Rh-Catalyzed Intermolecular Reactions of Alkynes with α-Diazoesters That Possess β-Hydrogens:  Ligand-Based Control over Divergent Pathways

Panne, Patricia; Fox, Joseph M.

doi:10.1021/ja0660195

Cited by 169 publications

(67 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[204] Mit Au-Katalysatoren kçnnen komplexe, mehrstufige Katalyseprozesse ermçglicht werden, wobei die besonders hohe Affinität der Allenaktivierung in Anwesenheit anderer funktioneller Gruppen hervorsticht. Im Folgenden heben wir zwei Beispiele für katalytische Divergenz zwischen Au-und Pt-Katalysatoren [205] [210] Au-Katalysatoren ermçglichen in beeindruckender Weise die Feinabstimmung der Liganden und somit auch deren Einfluss auf die katalytischen Reaktionspfade. [211] Wie schon in Abschnitt 8.1 dargelegt, erreichen N-heterocyclische Carbene hervorragende Produktselektivitäten als Organokatalysatoren.…”

Section: Organokatalytische Produktselektive Katalyseunclassified

Katalytische selektive Synthese

2012

View full text Add to dashboard Cite

Der Verlauf und das Produkt einer Reaktion lassen sich gezielt über die Katalysatorstruktur steuern, selbst bei nahezu identischen Reaktionsbedingungen. Katalysatorkontrollierte Selektivität ist in der enantioselektiven Synthese gut etabliert, in katalytischen regio‐, chemo‐ und produktselektiven Reaktionen aber wenig verbreitet. Dieser Aufsatz beschreibt, wie eine Ausgangsverbindung lediglich durch die Auswahl des Katalysators selektiv in zwei oder mehr unterschiedliche Produkte umgewandelt werden kann. Wir stellen Beispiele selektiver Katalysen vor und hoffen, dass die bisher erzielten Fortschritte ermutigend für das Gebiet sind. Zugleich wollen auch die noch offenen Fragen beim Entwurf und dem mechanistischen Verständnis selektiver Katalysatoren thematisieren.

show abstract

Section: Organokatalytische Produktselektive Katalyseunclassified

Katalytische selektive Synthese

2012

View full text Add to dashboard Cite

show abstract

“…However, the b-hydrogens of these diazo compounds belonging to strong b-C-H (methyl) bonds, and the b-hydrogens of diazo compounds belonging to weaker b-C-H bonds were unknown. 21 A general method for Rh-catalyzed cyclopropenation as well as a Rh-catalyzed intermolecular alkyne insertion/Bu¨chner ring expansion cascade have been described by Fox et al 21 Ligand choice governs control over these divergent reaction pathways: hindered carboxylate ligands lead to dramatic improvements in cyclopropenation and dihydroazulenes formation. The Rh 2 Piv 4 3 catalyzed cyclopropenation is successful for a range of terminal alkynes 1 with a-diazopropionate (R 1 = H), a-diazobutanoate (R 1 = Me), and a-diazohydrocinnamate (R 1 = Ph) to produce the corresponding cyclopropenes 5 in 40-75% yields, and only a minor amount of b-hydride elimination product 8 is isolated.…”

Section: -Catalyzed [2+1]mentioning

confidence: 99%

Recent developments of cyclopropene chemistry

2011

View full text Add to dashboard Cite

This critical review discusses recent developments in the field of cyclopropene chemistry. Although several excellent reviews that mainly focused on the thermolysis and pyrolysis as well as metal-mediated reactions of cyclopropenes have been published, significant new developments have also been achieved in recent years. This brand new review provides an overview of the progress from 2007 to 2011 on the syntheses and transformations of cyclopropenes as well as their related mechanistic studies (238 references).

show abstract

“…Later, the works independently published by Hubert et al among others showed the use of complex I as a catalyst for the cyclopropanation of olefins and allylic activation by diazo-esters [19,20,[27][28][29][31][32][33][34][35][36][37][38][39].…”

Section: Introductionmentioning

confidence: 99%

Microwave-Assisted Synthesis and Characterization of [Rh₂(OAc)₄(L)₂] Paddlewheel Complexes: A Joint Experimental and Computational Study

González-Belman

Varela

Flores‐Álamo

et al. 2017

International Journal of Inorganic Chemistry

View full text Add to dashboard Cite

The synthesis of four rhodium(II) paddlewheel complexes bearing axial aromatic amines and coumarin ligands, with formula [Rh 2 (OAc) 4 (L) 2 ] (L = NH 2 Mesityl (1), NH 2 Dip (2), NH 2 Couma (3), coumarin (4)), prompted by microwave irradiation, was carried out successfully. All of the complexes were characterized by the melting point, elemental analysis, NMR, IR, and UV/Visible spectroscopy. Additionally, the structure of complexes 1-2 and 4 was corroborated by single-crystal X-ray diffraction. Cyclic voltammetry, ESI-MS, and tandem MS analyses were carried out in compound 1 for gaining further insight into its stability. Finally, a DFT study shows that complexes 1-4 are the thermodynamic products, having as intermediates complexes 1 -4 which, under our experimental conditions, cannot be isolated.

show abstract

Rh-Catalyzed Intermolecular Reactions of Alkynes with α-Diazoesters That Possess β-Hydrogens: Ligand-Based Control over Divergent Pathways

Cited by 169 publications

References 21 publications

Katalytische selektive Synthese

Katalytische selektive Synthese

Recent developments of cyclopropene chemistry

Microwave-Assisted Synthesis and Characterization of [Rh₂(OAc)₄(L)₂] Paddlewheel Complexes: A Joint Experimental and Computational Study

Contact Info

Product

Resources

About

Rh-Catalyzed Intermolecular Reactions of Alkynes with α-Diazoesters That Possess β-Hydrogens: Ligand-Based Control over Divergent Pathways

Cited by 169 publications

References 21 publications

Katalytische selektive Synthese

Katalytische selektive Synthese

Recent developments of cyclopropene chemistry

Microwave-Assisted Synthesis and Characterization of [Rh2(OAc)4(L)2] Paddlewheel Complexes: A Joint Experimental and Computational Study

Contact Info

Product

Resources

About

Microwave-Assisted Synthesis and Characterization of [Rh₂(OAc)₄(L)₂] Paddlewheel Complexes: A Joint Experimental and Computational Study