Palladium-Catalyzed Enantioselective 1,1-Fluoroarylation of Aminoalkenes

He, Ying; Yang, Zhen‐Yu; Thornbury, Richard T.; Toste, F. Dean

doi:10.1021/jacs.5b07795

Cited by 118 publications

(65 citation statements)

References 63 publications

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“…The transformation likely proceeded through an oxidative Heck mechanism to afford 1,1-difunctionalized alkenes (245) in one pot [112], which was different from the pathway proposed for the 1,2-fluoroarylation [111]. The 1,1-fluoroarylation could also be extended to an asymmetric transformation, generating chiral benzylic fluorides (246) in good to excellent enantioselectivies [112]. These reactions promised powerful strategies for the difunctionalization of alkenes to chiral fluorinated molecules.…”

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 98%

“…Later, palladium-catalyzed 1,1-fluoroarylation of amino-alkenes (243) using arylboronic acids (244) as an arene source and Selectfluor ® as a fluorine source was developed by the same research group (Scheme 48) [112]. The transformation likely proceeded through an oxidative Heck mechanism to afford 1,1-difunctionalized alkenes (245) in one pot [112], which was different from the pathway proposed for the 1,2-fluoroarylation [111]. The 1,1-fluoroarylation could also be extended to an asymmetric transformation, generating chiral benzylic fluorides (246) in good Toste and co-workers disclosed the Pd-catalyzed 1,2-fluoroarylation of styrenes (239) with arylboronic acids (240) and Selectfluor ® using amides (e.g., 8-aminoquinoline (AQ)) as the directing groups (Scheme 48) [111].…”

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

“…This strategy was also successfully used for the asymmetric 1,2-fluoroarylation of styrenes, furnishing chiral monofluorinated compounds (242) in good yields and with high enantioselectivies. Later, palladium-catalyzed 1,1-fluoroarylation of amino-alkenes (243) using arylboronic acids (244) as an arene source and Selectfluor ® as a fluorine source was developed by the same research group (Scheme 48) [112]. The transformation likely proceeded through an oxidative Heck mechanism to afford 1,1-difunctionalized alkenes (245) in one pot [112], which was different from the pathway proposed for the 1,2-fluoroarylation [111].…”

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

“…Nevertheless, the exact mechanism of the reaction remained unclear [113]. to excellent enantioselectivies [112]. These reactions promised powerful strategies for the difunctionalization of alkenes to chiral fluorinated molecules.…”

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

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Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Yang

Zhao

et al. 2018

Catalysts

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Abstract:The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes. Variants of the Pd-catalyzed Mizoroki-Heck reactions with fluorine-containing reagents are also briefly depicted. This work supplies an overview, as well as a guide, to both younger and more established researchers in order to attract more attention and contributions in the realm of Mizoroki-Heck reactions with fluorine-containing participants.

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Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 98%

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

Section: Fluoroalkylation Reagents As the Precursors Of The Cross-coumentioning

confidence: 99%

See 2 more Smart Citations

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Yang

Zhao

et al. 2018

Catalysts

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“…435 The racemic arylfluorination products (±)-417 could be obtained in moderate to good yields using Selectfluor in a trisolvent mixture of DCM:H 2 O:MeCN (Scheme 265).…”

Section: Synthesis Of Alkyl Halidesmentioning

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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Catalytic, Enantioselective Fluorination Reactions

Thornbury

Toste

2019

Organic Reactions

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The unique properties conferred by the incorporation of fluorine into organic molecules has resulted in the widespread use of organofluorine compounds in the pharmaceutical and agrochemical industries. In contrast, organofluorine compounds are exceedingly rare in nature. The dearth of chiral pool organofluorine compounds necessitates the development of stereoselective methods for the incorporation of carbon–fluorine bonds into organic molecules. A wide variety of catalytic, enantioselective fluorination methods have been developed to address this challenge, including Lewis acid catalysis, organocatalysis, transition metal catalysis, and phase transfer catalysis. Using these methods, carbonyl compounds, alkenes, allylic electrophiles, aziridines, and epoxides have been engaged in catalytic, enantioselective fluorination reactions. This chapter provides a comprehensive review of the methods available for the catalytic, enantioselective construction of carbon–fluorine bonds and is subdivided into electrophilic and nucleophilic fluorination reactions. The chapter also provides a comparison with diastereoselective transformations and enantioselective functionalization reactions of fluorinated substrates.

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Palladium-Catalyzed Enantioselective 1,1-Fluoroarylation of Aminoalkenes

Cited by 118 publications

References 63 publications

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Catalytic, Enantioselective Fluorination Reactions

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