Chemoselective Cross-Coupling Reactions with Differentiation between Two Nucleophilic Sites on a Single Aromatic Substrate

Linshoeft, Julian; Heinrich, A.; Segler, Stephan A. W.; Gates, Paul J.; Staubitz, Anne

doi:10.1021/ol302571t

Cited by 55 publications

(34 citation statements)

References 76 publications

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“…Besides the intended product 14 a , the main side product in the crude 1 H NMR spectrum could be identified as the hydrazine species 15 . Subsequent column chromatography gave hydrolyzed50 species 16 in a purity of 90 % and a yield of 34 % of isolated product 51…”

Section: Resultsmentioning

confidence: 99%

High‐Yield Lithiation of Azobenzenes by Tin–Lithium Exchange

Strueben

Lipfert

Springer

et al. 2015

Chemistry A European J

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The lithiation of halogenated azobenzenes by halogen-lithium exchange commonly leads to substantial degradation of the azo group to give hydrazine derivatives besides the desired aryl lithium species. Yields of quenching reactions with electrophiles are therefore low. This work shows that a transmetalation reaction of easily accessible stannylated azobenzenes with methyllithium leads to a near-quantitative lithiation of azobenzenes in para, meta, and ortho positions. To investigate the scope of the reaction, various lithiated azobenzenes were quenched with a variety of electrophiles. Furthermore, mechanistic (119) Sn NMR spectroscopic studies on the formation of lithiated azobenzenes are presented. A tin ate complex of the azobenzene was detected and characterized at low temperature.

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Section: Resultsmentioning

confidence: 99%

High‐Yield Lithiation of Azobenzenes by Tin–Lithium Exchange

Strueben

Lipfert

Springer

et al. 2015

Chemistry A European J

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“…Wirv ersuchten daher,d as KAT-Tr ansfer-Reagenz 1 mithilfe eines zweiten Hauptgruppensubstituenten in ein Nukleophil zu überführen. [11] Es stellte sich heraus,d ass das Stannyliminiumtrifluoroborat 2 im Gramm-Maßstab ausgehend von zwei einfach zugänglichen Reagenzien -L ithiumtributylstannat (hergestellt aus Tr ibutylzinnhydrid und Lithiumdiisopropylamid) und dem KAT-Tr ansfer-Reagenz 1 (kommerziell erhältlich)herzustellen ist. [8] Suginome,Ito et al berichteten später über die Synthese von (Boryl)(silyl)iminomethanen,d ie durch Aza-Brook-Umlagerungen zu Azaboretidinen reagieren.…”

Section: Kaliumacyltrifluoroborate (Kats) Sind Eine Faszinierendeunclassified

“…Aldridge und Campos publizierten die Negishi-Kupplung einer Acylverbindung und eines Bis(boryl)dizink-Reagenzes, [4b] [10] Diese kçnnen unter anderem auch in der Gegenwart von Boronsäure-Derivaten ablaufen. [11] Es stellte sich heraus,d ass das Stannyliminiumtrifluoroborat 2 im Gramm-Maßstab ausgehend von zwei einfach zugänglichen Reagenzien -L ithiumtributylstannat (hergestellt aus Tr ibutylzinnhydrid und Lithiumdiisopropylamid) und dem KAT-Tr ansfer-Reagenz 1 (kommerziell erhältlich)herzustellen ist. Hierfürw urde eine Synthese fürd ie Iminstannylierung nach Chong und Kells modifiziert.…”

Section: Kaliumacyltrifluoroborate (Kats) Sind Eine Faszinierendeunclassified

Katalytische Synthese von Kaliumacyltrifluoroboraten mithilfe chemoselektiver Kreuzkupplung eines bifunktionalen Reagenzes

Fohn

Bode

2019

Angewandte Chemie

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Kaliumacyltrifluoroborate (KATs) werden immer wichtigere funktionelle Gruppen, und somit werden aucha llgemeine Methoden füri hre Synthese bençtigt. Wirb erichten hier über ein bifunktionelles Iminiumreagenz, das sowohle in Zinn-Nukleophil als aucheine Trifluoroboratgruppe aufweist. Durchd iese Kombination kann man mit Aryl-und Vinylhalogeniden chemoselektive Pd 0 -katalysierte Migita-Kosugi-Stille-Kreuzkupplungen durchführen, um das entsprechende KATz ue rhalten. Diese Methode machte sz um ersten Mal mçglich, a,b-ungesättigte Acyltrifluoroborate sowieV orstufen zu Aminosäure-KATs herzustellen.

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“…There are fewer reports that are based on the chemoselective approach (category 3) compared with those of regio‐ and site‐selective approaches (categories 1 and 2). As far as we could ascertain, only Staubitz and co‐workers, in 2012, have reported a chemoselective, one‐pot, Migita–Kosugi–Stille (MKS) coupling8/SM coupling approach based on the unique thiophene scaffold C (category 3) 9. Although several useful one‐pot approaches have been reported, as described above, the development of high‐yielding and mild one‐pot approaches based on readily available thiophene scaffolds continues to be important.…”

Section: Introductionmentioning

confidence: 99%

Rapid Synthesis of Thiophene‐Based, Organic Dyes for Dye‐Sensitized Solar Cells (DSSCs) by a One‐Pot, Four‐Component Coupling Approach

Matsumura¹,

Maitani²,

Wada³

et al. 2015

Chemistry A European J

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This one-pot, four-component coupling approach (Suzuki-Miyaura coupling/C-H direct arylation/Knoevenagel condensation) was developed for the rapid synthesis of thiophene-based organic dyes for dye-sensitized solar cells (DSSCs). Seven thiophene-based, organic dyes of various donor structures with/without the use of a 3,4-ethylenedioxythiophene (EDOT) moiety were successfully synthesized in good yields based on a readily available thiophene boronic acid pinacol ester scaffold (one-pot, 3-step, 35-61%). Evaluation of the photovoltaic properties of the solar cells that were prepared using the synthesized dyes revealed that the introduction of an EDOT structure beside a cyanoacrylic acid moiety improved the short-circuit current (Jsc) while decreasing the fill factor (FF). The donor structure significantly influenced the open-circuit voltage (Voc), the FF, and the power conversion efficiency (PCE). The use of a n-hexyloxyphenyl amine donor, and our originally developed, rigid, and nonplanar donor, both promoted good cell performance (η=5.2-5.6%).

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Chemoselective Cross-Coupling Reactions with Differentiation between Two Nucleophilic Sites on a Single Aromatic Substrate

Cited by 55 publications

References 76 publications

High‐Yield Lithiation of Azobenzenes by Tin–Lithium Exchange

High‐Yield Lithiation of Azobenzenes by Tin–Lithium Exchange

Katalytische Synthese von Kaliumacyltrifluoroboraten mithilfe chemoselektiver Kreuzkupplung eines bifunktionalen Reagenzes

Rapid Synthesis of Thiophene‐Based, Organic Dyes for Dye‐Sensitized Solar Cells (DSSCs) by a One‐Pot, Four‐Component Coupling Approach

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