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  • 1.
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Catalytic Methods to Convert Allylic Substrates through Hydride and Proton Shifts: Transition Metal-Catalyzed and Organocatalyzed Approaches2019Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The present thesis describes the development of new catalytic protocols to transform allylic substrates into a wide variety of versatile carbonyl and vinyl organic compounds. All procedures that are described in this work have in common the existence of one or more hydrogen shifts as key steps in the mechanism of the reactions. The thesis is divided into two mayor sections depending on the strategy employed, metal catalysis or organocatalysis. 

    The introductory chapter (Chapter 1) starts with an overview of the different types of catalysis and the importance of allylic substrates in organic chemistry. The chapter continues with an extensive description of the isomerization of allylic alcohols and finishes with a short introduction about hypervalent iodine chemistry. The goals of the thesis are also depicted at the end of this chapter.

    Chapters 2, 3 and 4 embody the use of iridium catalysis as an effective tool to synthesize α-functionalized carbonyl compounds selectively as single constitutional isomers from allylic alcohols. The first two chapters of this section describe the employment of several electrophiles to trap enolate derivatives formed from the corresponding allylic alcohols. Chapter 2 shows the development of two new protocols for the preparation of challenging α-iodinated carbonyl compounds. In chapter 3, the synthesis of α-aminooxy and α-hydroxyketones is investigated by employing an N-oxoammonium salt as electrophilic agent. Chapter 4 describes the development of an umpolung strategy that allows the synthesis of α-functionalized carbonyls through the reaction of two formal nucleophiles: enolate derivatives and alcohols. Mechanistic investigations performed in this section point to the presence of an iridium-catalyzed hydride shift operating in the reaction pathways.

    The last three chapters (5, 6 and 7) describe the development of metal-free methods for the conversion of allylic substrates into valuable products by means of base catalysis. Chapter 5 and 6 depict the stereospecific isomerization of a large scope of allylic alcohols, ethers and halides. A simple guanidine-type base, TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), is an effective catalyst to isomerize allylic substrates with excellent levels of transfer of chirality. The mechanism of this transformation is studied in detail experimentally and computationally and it is suggested to involve a [1,3]-proton shift through the formation of a tight ion-pair. Chapter 7 shows that base-catalysis allows the isomerization of conjugated polyenyl alcohols and ethers which has been proved to be challenging with metal–catalysis. Experimental and computational investigations in this last chapter suggests that the mechanism may proceed through a series of iterative [1,3]-proton shifts or “base-walk”. 

    The full text will be freely available from 2020-08-01 09:00
  • 2.
    Martinez-Erro, Samuel
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bermejo Gómez, Antonio
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Vazquez-Romero, Ana
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Erbing, Elis
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    2,2-Diiododimedone: a mild electrophilic iodinating agent for the selective synthesis of alpha-iodoketones from allylic alcohols2017In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 53, no 71, p. 9842-9845Article in journal (Refereed)
    Abstract [en]

    2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a new electrophilic iodinating agent that selectively iodinates electron-rich aromatics. In contrast to other common electrophilic iodinating reagents, its mild nature allows it to be used for the selective synthesis of alpha-iodinated carbonyl compounds from allylic alcohols through a 1,3-hydrogen shift/iodination process catalyzed by iridium(III) complexes.

  • 3.
    Martinez-Erro, Samuel
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    García-Vázquez, Víctor
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sanz-Marco, Amparo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selective Synthesis and Stereospecific Isomerization of Chiral Allylic HalidesManuscript (preprint) (Other academic)
  • 4.
    Martinez-Erro, Samuel
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sanz-Marco, Amparo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bermejo Gómez, Antonio
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Vazquez-Romero, Ana
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ahlquist, Mårten S. G.
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing2016In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 40, p. 13408-13414Article in journal (Refereed)
    Abstract [en]

    A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.

  • 5.
    Molleti, Nagaraju
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Carretero Cerdán, Alba
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Universidad País Vasco, Spain.
    Sanz-Marco, Amparo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Gomez-Bengoa, Enrique
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Base-Catalyzed [1,n]-Proton Shifts in Conjugated Polyenyl Alcohols and Ethers2019In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 9, no 10, p. 9134-9139Article in journal (Refereed)
    Abstract [en]

    The isomerization of dienyl alcohols and polyenyl alkyl ethers catalyzed by TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) under metal-free conditions is presented. Two reaction pathways have been observed. For dienyl alcohols, the reaction proceeds by a [1,3]-proton shift to give γ,δ-unsaturated ketones exclusively. On the other hand, the reaction with polyenyl alkyl ethers gives the corresponding conjugated vinyl ethers in good yields (up to 85%), with regioselectivities up to >20:1. Experimental and computational investigations suggest that the mechanism proceeds through consecutive “chain-walking” proton shifts (“base walk”) mediated by TBD.

  • 6.
    Sanz-Marco, Amparo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selective Synthesis of Unsymmetrical Aliphatic Acyloins through Oxidation of Iridium Enolates2018In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 45, p. 11564-11567Article in journal (Refereed)
    Abstract [en]

    The first method to access unsymmetrical aliphatic acyloins is presented. The method relies on a fast 1,3-hydride shift mediated by an Ir-III complex in allylic alcohols followed by oxidation with TEMPO+. The direct conversion of allylic alcohols into acyloins is achieved in a one-pot procedure. Further functionalization of the C alpha' of the alpha-amino-oxylated ketone products gives access to highly functionalized unsymmetrical aliphatic ketones, which further highlights the utility of this transformation.

  • 7.
    Sanz-Marco, Amparo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pauze, Martin
    Gómez-Bengoa, Enrique
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    An Umpolung Strategy to React Catalytic Enols with NucleophilesManuscript (preprint) (Other academic)
  • 8.
    Sanz-Marco, Amparo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pauze, Martin
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Universidad del PaísVasco/UPV-EHU, Spain.
    Gómez-Bengoa, Enrique
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    An umpolung strategy to react catalytic enols with nucleophiles2019In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 10, article id 5244Article in journal (Refereed)
    Abstract [en]

    The selective synthesis of a-functionalized ketones with two similar enolizable positions can be accomplished using allylic alcohols and iridium(III) catalysts. A formal 1,3-hydrogen shift on allylic alcohols generates catalytic iridium-enolates in a stereospecific manner, which are able to react with electrophiles to yield alpha-functionalized ketones as single constitutional isomers. However, the employment of nucleophiles to react with the nucleophilic catalytic enolates in this chemistry is still unknown. Herein, we report an umpolung strategy for the selective synthesis of alpha-alkoxy carbonyl compounds by the reaction of iridium enolates and alcohols promoted by an iodine(III) reagent. Moreover, the protocol also works in an intra-molecular fashion to synthesize 3(2H)-furanones from gamma-keto allylic alcohols. Experimental and computational investigations have been carried out, and mechanisms are proposed for both the inter- and intramolecular reactions, explaining the key role of the iodine(III) reagent in this umpolung approach.

  • 9.
    Sanz-Marco, Amparo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Možina, Štefan
    Martinez-Erro, Samuel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Iskra, Jernej
    Martín‐Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis of alpha-Iodoketones from Allylic Alcohols through Aerobic Oxidative Iodination2018In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 360, no 20, p. 3884-3888Article in journal (Refereed)
    Abstract [en]

    An efficient method for the synthesis of alpha-iodoketones from allylic alcohols and elemental iodine is reported. We show in this paper that the isomerization of allylic alcohols catalyzed by iridium(III) complexes can be combined with an aerobic oxidative iodination protocol, resulting in a straightforward method for the synthesis of a wide range of alpha-iodoketones as single constitutional isomers and in high yields under mild reaction conditions.

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