Academic literature on the topic 'Suzuki-Miyaura domino coupling'

The Suzuki–Miyaura reaction is one of the most powerful tools for the formation of carbon–carbon bonds in organic synthesis. The utilization of alcohols in this powerful reaction is a challenging task. This short review covers progress in the transition-metal-catalyzed Suzuki­–Miyaura-type cross-coupling reaction of π-activated alcohol, such as aryl, benzylic, allylic, propargylic and allenic alcohols, between 2000 and June 2019.1 Introduction2 Suzuki–Miyaura Cross-Coupling Reactions of Aryl Alcohols2.1 One-Pot Reactions with Pre-activation of the C–O Bond2.1.1 Palladium Catalysis2.1.2 Nickel Catalysis2.2 Direct Activation of the C–O Bond2.2.1 Nickel Catalysis3 Suzuki–Miyaura-Type Cross-Coupling Reactions of Benzylic Alcohols4 Suzuki–Miyaura-Type Cross-Coupling Reactions of Allylic Alcohols4.1 Rhodium Catalysis4.2 Palladium Catalysis4.3 Nickel Catalysis4.4 Stereospecific Reactions4.5 Stereoselective Reactions4.6 Domino Reactions5 Suzuki–Miyaura-Type Cross-Coupling Reactions of Propargylic Alcohols5.1 Palladium Catalysis5.2 Rhodium Catalysis6 Suzuki–Miyaura-Type Cross-Coupling Reactions of Allenic Alcohols6.1 Palladium Catalysis6.2 Rhodium Catalysis7 Conclusions

A new Ni/Pd bimetallic multifunctional catalytic system has been developed for the domino Suzuki–Miyaura cross-coupling of benzyl alcohols with phenyl boronic acid and domino reduction C–N cross-coupling of the nitro compounds with aryl halides.

An Ugi four-component reaction was used to construct propargylamide starting materials for a subsequent domino Heck–Suzuki–Miyaura cross-coupling reaction to give derivatives of 4-benzylidene-1-oxo-3,4-dihydro-1H-isoquinoline.

The development of peptide stapling techniques to stabilise α-helical secondary structure motifs of peptides led to the design of modulators of protein–protein interactions, which had been considered undruggable for a long time. We disclose a novel approach towards peptide stapling utilising macrocyclisation by late-stage Suzuki–Miyaura cross-coupling of bromotryptophan-containing peptides of the catenin-binding domain of axin. Optimisation of the linker length in order to find a compromise between both sufficient linker rigidity and flexibility resulted in a peptide with an increased α-helicity and enhanced binding affinity to its native binding partner β-catenin. An increased proteolytic stability against proteinase K has been demonstrated.

Le myricanol est un [7,0]-métacyclophane naturel qui appartient à la famille des diarylheptanoïdes cycliques et qui possède des propriétés structurales et biologiques intéressantes (activité anti-Alzheimer ou anticancéreuse). L’objectif de ce travail de thèse est la préparation ambitieuse en voie racémique puis atropostéréosélective du myricanol, rendue délicate de part la tension de cycle existante. Pour se faire, deux nouvelles approches rétrosynthétiques ont été considérées. Une première route racémique a été envisagée et a permis de préparer le macrocycle par le biais d’une réaction de métathèse croisée suivie d’une réaction de Suzuki-Miyaura domino intramoléculaire avec un rendement de 2.55% en 11 étapes. Une autre voie racémique a également été explorée où la préparation du noyau biarylique du myricanol a été envisagé par une réaction de couplage intermoléculaire métallo-catalysée suivie d’une réaction de métathèse cyclisante. Des intermédiaires avancés ont également été préparés
The myricanol, a natural [7.0]-meta-cyclophane which belongs to the family of strained and cyclic diarylheptanoids, possess an interesting structure and attractive biologically activities (anti Alzheimer and anti cancer properties). Actually only two synthesis of racemic (+/-)-myricanol have been reported in the literature. The goal of this research was to prepare this strained cyclophane in a racemic and then in an atropostereoselective route taking into account the challenging ring closure. Thus a linear diarylheptanoid was prepared using an efficient cross-metathesis reaction followed by an intramolecular Suzuki-Miyaura domino reaction giving rise to the desired cyclophane with 2.55% overall yield in 11 steps. On the other side, the biaryl core of myricanol was envisaged by an intermolecular metallo-catalysed coupling reaction between already highly functionalized fragments, followed by a ring closure metathesis. Two advanced intermediates were already attempted

L'objectif principal de cette thèse de doctorat est la synthèse totale du myricanol, un composé naturel important aux activités biologiques intéressantes. En particulier, ses remarquables propriétés anti-Alzheimer en font un candidat potentiel pour le traitement de diverses taupathies, car il est capable de réduire les niveaux de protéine Tau qui ont tendance à s'accumuler sous forme phosphorylée dans certaines maladies neurodégénératives.. Actuellement, seules trois synthèses racémiques du (+/-)-myricanol sont rapportées dans la littérature. Tout d'abord, cette thèse vise principalement à explorer les conditions optimales pour rendre la cyclisation moins défavorable en utilisant un séco-précurseur insaturé et donc "rigide" en limitant les variations des degrés de liberté conformationnelles pendant la cyclisation. Deux approches synthétiques ont été explorées au cours de cette thèse, d’une part l'étape de macrocyclisation est réalisée à partir d’un système biarylique fonctionnalisé, d’autre part, l'étape de macrocyclisation est effectuée sur un diarylheptanoïde linéaire
The main objective of this thesis is the total synthesis of myricanol, a natural compound with significant biological activities. In particular, its remarkable anti-Alzheimer's properties make it a potential drug for the treatment of various tauopathies, as it has the ability to reduce levels of tau protein that tend to pathologically accumulate in phosphorylated forms in certain neurodegenerative diseases. Actually only three synthesis of racemic (+/-) - myricanol have been reported in the literature. Firstly, this thesis aims primarily to investigate the optimal conditions to make cyclization less unfavorable using an unsaturated and thus "rigid" seco-precursor to limit conformational degrees of freedom during cyclization. Two main synthetic approacheshave been explored in the course of this thesis, on one side, the macrocyclization involves the properly functionalized biaryl system, on the other side the macrocyclization is performed on a linear diarylheptanoid