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Direct, Sequential, and Stereoselective Alkynylation of C,C-Dibromophosphaalkenes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 30, 10614-10619 p.Article in journal (Refereed) Published
Abstract [en]

The first direct alkynylation of C,C-dibromophosphaalkenes by a reaction with sulfonylacetylenes is reported. Alkynylation proceeds selectively in the trans position relative to the P substituent to afford bromoethynylphosphaalkenes. Owing to the absence of transition metals in the procedure, the previously observed conversion of dibromophosphaalkenes into phosphaalkynes through the phosphorus analog of the Fritsch-Buttenberg-Wiechell rearrangement is thus suppressed. The bromoethynylphosphaalkenes can subsequently be converted to C,C-diacetylenic, cross-conjugated phosphaalkenes by following a Sonogashira coupling protocol in good overall yields. By using the newly described method, full control over the stereochemistry at the P=C double bond is achieved. The substrate scope of this reaction is demonstrated for different dibromophosphaalkenes as well as different sulfonylacetylenes.

Place, publisher, year, edition, pages
2016. Vol. 22, no 30, 10614-10619 p.
Keyword [en]
alkynylation, cross-conjugation, phosphaalkenes, Sonogashira coupling, sulfonyl coupling
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-302705DOI: 10.1002/chem.201601955ISI: 000380273300043PubMedID: 27310813OAI: oai:DiVA.org:uu-302705DiVA: diva2:967390
Funder
Swedish Research CouncilCarl Tryggers foundation
Available from: 2016-09-08 Created: 2016-09-08 Last updated: 2017-08-21Bibliographically approved
In thesis
1. Novel Organophosphorus Compounds for Materials and Organic Synthesis
Open this publication in new window or tab >>Novel Organophosphorus Compounds for Materials and Organic Synthesis
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is devoted to the development of new organophosphorus compounds for potential uses in material science and as reagents in Organic Chemistry. Organophosphorus compounds in a single molecule or organic electronics context are appealing as the phosphorous centers perturb the electronic properties of the π-conjugated systems while at the same time provide synthetic handles for subsequent synthetic modifications. As such, new synthetic methodology to such compounds and the exploration of new building blocks is of considerable interest. In a different study, novel organophosphorus compounds are synthesized and shown to promote a reaction in Organic Chemistry that has previously not been possible, i.e. the stereoselective reductive coupling of aldehydes to alkenes. Such developments enlarge the toolkit of reactions that are available to Organic Chemists, and may impact the synthetic routes to pharmaceuticals and other important commodity chemicals.

A general introduction of the key structural unit of this thesis, phosphaalkenes, is given in the first chapter. The synthesis, reactivity, properties and applications of these P=C double bond containing compounds are highlighted. The Wittig reaction and its variations as well as the phosphorus analogues that produce phosphaalkenes are outlined in detail.

The second chapter is dedicated to the synthesis of a precursor that is used for the preparation of novel π-conjugated, organophosphorus compounds. C,C-Dibromophosphaalkenes are prepared and the halide substituents are used for the selective introduction of acetylene units. Besides the phosphaalkenes, the successful syntheses of two new diphosphenes is presented, indicating a broad applicability of the precursors.

The third chapter is dedicated to the isolation of a metal-free phosphanylphosphonate that transforms aldehydes quantitatively to their corresponding E-phosphaalkenes in a transition metal-free phospha-HWE (Horner-Wadsworth-Emmons) reaction. The reaction benefits from mild conditions, high E-stereoselectivity, and a broad substrate scope.

In the last chapter, a novel method for the reductive coupling of aldehydes to olefins is introduced. The reaction, which is a vast improvement over the McMurry coupling, allows for the selective synthesis of symmetrical and most importantly unsymmetrical E-alkenes. The phosphanylphosphonate mentioned above is the reagent that facilitates the coupling of the aldehydes via a phosphaalkene intermediate. This one-pot reaction benefits from mild conditions, good conversions, and high E-stereoselectivity.

In summary, the thesis presents novel aspects of organophosphorus chemistry. These include the preparations and exploration of interesting precursors for the construction of π-conjugated organophosphorus compounds, and the use of organophosphorus reagents for unprecedented transformations in Organic Chemistry.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 84 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1546
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-328295 (URN)978-91-513-0045-0 (ISBN)
Public defence
2017-10-13, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:00 (English)
Opponent
Supervisors
Available from: 2017-09-20 Created: 2017-08-21 Last updated: 2017-10-17

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