Chloride-Tolerant Gold(I)-Catalyzed Regioselective Hydrochlorination of Alkynes

Ebule, Rene; Liang, Shengzong; Hammond, Gerald B.; Xu, Bo

doi:10.1021/acscatal.7b02567

Cited by 58 publications

(41 citation statements)

References 54 publications

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“…This impairs the reactivity in this context of strong acids with strongly coordinating conjugated bases, such as hydrochloric acid. Indeed, hydrofunctionalization using this acid as nucleophile has been achieved only recently, employing gold(I) complexes with Buchwald biphenylphosphines as ligands and using HCl/DMPU as the HCl source [123]; use of this peculiar HCl source enhances its nucleophilicity upon the establishment of a strong hydrogen bond to DMPU without the formation of high concentrations of free chloride. The process requires 2 mol% Au and delivers mainly the trans hydrochlorinated product with high Markovnikov regioselectivity in the case of terminal alkynes.…”

Section: Addition Of Acidsmentioning

confidence: 99%

Gold-Catalyzed Intermolecular Alkyne Hydrofunctionalizations—Mechanistic Insights

2020

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An overview of the current state of mechanistic understanding of gold-catalyzed intermolecular alkyne hydrofunctionalization reactions is presented. Moving from the analysis of the main features of the by-now-generally accepted reaction mechanism, studies and evidences pointing out the mechanistic peculiarities of these reactions using different nucleophiles HNu that add to the alkyne triple bond are presented and discussed. The effects of the nature of the employed alkyne substrate and of the gold catalyst (employed ligands, counteranions, gold oxidation state), of additional additives and of the reaction conditions are also considered. Aim of this work is to provide the reader with a detailed mechanistic knowledge of this important reaction class, which will be invaluable for rapidly developing and optimizing synthetic protocols involving a gold-catalyzed alkyne hydrofunctionalization as a reaction step.

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Section: Addition Of Acidsmentioning

confidence: 99%

Gold-Catalyzed Intermolecular Alkyne Hydrofunctionalizations—Mechanistic Insights

2020

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“…So berichteten DØrien und Mitarbeiter von einer Ruthenium-katalysierten Hydrochlorierung von Alkinen mit HCl (Schema 1a), [9] und Hammond, Xu und Mitarbeiter verwendeten kürzlich HCl (als DMPU/HCl-Addukt) in einer Gold-katalysierten Reaktion (Schema 1b). [10] Die Verwendung von HCl als Reagens schränkt jedoch die Verträglichkeit dieser Methoden gegenüber funktionellen Gruppen ein. Eine Palladium-katalysierte gerichtete anti-Hydrochlorie-rung nichtaktivierter Alkine wurde kürzlich von Engle und Mitarbeitern realisiert (Schema 1c).…”

Section: Einführungunclassified

Iridium‐katalysierte Hydrochlorierung und Hydrobromierung von Alkinen durch Shuttlekatalyse

Bismuto

Morandi

2020

Angewandte Chemie

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Hier beschreiben wir zwei verschiedene Methoden zur Synthese von Vinylhalogeniden über eine Shuttlekatalysebasierte Iridium-katalysierte Transfer-Hydrohalogenierung nichtaktivierter Alkine.Die Verwendung von 4-Chlorbutan-2on oder tert-Butylhalogenid als Donoren von Halogenwasserstoffen hat es ermçglicht, diese Umwandlung in Abwesenheit korrosiver Reagenzien wie Halogenwasserstoff oder Säurechloriden durchzuführen. Daher verbessern diese Reaktionen die Toleranz gegenüber funktionellen Gruppen sowie Sicherheitsaspekte verglichen zum aktuellen Stand der Forschung. Dies hat den Zugang zu Alkenylhalogenidverbindungen mit säureempfindlichen Gruppen wie tertiären Alkoholen, Silylethern und Acetalen ermçglicht. Der synthe-tischeW ert dieser Methoden wurded urch eine Synthese im Gramm-Maßstab,d ie mit einer geringen Katalysatorbeladung durchgeführt werden konnte,gezeigt. Schema 1. Kontext dieser Arbeit.

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“…Fore xample,D Ørien and co-workers have reported aruthenium-catalyzed hydrochlorination of alkynes with HCl (Scheme 1a), [9] and Hammond, Xu, and co-workers have recently employed HCl (as aD MPU/HCl adduct) in ag old-catalyzed reaction (Scheme 1b). [10] However, the use of HCl as ar eagent inherently limits the functional-group tolerance of these methods.Apalladium-catalyzed directed anti-hydrochlorination of unactivated alkynes has recently been realized by Engle and co-workers (Scheme 1c). [11] Through the introduction of abidentate directing group,they could efficiently control the regioselectivity of the transformation.…”

Section: Introductionmentioning

confidence: 99%

Iridium‐Catalyzed Hydrochlorination and Hydrobromination of Alkynes by Shuttle Catalysis

Bismuto

Morandi

2020

Angew Chem Int Ed

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Described herein are two different methods for the synthesis of vinyl halides by as huttle catalysis based iridiumcatalyzedt ransfer hydrohalogenation of unactivated alkynes. The use of 4-chlorobutan-2-one or tert-butyl halide as donors of hydrogen halides allows this transformation in the absence of corrosive reagents,s uch as hydrogen halides or acid chlorides,t hus largely improvingt he functional-group tolerance and safety profile of these reactions compared to the stateof-the-art. This method has granted access to alkenyl halide compounds containing acid-sensitive groups,s uch as tertiary alcohols,s ilyl ethers,a nd acetals.T he synthetic value of those methodologies has been demonstrated by gram-scale synthesis where low catalyst loading was achieved.Scheme 1. Context of the work.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.

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Chloride-Tolerant Gold(I)-Catalyzed Regioselective Hydrochlorination of Alkynes

Cited by 58 publications

References 54 publications

Gold-Catalyzed Intermolecular Alkyne Hydrofunctionalizations—Mechanistic Insights

Gold-Catalyzed Intermolecular Alkyne Hydrofunctionalizations—Mechanistic Insights

Iridium‐katalysierte Hydrochlorierung und Hydrobromierung von Alkinen durch Shuttlekatalyse

Iridium‐Catalyzed Hydrochlorination and Hydrobromination of Alkynes by Shuttle Catalysis

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