nach oben

2015 | Buch

Kapitel lesen Erstes Kapitel lesen

Homogeneous Gold Catalysis

herausgegeben von: LeGrande M. Slaughter

Verlag: Springer International Publishing

Buchreihe : Topics in Current Chemistry

Enthalten in: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik"

Einloggen, um Zugang zu erhalten

Über dieses Buch

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science.

The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience.

Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.

Review articles for the individual volumes are invited by the volume editors.

Readership: research chemists at universities or in industry, graduate students.

Inhaltsverzeichnis

Frontmatter

Ligand Design in Gold Catalysis and Chemistry of Gold–Oxonium Intermediates

Abstract

Gold catalysis is considered one of the most important breakthroughs in organic synthesis during the last decade. Many gold-catalyzed reactions suffer from high catalyst loading, which is a serious limitation on the application of gold catalysis in larger scale synthesis. Because ligands play a major role in the tuning of reactivity of transition metal catalysts, there has been an increased effort on rationally understanding ligand effects in gold catalysis and using a rational ligand design to achieve higher efficiency. In the first part of this chapter, selected examples of ligand design in gold catalysis are discussed. In the second part, the chemistry of gold–oxonium intermediate is examined. An oxonium intermediate is generated when a oxygen nucleophile (ketone, aldehyde, or ether) attacks a cationic gold-activated multiple bond. This oxonium intermediate, being a highly energetic species, has the potential to undergo further transformations such as electron transfer/rearrangement/protodeauration to form diverse products.

Deepika Malhotra, Gerald B. Hammond, Bo Xu

Gold-Catalyzed Carbene Transfer Reactions

Abstract

In homogeneous gold catalysis, generations and reactions of metal carbenes have been one of the most rapidly developing areas because of their diverse reactivity under mild conditions. This review covers recent advances in the gold-catalyzed oxygen atom transfer and carbene transfer reactions to alkynes. Atom transfer to an alkyne enables alkynes to function as metal carbene synthons. Many such reactions fulfill redox neutrality starting from safe and easily handled precursors.

Seunghoon Shin

Gold-Catalyzed Transformation of Unsaturated Alcohols

Abstract

The use of gold-complexes to activate carbon–carbon π-bonds has become a well-known and highly reliable mode of reactivity for applications in organic synthesis. This review covers the use of gold-catalysts for activation of unsaturated alcohols to effect substitution with concomitant loss of water and is mostly focused on reactions where the π-acidity appears to overcome the inherent Lewis acidity of the complexes for alcohol activation. Select examples from the literature which demonstrate advances made between 2011 and 2014 are presented.

Paulo H. S. Paioti, Aaron Aponick

Gold-Catalyzed Domino Reactions

Abstract

Gold-catalyzed reactions have appeared to be highly attractive tools for chemists to promote novel transformations to prepare elaborated structures from simple starting materials. This chapter presents selected and original examples of domino processes in the presence of gold catalysts, highlighting reports implying hydration, hydroxylation, and hydroamination as key starting point for cascade transformations. Domino processes implying 1,n-enynes, asymmetric domino transformations, and applications of all the presented processes in total synthesis are presented.

Véronique Michelet

Gold π-Complexes as Model Intermediates in Gold Catalysis

Abstract

Homogeneous gold catalysis has emerged as a powerful method for activating hydrocarbon double and triple bonds. Methodology development and computational studies have blossomed in the past 20 years. In contrast, experimental exploration of mechanisms and structure-reactivity relationships has gained traction only in the past 5 years. Recent developments in the synthesis of organometallic intermediates have revealed exciting new details about the mechanisms of gold catalysis. Central to these studies are the structure and reactivity of gold π-complexes. Following successes in structurally characterizing these key structures, advancements are gradually being made in placing them in the context of an overall catalytic cycle. As a result, a research field has emerged which is rich with potential for continued discovery and catalyst improvement.

Amanda C. Jones

Aurophilicity in Gold(I) Catalysis: For Better or Worse?

Abstract

This book chapter discusses the effects of aurophilicity on gold catalysis. First, a brief historic account of aurophilicity in organogold chemistry is given, focusing on the pioneering results which set the stage for its association with catalytic intermediates (gold vinyl and gold aryl complexes); this is followed by an introduction to cationic gold(I) as an electrophilic catalyst, and the first isolation of organogold intermediates from catalysis. In the main section, the growing number of reports observing aurophilic interactions in catalysis or illustrative model systems is reviewed in a non-comprehensive tutorial way. The effects of aurophilicity are discussed in the following structures: (1) the geminal diauration of C(sp²)-atoms; (2) geminal diauration of other atoms; (3) σ-π-diauration of terminal alkynes. It is apparent that in most cases efficient catalysis is hindered by aurophilic effects as less active aggregates tend to be formed from more active species [LAu]⁺, but there are a growing number of reports using aurophilicity as a driving force to access new reactivity and selectivity.

Graphical Abstract

Dieter Weber, Michel R. Gagné

Computational Approaches to Homogeneous Gold Catalysis

Abstract

Homogenous gold catalysis has been exploding for the last decade at an outstanding pace. The best described reactivity of Au(I) and Au(III) species is based on gold’s properties as a soft Lewis acid, but new reactivity patterns have recently emerged which further expand the range of transformations achievable using gold catalysis, with examples of dual gold activation, hydrogenation reactions, or Au(I)/Au(III) catalytic cycles.

In this scenario, to develop fully all these new possibilities, the use of computational tools to understand at an atomistic level of detail the complete role of gold as a catalyst is unavoidable. In this work we aim to provide a comprehensive review of the available benchmark works on methodological options to study homogenous gold catalysis in the hope that this effort can help guide the choice of method in future mechanistic studies involving gold complexes. This is relevant because a representative number of current mechanistic studies still use methods which have been reported as inappropriate and dangerously inaccurate for this chemistry.

Together with this, we describe a number of recent mechanistic studies where computational chemistry has provided relevant insights into non-conventional reaction paths, unexpected selectivities or novel reactivity, which illustrate the complexity behind gold-mediated organic chemistry.

Olalla Nieto Faza, Carlos Silva López

Backmatter

Titel: Homogeneous Gold Catalysis
herausgegeben von: LeGrande M. Slaughter
Verlag: Springer International Publishing
Electronic ISBN: 978-3-319-13722-3
Print ISBN: 978-3-319-13721-6
DOI: https://doi.org/10.1007/978-3-319-13722-3

Premium Partner

Marktübersichten

Die im Laufe eines Jahres in der „adhäsion“ veröffentlichten Marktübersichten helfen Anwendern verschiedenster Branchen, sich einen gezielten Überblick über Lieferantenangebote zu verschaffen.

Zur Marktübersicht