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Dual Gold (I) Catalysed Cyclisation of Dialkynyl Pyridinium salts
Ruprecht-Karls-Universität Heidelberg.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry. (Joseph Samec)ORCID iD: 0000-0001-7779-1849
Ruprecht-Karls-Universität Heidelberg.
Ruprecht-Karls-Universität Heidelberg.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Novel dialkynyl pyridines were synthesised and protected as alkyl salts for dual gold (I) catalysed cycloisomerisation. Different alkyl groups and counter ions were screened for the salts, with benzyl and PF6- providing the best results. The cyclisation led to NMR yields of >95% being obtained for a number of substrates. Step-wise hydrogenation of products could be carried out in one-pot by Pd/C, with selective reduction of the double bonds, followed by deprotection of the Bn group.

Keyword [en]
chemistry
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-272369OAI: oai:DiVA.org:uu-272369DiVA: diva2:893884
Available from: 2016-01-13 Created: 2016-01-13 Last updated: 2016-02-12Bibliographically approved
In thesis
1. Noble Metal Catalysed Reductions and Rearrangements
Open this publication in new window or tab >>Noble Metal Catalysed Reductions and Rearrangements
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The focus of this thesis has been organometallic catalysis applied to compounds containing heteroatoms which are usually poisonous to metal catalysts, by channelling their innate reactivity advantageously. The studies described in this thesis concentrate, in the first part, on iridium catalysed asymmetric hydrogenation (papers I and II) and in the second part, on gold catalysed internal rearrangements (papers III and IV). In each case, two classes of compounds are studied: pyridinium salts or sulphurous compounds. The asymmetric hydrogenation of pyridinium compounds was performed with 2% loading of N,P-ligated Ir catalyst with I2 additive (paper I) to achieve moderate to good enantiomeric excess (up to 98%). In paper II, olefinic sulphones were hydrogenated with an efficient 0.5% catalytic loading. In most cases full conversion was obtained and with good to excellent ees (up to 99%). The products of these reductions are chiral compounds, which could constitute further chemical building blocks. Palladium and gold were used sequentially in paper III, in order to perform a “Click” thiol-yne reaction followed by a semi-Pinacol rearrangement, leading to isolated yields of up to 98%. In paper IV The gold catalysed rearrangement of alkyl-pyridinium diynes was conducted, with a number of substrates providing >90% NMR yield. A highly selective hydrogenation was performed with a heterogeneous palladium catalyst to yield single diastereomer products. This methodology consists of up to three steps, with two catalysts in one pot.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2016. 63 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1337
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-272383 (URN)978-91-554-9453-7 (ISBN)
Public defence
2016-02-25, B/B21, BMC, Husargatan 3, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2016-02-03 Created: 2016-01-13 Last updated: 2016-02-12

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Cadu, AlbanSamec, Joseph

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