Vielfältige Reaktivitäten: aktuelle Entwicklungen bei metallkatalysierten Alkinreaktionen

Parrodi, Cecilia Anaya de; Walsh, Patrick J.

doi:10.1002/ange.200900900

Angewandte Chemie

2009

DOI: 10.1002/ange.200900900

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Vielfältige Reaktivitäten: aktuelle Entwicklungen bei metallkatalysierten Alkinreaktionen

Cecilia Anaya de Parrodi

Patrick J. Walsh

Abstract: Was Alkine alles können: Dank entscheidender Fortschritte bei metallkatalysierten Alkinreaktionen konnte der präparative Nutzen von Alkinen in letzter Zeit deutlich erhöht werden. Damit ist nun ein breiteres Spektrum von Alkinen durch C‐N‐ und C‐C‐Bindungsbildung zugänglich, und darüber hinaus wurde gezeigt, dass difunktionelle Heterodimetallkatalysatoren zu neuen Reaktivitäten und hervorragenden Enantioselektivitäten führen können (siehe Schema).magnified image

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Cited by 13 publications

References 28 publications

(22 reference statements)

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A Novel Strategy for the Construction of Functionalized 1,5‐ Benzodiazepines via a Tandem Conjugated Addition/Cyclization Process

Li¹,

Li²,

Li³

et al. 2010

Adv Synth Catal

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A novel approach for the synthesis of functionalized 1,5-benzodiazepine is described. The protocol is triggered by a tandem conjugated addition/cyclization process from the readily available starting materials 1,2-phenylenediamine and ethyl propiolate. The products have secondary amino and ester groups, and a b-enamino ester, which can serve in further functionalizations to produce molecular diversity.

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A Novel Strategy for the Construction of Functionalized 1,5‐ Benzodiazepines via a Tandem Conjugated Addition/Cyclization Process

Li¹,

Li²,

Li³

et al. 2010

Adv Synth Catal

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show abstract

Metallacyclic Pyridylidene Structures from Reactions of Terminal Pyridylidenes with Alkenes and Acetylene

et al. 2010

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Iridiumpyridyle sind Schlüsselintermediate in den Titelreaktionen. Die thermische Eliminierung von Benzol aus Komplexen 1 (R=Me, Ph) erzeugt eine freie Koordinationsstelle, die für ungesättigte Kohlenwasserstoffe zugänglich ist. Der nachfolgende intramolekulare nucleophile Angriff durch das Pyridyl‐Stickstoffatom an die Alken‐ oder Vinylidengruppe führt zu iridacyclischen Pyridylidenstrukturen (siehe Schema).

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Nickel‐Catalyzed Asymmetric Addition of Alkyne CH Bonds across 1,3‐Dienes Using Taddol‐Based Chiral Phosphoramidite Ligands

Shirakura

Suginome

2010

Angewandte Chemie

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Much interest has been focused on the catalytic, direct conversion of alkyne C À H bonds through C À C bond-forming reactions without the stoichiometric generation of acetylides. [1] One of the most widely used procedures for such an atom-economical process is the nucleophilic alkynylation of carbonyl compounds, a,b-unsaturated carbonyl compounds, or related electrophiles, in which catalytically generated metal acetylides often play a key role. [2, 3] Recent attention has focused on the development of asymmetric variants of these nucleophilic alkynylation reactions for the synthesis of highly functionalized chiral alkyne derivatives. [4,5] Besides these nucleophilic alkynylation reactions, hydroalkynylation, i.e. the addition of alkyne C À H bonds, across unactivated carbon-carbon multiple bonds has attracted increasing attention. [1b] After extensive studies on the homoand cross-dimerization reactions of alkynes using rhodium, palladium, and nickel catalysts, [6] hydroalkynylation has been extended to carbon-carbon double bonds, such as those in allenes and cyclopropenes. [7,8] However, the scope of the hydroalkynylation reaction is still significantly limited. [9,10] As a consequence, no successful catalytic asymmetric hydroalkynylation reactions have been established, except for the rhodium-catalyzed hydroalkynylation of allenes. [10] We recently showed that bulky triisopropylsilylacetylene underwent addition to C = C bonds in 1,3-dienes, norbornene, styrenes, and methylenecyclopropanes in the presence of nickel triorganophosphine catalysts. [9] The relatively narrow scope for the choice of phosphine ligands in these reactions could be a major difficulty in applying this system to asymmetric synthesis. Herein, we report the nickel-catalyzed asymmetric hydroalkynylation reactions of 1-aryl-1,3-butadienes involving the essential use of taddol-derived phosphoramidite ligands (taddol = 2,2-dimethyl-a,a,a',a'-tetraphenyldioxolane-4,5-dimethanol). In addition to the significance of the chiral ligands, the use of a terminal alkyne that contains an a-siloxy-sec-alkyl group on the alkynyl carbon is important to achieve sufficient reaction efficiency.

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Vielfältige Reaktivitäten: aktuelle Entwicklungen bei metallkatalysierten Alkinreaktionen

Cited by 13 publications

References 28 publications

A Novel Strategy for the Construction of Functionalized 1,5‐ Benzodiazepines via a Tandem Conjugated Addition/Cyclization Process

A Novel Strategy for the Construction of Functionalized 1,5‐ Benzodiazepines via a Tandem Conjugated Addition/Cyclization Process

Metallacyclic Pyridylidene Structures from Reactions of Terminal Pyridylidenes with Alkenes and Acetylene

Nickel‐Catalyzed Asymmetric Addition of Alkyne CH Bonds across 1,3‐Dienes Using Taddol‐Based Chiral Phosphoramidite Ligands

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