The Chemistry of Organic Gold Compounds. Iii. Direct Introduction of Gold Into the Aromatic Nucleus (Preliminary Communication)

Kharasch, M. S.; Isbell, Horace S.

doi:10.1021/ja01359a030

Cited by 190 publications

(70 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Kharasch showed in 1931 that arenes are aurated by gold(III) chloride, demonstrating that transition-metal complexes can participate in C–H activation chemistry. 5 Kharasch also reported that arene chlorination is catalyzed by AuCl 3 , which presumably is the first example of transition-metal catalysis in C–H bond functionalization. In these early reports, the regioselectivity of C–H activation/functionalization was determined by the acidity of the C–H bond, the electrophilic reactivity of the arene, or factors that influence the concerted metalation–deprotonation (CMD) pathway.…”

Section: Brief Historical Backgroundmentioning

confidence: 96%

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

2015

View full text Add to dashboard Cite

CONSPECTUS In recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to mainstream applications in the synthesis of complex natural products and drugs. The use of C–H bonds as a transformable functional group is advantageous because these bonds are the most abundant functionality in organic molecules. One-step conversion of these bonds to the desired functionality shortens synthetic pathways, saving reagents, solvents, and labor. Less chemical waste is generated as well, showing that this chemistry is environmentally beneficial. This Account describes the development and use of bidentate, monoanionic auxiliaries for transition-metal-catalyzed C–H bond functionalization reactions. The chemistry was initially developed to overcome the limitations with palladium-catalyzed C–H bond functionalization assisted by monodentate directing groups. By the use of electron-rich bidentate directing groups, functionalization of unactivated sp3 C–H bonds under palladium catalysis has been developed. Furthermore, a number of abundant base-metal complexes catalyze functionalization of sp2 C–H bonds. At this point, aminoquinoline, picolinic acid, and related compounds are among the most used and versatile directing moieties in C–H bond functionalization chemistry. These groups facilitate catalytic functionalization of sp2 and sp3 C–H bonds by iron, cobalt, nickel, copper, ruthenium, rhodium, and palladium complexes. Exceptionally general reactivity is observed, enabling, among other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, and alkenylation of carbon–hydrogen bonds. The versatility of these auxilaries can be attributed to the following factors. First, they are capable of stabilizing high oxidation states of transition metals, thereby facilitating the C–H bond functionalization step. Second, the directing groups can be removed, enabling their use in synthesis and functionalization of natural products and medicinally relevant substances. While the development of these directing groups presents a significant advance, several limitations of this methodology are apparent. The use of expensive second-row transition metal catalysts is still required for efficient sp3 C–H bond functionalization. Furthermore, a disadvantage is the need to install and subsequently remove the relatively expensive directing group.

show abstract

Section: Brief Historical Backgroundmentioning

confidence: 96%

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

2015

View full text Add to dashboard Cite

show abstract

“…277 These reactions were found to proceed efficiently without decarbonylation and with typically high regioselectivities when the NHC ligand IPr or PCy 2 (o-Tol) was used. When refluxing conditions were used with RuPhos as the ligand, the corresponding decarbonylative process was dominant (vide supra).…”

Section: Carbohalogenation Of Alkynes By Halometalationmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

View full text Add to dashboard Cite

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.

show abstract

“…It is important to recall that the direct metalation (auration) of electron-rich arenes and heteroarenes by Au(I) [60] and Au(III) are well known reactions [61][62][63]. However, treatment of complexes ArAuX 2 L (19a,b) with terminal alkynes such as phenylacetylene results in the formation of diarylalkynes 20a,b [62b] instead of products of hydroarylation (Scheme 4).…”

Section: Intermolecular Hydroarylationmentioning

confidence: 99%

Synthesis of arenes and heteroarenes by hydroarylation reactions catalyzed by electrophilic metal complexes

Mendoza

Echavarren

2010

Pure and Applied Chemistry

View full text Add to dashboard Cite

show abstract

The Chemistry of Organic Gold Compounds. Iii. Direct Introduction of Gold Into the Aromatic Nucleus (Preliminary Communication)

Cited by 190 publications

References 0 publications

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Synthesis of arenes and heteroarenes by hydroarylation reactions catalyzed by electrophilic metal complexes

Contact Info

Product

Resources

About