhodium catalysed conjugate addition of organboron reagents demonstrates its utility as a key coupling step in recent syntheses.
Chapter 2 describes synthetic methods towards alkenylboron reagents and describes the synthesis of functionalised and enantiopure alkenyl trifluoroborate salts.
Chapter 3 discusses the rhodium catalysed addition of potassium alkenyl trifluoroborate salts to α,β-unsaturated compounds. A gas chromatography study addresses issues concerning protodeboronation and highlights the potential for olefin transposition. A new rhodium catalysed olefin transposition reaction has been thoroughly investigated and applied using the synthesised potassium alkenyl trifluoroborate salts.
Chapter 4 describes the synthesis of biologically relevant, enantiopure dihydropyranones for use as acceptors in the rhodium catalysed conjugate addition reaction. The hetero-Diels-Alder reaction is employed to synthesise the dihydropyranones. Rhodium catalysed conjugate addition of arylboronic acids and potassium alkenyl trifluoroborates is utilised to concisely assemble late stage intermediates of natural products including diospongin B.
Chapter 5 describes the synthesis and characterisation of the compounds discussed in chapters 2, 3 and 4.
LanguageEnglish
QualificationPh.D.
Awarding Institution
  • University of Bath
Supervisors/Advisors
  • Frost, Christopher, Supervisor
Award date31 Dec 2012
StatusUnpublished - Sep 2011

Fingerprint

Rhodium
Potassium
Salts
Alkenes
Unsaturated compounds
Addition reactions
Biological Products
Gas chromatography
Acids

Keywords

  • 1,4-addition
  • enantioselective synthesis
  • organoboron reagents
  • alkenyl trifluroborates
  • vinylboronic esler

Cite this

Organoboron Reagents and Recent Strategies in Rhodium Catalysed Additions. / Edwards, Hannah Joy.

2011. 293 p.

Research output: ThesisDoctoral Thesis

@phdthesis{9ff41dfbf77944f9a958f0546abe1403,
title = "Organoboron Reagents and Recent Strategies in Rhodium Catalysed Additions",
abstract = "The research presented herein is concerned with the exploration of the rhodium catalysed addition of organoboron reagents.Chapter 1 firstly introduces the area of organoboron reagents, focussing on the applications of potassium alkenyl trifluoroborate reagents. Secondly, an extensive discussion of the rhodium catalysed conjugate addition of organboron reagents demonstrates its utility as a key coupling step in recent syntheses.Chapter 2 describes synthetic methods towards alkenylboron reagents and describes the synthesis of functionalised and enantiopure alkenyl trifluoroborate salts.Chapter 3 discusses the rhodium catalysed addition of potassium alkenyl trifluoroborate salts to α,β-unsaturated compounds. A gas chromatography study addresses issues concerning protodeboronation and highlights the potential for olefin transposition. A new rhodium catalysed olefin transposition reaction has been thoroughly investigated and applied using the synthesised potassium alkenyl trifluoroborate salts.Chapter 4 describes the synthesis of biologically relevant, enantiopure dihydropyranones for use as acceptors in the rhodium catalysed conjugate addition reaction. The hetero-Diels-Alder reaction is employed to synthesise the dihydropyranones. Rhodium catalysed conjugate addition of arylboronic acids and potassium alkenyl trifluoroborates is utilised to concisely assemble late stage intermediates of natural products including diospongin B.Chapter 5 describes the synthesis and characterisation of the compounds discussed in chapters 2, 3 and 4.",
keywords = "1,4-addition, enantioselective synthesis, organoboron reagents, alkenyl trifluroborates, vinylboronic esler",
author = "Edwards, {Hannah Joy}",
year = "2011",
month = "9",
language = "English",
school = "University of Bath",

}

TY - THES

T1 - Organoboron Reagents and Recent Strategies in Rhodium Catalysed Additions

AU - Edwards,Hannah Joy

PY - 2011/9

Y1 - 2011/9

N2 - The research presented herein is concerned with the exploration of the rhodium catalysed addition of organoboron reagents.Chapter 1 firstly introduces the area of organoboron reagents, focussing on the applications of potassium alkenyl trifluoroborate reagents. Secondly, an extensive discussion of the rhodium catalysed conjugate addition of organboron reagents demonstrates its utility as a key coupling step in recent syntheses.Chapter 2 describes synthetic methods towards alkenylboron reagents and describes the synthesis of functionalised and enantiopure alkenyl trifluoroborate salts.Chapter 3 discusses the rhodium catalysed addition of potassium alkenyl trifluoroborate salts to α,β-unsaturated compounds. A gas chromatography study addresses issues concerning protodeboronation and highlights the potential for olefin transposition. A new rhodium catalysed olefin transposition reaction has been thoroughly investigated and applied using the synthesised potassium alkenyl trifluoroborate salts.Chapter 4 describes the synthesis of biologically relevant, enantiopure dihydropyranones for use as acceptors in the rhodium catalysed conjugate addition reaction. The hetero-Diels-Alder reaction is employed to synthesise the dihydropyranones. Rhodium catalysed conjugate addition of arylboronic acids and potassium alkenyl trifluoroborates is utilised to concisely assemble late stage intermediates of natural products including diospongin B.Chapter 5 describes the synthesis and characterisation of the compounds discussed in chapters 2, 3 and 4.

AB - The research presented herein is concerned with the exploration of the rhodium catalysed addition of organoboron reagents.Chapter 1 firstly introduces the area of organoboron reagents, focussing on the applications of potassium alkenyl trifluoroborate reagents. Secondly, an extensive discussion of the rhodium catalysed conjugate addition of organboron reagents demonstrates its utility as a key coupling step in recent syntheses.Chapter 2 describes synthetic methods towards alkenylboron reagents and describes the synthesis of functionalised and enantiopure alkenyl trifluoroborate salts.Chapter 3 discusses the rhodium catalysed addition of potassium alkenyl trifluoroborate salts to α,β-unsaturated compounds. A gas chromatography study addresses issues concerning protodeboronation and highlights the potential for olefin transposition. A new rhodium catalysed olefin transposition reaction has been thoroughly investigated and applied using the synthesised potassium alkenyl trifluoroborate salts.Chapter 4 describes the synthesis of biologically relevant, enantiopure dihydropyranones for use as acceptors in the rhodium catalysed conjugate addition reaction. The hetero-Diels-Alder reaction is employed to synthesise the dihydropyranones. Rhodium catalysed conjugate addition of arylboronic acids and potassium alkenyl trifluoroborates is utilised to concisely assemble late stage intermediates of natural products including diospongin B.Chapter 5 describes the synthesis and characterisation of the compounds discussed in chapters 2, 3 and 4.

KW - 1,4-addition

KW - enantioselective synthesis

KW - organoboron reagents

KW - alkenyl trifluroborates

KW - vinylboronic esler

M3 - Doctoral Thesis

ER -