The Application of sSPhos as a Chiral Ligand in Palladium-Catalysed Reactions: Arylative Dearomatisations, and Heteroarylative Cyclisations with Alkenes
type: CreativeWork
description: Pd(0)-catalysed arylative dearomatisation of phenols generates complex stereocentre-containing products from simple planar phenols. The first half of this thesis will summarise our efforts to develop general enantioselective variants of these methods. The second half of this thesis focuses on the development of enantioselective heteroarylative cyclisations with alkenes. Central to all our results is the use of a sulfonated chiral ligand, sSPhos. This ligand was first reported in 2005 by Anderson and Buchwald for performing cross-coupling reactions in water. It was repurposed by the Phipps group, first to control site-selectivity in cross-coupling reactions, and then to control enantioselectivity in atroposelective Suzuki-Miyaura couplings. The work described in this thesis extends its use as a chiral ligand to new reaction types. In all cases, enantioinduction is thought to arise from the involvement of the ligand sulfonate group in attractive substrate-ligand ionic interactions. The first results chapter will discuss the application of the Pd/sSPhos catalytic system in enantioselective intramolecular arylative dearomatisations of phenols. This work was conducted in collaboration with a former postdoc in the Phipps group, Dr David Whalley, and most of the results were published in 2023 (J. Am. Chem. Soc. 2023, 145, 47, 25553–25558). The second results chapter will present the extension of this concept to an intermolecular arylative dearomatisation reaction, with selected results published in 2024 (J. Am. Chem. Soc. 2024, 146, 34970-34978). The third chapter discusses unpublished results on the application of the same catalytic system to the cyclisation of 2-allylanilines and 2-allylphenols with aryl bromide electrophiles, for the synthesis of chiral indolines and 2,3-dihydrobenzofurans. This project is ongoing and being continued by Paul Jirsch, a visiting Master’s student in the Phipps group. The final chapter presents an enantioselective formal synthesis of a natu…
abstract: Pd(0)-catalysed arylative dearomatisation of phenols generates complex stereocentre-containing products from simple planar phenols. The first half of this thesis will summarise our efforts to develop general enantioselective variants of these methods. The second half of this thesis focuses on the development of enantioselective heteroarylative cyclisations with alkenes. Central to all our results is the use of a sulfonated chiral ligand, sSPhos. This ligand was first reported in 2005 by Anderson and Buchwald for performing cross-coupling reactions in water. It was repurposed by the Phipps group, first to control site-selectivity in cross-coupling reactions, and then to control enantioselectivity in atroposelective Suzuki-Miyaura couplings. The work described in this thesis extends its use as a chiral ligand to new reaction types. In all cases, enantioinduction is thought to arise from the involvement of the ligand sulfonate group in attractive substrate-ligand ionic interactions. The first results chapter will discuss the application of the Pd/sSPhos catalytic system in enantioselective intramolecular arylative dearomatisations of phenols. This work was conducted in collaboration with a former postdoc in the Phipps group, Dr David Whalley, and most of the results were published in 2023 (J. Am. Chem. Soc. 2023, 145, 47, 25553–25558). The second results chapter will present the extension of this concept to an intermolecular arylative dearomatisation reaction, with selected results published in 2024 (J. Am. Chem. Soc. 2024, 146, 34970-34978). The third chapter discusses unpublished results on the application of the same catalytic system to the cyclisation of 2-allylanilines and 2-allylphenols with aryl bromide electrophiles, for the synthesis of chiral indolines and 2,3-dihydrobenzofurans. This project is ongoing and being continued by Paul Jirsch, a visiting Master’s student in the Phipps group. The final chapter presents an enantioselective formal synthesis of a natu…
author: Kadarauch, Maximilian
language: eng
keywords: palladium, catalysis, asymmetric, dearomatisation
license: https://www.repository.cam.ac.uk/bitstreams/5a0ed739-7f2c-4a18-bae7-30e16f0b16be/download
license: http://purl.org/NET/rdflicense/allrightsreserved
date published: 2025-09-27
date modified: 2026-07-22T22:24:24Z
provider: Cambridge University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Cambridge

PropertyValue
property ID: DOI
value: 10.17863/CAM.123439