Orthogonal Pd- and Cu-Based Catalyst Systems for C- and N-Arylation of Oxindoles

Altman, Ryan A.; Hyde, Alan M.; Huang, Xiaohua; Buchwald, Stephen L.

doi:10.1021/ja803179s

Cited by 184 publications

(69 citation statements)

References 50 publications

(40 reference statements)

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“…From inspection of these results, it is apparent that, the more electron-rich the BODIPYc ore, the shorter the reaction times (entries1-4). Also, with less electron-richB ODIPY cores, slightly betterc hemical yields were obtained (entries [5][6][7][8].…”

Section: Resultsmentioning

confidence: 99%

Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

Gómez‐Durán

Esnal

Valois‐Escamilla

et al. 2015

Chemistry A European J

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Herein, we report the synthesis of polyfunctional BODIPY building blocks suitable to be subjected to several reaction sequences with complete chemoselectivity, thereby allowing the preparation of complex BODIPY derivatives in a versatile and programmable manner. The reactions included the Liebeskind-Srogl cross-coupling reaction (LSCC), nucleophilic aromatic substitution (SN Ar), Suzuki, Sonogashira, and Stille couplings, and a desulfitative reduction of the MeS group. This novel synthetic protocol is a powerful route to design a library of compounds with tailored photophysical properties for advanced applications. In this context, it is noteworthy that it offers a straightforward and cost-effective strategy to shift the BODIPY emission deep into the near-infrared spectral region while retaining high fluorescence quantum yields as well as highly efficient and stable laser action. These new dyes outperform the lasing behaviour of dyes considered as benchmarks over the red spectral region, overcoming the important drawbacks associated with these commercial laser dyes, namely low absorption at the standard pump wavelengths (355 and 532 nm) and/or poor photostability.

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Section: Resultsmentioning

confidence: 99%

Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

Gómez‐Durán

Esnal

Valois‐Escamilla

et al. 2015

Chemistry A European J

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“…Buchwald and co-workers reported conditions for the chemoselective arylation of oxindole 147 at either N or C3 (Scheme 68). [130] The use of 1 mol % [Pd 2 -(dba) 3 ], 5 mol % XPhos, and K 2 CO 3 as the base efficiently produced C3-arylated products 148 in yields of up to 94 % from the unprotected N-H oxindoles. A catalyst system comprising CuI (1-5 %), CyDMEDA (4-10 %), and K 2 CO 3 chemoselectively delivered similarly high yields of N-arylated products 149.…”

Section: Selecting Between Carbon-carbon and Carbon-heteroatom Couplingmentioning

confidence: 99%

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

2009

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Achieving high levels of chemoselectivity has been the Achilles' heel of chemical synthesis. The excitement generated by the successful realization of chemoselective strategies underscores the painstaking efforts to define a set of conditions conducive to selection among the available reaction pathways. We discuss in this Review various aspects of chemoselectivity that have been addressed in a range of synthetic methods over the past decade. We have focused on the proposed mechanistic basis of the reactions under consideration in an attempt to categorize them and highlight the key concepts that have been emerging on the basis of these studies. Our overview of recent advances in chemoselective processes suggests that significant progress has been made, but a lot of challenges lie ahead.

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“…[184] Beispielsweise berichteten Buchwald et al, dass Lactame wie 187 selektiv a-aryliert (ergibt 188) oder selektiv N-aryliert (zu 189) werden kçnnen (Schema 47). [185] Eine Computerstudie ergab, dass die N-Arylierung mit dem Cu-Katalysator thermodynamisch [186] Eine konzeptuell verwandte Umsetzung über ein katalytisch hergestelltes Pd-Homoenolat ist bisher nicht beschrieben worden. Trotzdem wurden von Clot und Baudoin ligandenkontrollierte, Pd-katalysierte b-Arylierungen elektronenarmer Arylhalogene vorgestellt (Schema 48 unten).…”

Section: Weitere Katalytische Chemoselektive Funktionalisierungenunclassified

Katalytische selektive Synthese

2012

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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.

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Orthogonal Pd- and Cu-Based Catalyst Systems for C- and N-Arylation of Oxindoles

Cited by 184 publications

References 50 publications

Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

Katalytische selektive Synthese

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