Rhodium‐Catalyzed Enantioselective Nucleophilic Fluorination: Ring Opening of Oxabicyclic Alkenes

Zhu, Jianbo; Tsui, Gavin Chit; Lautens, Mark

doi:10.1002/ange.201207356

Cited by 33 publications

(7 citation statements)

References 94 publications

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“…[14] As a typical example, the DA adduct, distal-5 Aa, was further transformed into various substituted isoquinolines 6 a-6 g, 7 a', and 7 b (Scheme 2). The 1,4-epoxide of 5 Aa [15] was opened by treatment with trimethylsilyl triflate (Me 3 SiOTf), followed by quenching with H 2 O, to afford 8-hydroxyisoquinoline 6 a. In contrast, the same reaction without quenching with H 2 O afforded 7 a'.…”

Section: Resultsmentioning

confidence: 99%

Concise Synthesis of Multisubstituted Isoquinolines from Pyridines by Regioselective Diels–Alder Reactions of 2‐Silyl‐3,4‐pyridynes

Ikawa

Urata

Fukumoto

et al. 2014

Chemistry A European J

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A four-step regioselective synthesis of multisubstituted isoquinoline derivatives from 3-bromopyridines was developed by the Diels-Alder (DA) reactions of 2-silyl-3,4-pyridynes with furans, followed by functional-group transformations. In particular, the silyl group at the C2-position of the 3,4-pyridynes played two important roles: firstly, it functioned as the directing group for the DA reaction, and secondly, it served to introduce diverse substituents at the C1-position of the isoquinolines by electrophilic ipso-substitution.

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Section: Resultsmentioning

confidence: 99%

Concise Synthesis of Multisubstituted Isoquinolines from Pyridines by Regioselective Diels–Alder Reactions of 2‐Silyl‐3,4‐pyridynes

Ikawa

Urata

Fukumoto

et al. 2014

Chemistry A European J

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“…520 521 This was the first example of a halide being used as a nucleophile in this class of transformation. The scope of this reaction was moderately broad and exhibited highly selective enantiodivergent resolutions when racemic bicyclic alkenes were used.…”

Section: Co- Rh- and Ir-catalyzed Reactionsmentioning

confidence: 98%

“…In 2012, Lautens reported the asymmetric Rh-catalyzed ringopening of oxabicyclic alkenes 543 to generate fluorohydrins 544 using nucleophilic fluoride (Scheme 333). 521 This was the first example of a halide being used as a nucleophile in this class of transformation. The scope of this reaction was moderately broad and exhibited highly selective enantiodivergent resolutions when racemic bicyclic alkenes were used.…”

Section: Co- Rh- and Ir-catalyzed Reactionsmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…[160] Ein interessanter Zugang zu Allylfluoriden ist der Tsuji-Trost-Austausch einer Abgangsgruppe durch Fluorid, der durch einen Übergangsmetallkomplex katalysiert wird. [165] Sekundäre und tertiäre Allylfluoride lassen sich aus den Allyltrichloracetamidaten 1.16 unter Iridiumkatalyse herstellen (Schema 38), [166] und terminale Allylfluoride wurden palladiumkatalysiert von Gouverneur und Brown [167] aus Cinnamylallylcarbonaten sowie von Wu und Lauer [168] aus Cinnamylallylphosphorthioatestern synthetisiert. Die selektive Synthese linearer oder verzweigter Allylfluoride ist ein weiteres Problem [162] der allylischen Tsuji-Trost-Austauschreaktion.…”

Section: Nucleophile Fluorierung Zur Synthese Fluorierter Sp 3 -Kohleunclassified

“…Oxabicyclische Alkene reagieren mit Fluorid und einem Rhodiumkatalysator unter Ringçffnung. [165] Sekundäre und tertiäre Allylfluoride lassen sich aus den Allyltrichloracetamidaten 1.16 unter Iridiumkatalyse herstellen (Schema 38), [166] und terminale Allylfluoride wurden palladiumkatalysiert von Gouverneur und Brown [167] aus Cinnamylallylcarbonaten sowie von Wu und Lauer [168] aus Cinnamylallylphosphorthioatestern synthetisiert.…”

Section: Nucleophile Fluorierung Zur Synthese Fluorierter Sp 3 -Kohleunclassified

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

2013

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Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo‐ und Übergangsmetallkatalyse ermöglicht. Die schwierigste Umwandlung ist weiterhin die Bildung der C‐F‐Stammbindung, was in erster Linie eine Folge der hohen Hydratationsenergie von Fluorid, starker Metall‐Fluor‐Bindungen und der hoch polarisierten Bindungen zu Fluor ist. Den meisten Fluorierungen fehlt es immer noch an Allgemeingültigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschränkungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zugänglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine großen Materialmengen benötigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

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Rhodium‐Catalyzed Enantioselective Nucleophilic Fluorination: Ring Opening of Oxabicyclic Alkenes

Abstract: for single-crystal X-ray structure analysis, and Solvias AG for the generous gift of chiral ligands. J.Z. thanks SIOC for a postdoctoral fellowship. G.C.T. thanks NSERC for a postgraduate scholarship.Supporting information for this article is available on the WWW under http://dx.

Cited by 33 publications

References 94 publications

Concise Synthesis of Multisubstituted Isoquinolines from Pyridines by Regioselective Diels–Alder Reactions of 2‐Silyl‐3,4‐pyridynes

Concise Synthesis of Multisubstituted Isoquinolines from Pyridines by Regioselective Diels–Alder Reactions of 2‐Silyl‐3,4‐pyridynes

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

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