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Universitat Rovira i Virgili

1. Wu, Yichen. Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds.

Degree: Departament de Química Analítica i Química Orgànica, 2017, Universitat Rovira i Virgili

The chemistry of organic hypervalent iodine compounds has been a potent and versatile toolbox in organic synthesis. In particular, organic λ3-iodanes have been utilized as terminal 2-electron oxidants, as well as group transfer agents in a wide range oxidative functionalization processes. With few exceptions, such transformations are accompanied by the liberation of the parent organoiodine fragment. A less explored, but synthetically attractive possibility consists in incorporating both the organic group and the iodine atom into the final product. Such approach presents a clear synthetic appeal, given that the iodine retention opens the door for downstream derivatization. This thesis describes a series of such “iodine-directed” coupling reaction employing organo-λ3-iodanes as substrates. In one approach, a new method for direct metal-free α-arylation of ketones is described. The aryl transfer takes place via the coupling ortho to iodine, and is based on in situ hypervalent activation of the iodine atom. The protocol shows good functional group compatibility on the arene core. The ortho-selectivity was rationalized by DFT calculations through an unusual low-barrier “iodonio-Claisen¨ process. We also developed a new approach for regioselective benzylation of the ArI(OAc)2 cores using benzyltrimethylsilane. Interestingly, the carbon-carbon coupling now takes place selectively at para position to the iodine atom. Finally, an approach for oxidative “iodoarylation” of imidazoles was uncovered. The procedure relies on an efficient activation of the parent NH-imidazole with ArI(OAc)2, followed by copper-catalyzed intramolecular 1,3 I-to-N aryl transfer to constitute the synthetically challenging N1-aryl-5-iodoimidazoles. The importance of this manifold resides in the ability of the 5-iodoimidazoles to act as precursors for a range of 1,5-substituted imidazoles. Advisors/Committee Members: [email protected] (authoremail), false (authoremailshow), Shafir, Alexandr, (director), true (authorsendemail).

Subjects/Keywords: iode hipervalent; iodoarene; yodo hipervalente; yodoareno; hypervalent iodine; iodoarene; Ciències; 54; 542; 547

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Wu, Y. (2017). Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds. (Thesis). Universitat Rovira i Virgili. Retrieved from http://hdl.handle.net/10803/461093

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16th Edition):

Wu, Yichen. “Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds.” 2017. Thesis, Universitat Rovira i Virgili. Accessed April 03, 2020. http://hdl.handle.net/10803/461093.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7th Edition):

Wu, Yichen. “Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds.” 2017. Web. 03 Apr 2020.

Vancouver:

Wu Y. Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds. [Internet] [Thesis]. Universitat Rovira i Virgili; 2017. [cited 2020 Apr 03]. Available from: http://hdl.handle.net/10803/461093.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Wu Y. Hypervalent Iodine as Directing Tool in Iodine-Retentive Transformation of C-H Bonds. [Thesis]. Universitat Rovira i Virgili; 2017. Available from: http://hdl.handle.net/10803/461093

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation


Université de Bordeaux I

2. Marguerit, Mélanie. Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa.

Degree: Docteur es, Chimie organique, 2009, Université de Bordeaux I

La réaction de désaromatisation hydroxylante de phénols (HPD) est un outil puissant pour accéder de façon biomimétique, en une seule étape à partir de 2-alkylphénols, aux ortho-quinols, c’est-à-dire les 6-alkyl-6-hydroxycyclohexa-2,4-diénones. Ces synthons peuvent être présentés tels quels par de nombreux produits naturels mais peuvent aussi servir d’intermédiaires hautement fonctionnalisés pour la construction rapide d’architectures structurales complexes. L’acide o-iodoxybenzoïque (IBX), un réactif de type iodane-?5, et sa formulation stabilisée non-explosible (SIBX) se sont révélés particulièrement efficaces pour promouvoir des réactions HPD de manière ortho-sélective. Ces travaux de thèse concernent l’application de cette réaction à l’élaboration d’un intermédiaire ortho-quinolique clé hautement fonctionnalisé pour la synthèse d’un antibiotique de type angucycline, la (+)-aquayamycine, ainsi qu’à la première synthèse totale d’un ortho-quinol naturel non dimérisant, la (+)-wasabidiénone B1. Enfin, le développement d’une version asymétrique de cette réaction a été entrepris. La génération in situ de iodanes à partir de iodoarènes chiraux et de m-CPBA comme co-oxydant permet de préparer soit des ortho-quinols de façon non racémique lorsque des quantités stoechiométriques des deux réactifs sont utilisées, soit des ortho-quinols régio- et diastéréosélectivement époxydés lorsqu’une quantité catalytique de iodoarène chiral est employée. Un suivi de ces réactions par spectrométrie de masse a conduit à la détection d’espèces de type iodanyl-?3 et/ou -?5, et à la proposition d’un mécanisme pour ces réactions de désaromatisation hydroxylante asymétrique.

The hydroxylative phenol dearomatization (HPD) reaction is a powerful tool to access, in one biomimetic step from various 2-alkylphenols, ortho-quinols, i.e., 6-alkyl-6-hydroxycyclohexa-2,4-dienones. These dearomatized moieties can be found as such in few natural products or can be used as highly functionalized intermediates. The ?5-iodane 2-iodoxybenzoic acid (IBX) and its stabilized nonexplosive formulation (SIBX) have proved particularly useful and efficient in mediating HPD reactions in a strictly ortho-selective manner. This PhD work describes the application of our SIBX-mediated HPD reaction to the elaboration of a key ortho-quinolic advanced intermediate for the synthesis of the angucycline-type antibiotic (+)-aquayamycin, and to the first total synthesis of the natural non-dimerizing ortho-quinol (+)-wasabidienone B1. An asymmetric version of this HPD reaction has been also developed. In situ generation of iodanes from chiral iodoarenes and m-CPBA as co-oxidant enables the preparation of either ortho-quinols in a non racemic form when using stoechiometric amounts of both reagents, or regio- and diastereoselectively epoxidized ortho-quinols when a catalytic amount of the chiral iodoarene is used. Monitoring of these reactions by mass spectrometry allowed the detection of ?3- and/or ?5-iodanyl-type species, and the proposition of a mechanism for these asymmetric…

Advisors/Committee Members: Quideau, Stéphane (thesis director).

Subjects/Keywords: Synthèse totale; Iodoarène; Réaction HPD; Désaromatisation oxydante de phénols; Ortho-quinol; Désaromatisation hydroxylante de phénols; Iode hypervalent; Cyclohexa-2,4-diénone; Iodane; Substances naturelles; Total synthesis; Phenol oxidative dearomatization; Hypervalent iodine; Iodane; Iodoarene; Ortho-quinol; Cyclohexa-2,4-dienone; Natural products; HPD reaction; Hydroxylative phenol dearomatization

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Marguerit, M. (2009). Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa. (Doctoral Dissertation). Université de Bordeaux I. Retrieved from http://www.theses.fr/2009BOR13924

Chicago Manual of Style (16th Edition):

Marguerit, Mélanie. “Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa.” 2009. Doctoral Dissertation, Université de Bordeaux I. Accessed April 03, 2020. http://www.theses.fr/2009BOR13924.

MLA Handbook (7th Edition):

Marguerit, Mélanie. “Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa.” 2009. Web. 03 Apr 2020.

Vancouver:

Marguerit M. Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa. [Internet] [Doctoral dissertation]. Université de Bordeaux I; 2009. [cited 2020 Apr 03]. Available from: http://www.theses.fr/2009BOR13924.

Council of Science Editors:

Marguerit M. Désaromatisation hydroxylante de phénols par des réactifs iodés hypervalents : application à la synthèse de substances naturelles : Function and dysfunction of active efflux systems in clinical strains of pseudomonas aeruginosa. [Doctoral Dissertation]. Université de Bordeaux I; 2009. Available from: http://www.theses.fr/2009BOR13924

.