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Distal Fluoroboronate Substituents for Remote Control of Aryne Distortion and Regioselectivity
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Division of Theoretical Chemistry & Biology, School of Biotechnology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
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(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-328748OAI: oai:DiVA.org:uu-328748DiVA, id: diva2:1137223
Available from: 2017-08-30 Created: 2017-08-30 Last updated: 2017-08-31
In thesis
1. New Arylation Strategies Based on Organomain Group Reactivity
Open this publication in new window or tab >>New Arylation Strategies Based on Organomain Group Reactivity
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work in this thesis describes the development of new heteroarylation methodology based on transition metal-catalysed C-H functionalisation and the properties of organomain group compounds. The underlying reaction mechanisms and reactivity patterns of the (hetero)arene substrates are also investigated. The selective C2-H arylation indoles, which are key pharmaceutically-relevant units, was achieved using N-pyrimidyl directing groups, RuII catalysis and arylboronic acids as the coupling reagents (paper I). The use of this set of conditions enabled a remarkable functional group tolerance, highlighted by the preservation of halide substituents on both coupling partners. Mechanistic experiments suggest that cleavage of the C2-H bond occurs through an electrophilic aromatic substitution type pathway. The dehydrogenative C2-H silylation of unprotected gramine and tryptamine alkaloids and other related heteroarenes using hydrosilanes under Ru0 catalysis is described in paper II. The protocol does not require protecting groups and undirected C2-H silylation of heteroarenes is possible at higher temperatures. Significantly, H/D-exchange studies revealed deuterium incorporation at the C4 and C7 positions of the indole unit, apart from C2-H silylation. This study represents the first account of C4-H activation using an electron-rich metal catalyst. Paper III describes an unexpected and profound influence of boronate substituents on the regioselectivity of aryne trapping reactions. The boronates may be introduced easily to the backbone of established fluoride-activated precursors via Ir-catalysed C-H functionalisation. Optimisation and mechanistic studies on the unprecedented level of regioselectivity control these substituents permit using external additives is presented.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 80
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1552
Keywords
C-H functionalisation, catalysis, ruthenium, indole, silylation, boronate, boryl aryne, aryne distortion
National Category
Chemical Sciences
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-328750 (URN)978-91-513-0055-9 (ISBN)
Public defence
2017-10-20, B21, Biomedical Centre (BMC), Husargatan 3, Uppsala, 13:30 (English)
Opponent
Supervisors
Available from: 2017-09-29 Created: 2017-08-31 Last updated: 2017-10-17

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