<i>cis</i>‐Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis through an Ionic Pathway

Emer, Enrico; Pfeifer, Lukas; Brown, John M.; Gouverneur, Véronique

doi:10.1002/ange.201310056

Cited by 24 publications

(2 citation statements)

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“…438 Using inexpensive Pd(PPh 3 ) 4 as catalyst with HSiEt 3 and Selectfluor as the hydride and fluoride sources, respectively, diverse benzylic fluorides 437 could be obtained under very mild conditions (Scheme 272).…”

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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Section: Synthesis Of Alkyl Halidesmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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“…[7] Although as toichiometric amount of iron was needed in the reaction, some unique characteristics, including ar apid reaction rate,h igh functional-group tolerance,and the use of abundant and biocompatible iron as the metal render this method attractive.T om ake this method more economical, much effort has been devoted to reducing the amount of iron needed. Despite significant progress made by the research groups of Hiroya [8] and Gouverneur [9] in developing cobalt-and palladium-catalyzed hydrofluorination reactions of alkenes,a ni ron-catalyzed version still remains an elusive challenge.H erein we report an ironcatalyzed hydrofluorination of unactivated alkenes under non-acidic conditions.T he combination of am ultidentate ligand, (EtO) 3 SiH, and N-fluorobenzenesulfonimide (NFSI) proved critical in facilitating the catalyzed reaction to provide avariety of substituted fluorinated compounds in up to 94 % yield (Scheme 1c).…”

mentioning

confidence: 99%

Ligand‐Promoted Iron(III)‐Catalyzed Hydrofluorination of Alkenes

Xie

Sun

et al. 2019

Angewandte Chemie

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An iron-catalyzedhydrofluorination of unactivated alkenes has been developed. The use of am ultidentate ligand and the fluorination reagent N-fluorobenzenesulfonimide (NFSI) proved to be critical for this reaction, whicha fforded various fluorinated compounds in up to 94 %y ield.Scheme 2. Optimization of the reaction conditions. Reactionsw ere carried out with 1a (0.2 mmol) in EtOH (2.0 mL for conditions A; 1.0 mL for conditions B)u nder N 2 .Y ields are for the isolated product. Ln-FeCl 3 : Ln (5 mol %), FeCl 3 (5 mol %). Angewandte ChemieZuschriften 7172 www.angewandte.de Scheme 4. Scope of the reaction of di-and trisubstituted alkenes. Reactionsw ere carried out with 1 (0.2 mmol) in EtOH (1.0 mL) or EtOH/CH 2 Cl 2 (1:2, 1.0 mL) at 75 8 8Cunder N 2 for 3h.Yields are for the isolated product.[a] Ratio of trans/cis isomers (trans isomer is major).[b] Ratio of regioisomers.[c] The trisubstituted alkene 3-methylbut-2en-1-yl 2-naphthoate was used. Piv = pivaloyl.Scheme 5. Competition experiments. 2-Np = 2-naphthyl.

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A Combination of Metal and Organic Catalysis: Highly Diastereo‐ and Enantioselective Construction of Fluorinated 2‐Aminocyclopenta[b]pyran Derivatives

Zhao

2015

Adv Synth Catal

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cis‐Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis through an Ionic Pathway

Cited by 24 publications

References 50 publications

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Ligand‐Promoted Iron(III)‐Catalyzed Hydrofluorination of Alkenes

A Combination of Metal and Organic Catalysis: Highly Diastereo‐ and Enantioselective Construction of Fluorinated 2‐Aminocyclopenta[b]pyran Derivatives

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