On phenylcopper

Costa, G.; Camus, A.; Gatti, L.; Marsich, N.

doi:10.1016/s0022-328x(00)85161-x

Cited by 100 publications

(25 citation statements)

References 6 publications

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“…To evaluate the potential that mechanism A occurs, we conducted the reaction between the known phenyl-copper 16 with [Me 3 pyF]PF 6 , AgF and t BuCN in THF. After 18 h at 50 °C no fluorobenzene was detected by 19 F NMR spectroscopy (eq 3).…”

Section: Resultsmentioning

confidence: 99%

Copper-Mediated Fluorination of Arylboronate Esters. Identification of a Copper(III) Fluoride Complex

2013

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A method for the direct conversion of arylboronate esters to aryl fluorides under mild conditions with readily available reagents is reported. Tandem reactions have also been developed for the fluorination of arenes and aryl bromides through aryl-boronate ester intermediates. Mechanistic studies suggest that this fluorination reaction occurs through facile oxidation of Cu(I) to Cu(III) followed by rate-limiting transmetallation of a bound arylboronate to Cu(III). Fast C-F reductive elimination is proposed to occur from an aryl-copper(III)-fluoride complex. Cu(III) intermediates have been generated independently and identified by NMR spectroscopy and ESI-MS.

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Section: Resultsmentioning

confidence: 99%

Copper-Mediated Fluorination of Arylboronate Esters. Identification of a Copper(III) Fluoride Complex

2013

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“…[25] In 1966 Costa et al isolated a complex between phenylcopper(i) and magnesium, as well as crystals of a lithium diphenylcuprate(i) complex. [26] Although the organocopper reagents derived from Grignard reagents are widely used and may be described as R 2 CuMgX, it is still uncertain to what extent this reflects the reality in solution. The organic chemistry of organocuprates started its rapid development in 1966, when House et al showed that the reactive species of conjugate addition is the lithium diorganocuprate(i) called the ªGilman reagentº.…”

Section: Historical Background and Recent Progressmentioning

confidence: 99%

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Nakamura

Mori

2000

Angew. Chem. Int. Ed.

270

186

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Organocopper reagents provide the most general synthetic tools in organic chemistry for nucleophilic delivery of hard carbanions to electrophilic carbon centers. A number of structural and mechanistic studies have been reported and have led to a wide variety of mechanistic proposals, some of which might even be contradictory to others. With the recent advent of physical and theoretical methodologies, the accumulated knowledge on organocopper chemistry is being put together into a few major mechanistic principles. This review will summarize first the general structural features of organocopper compounds and the previous mechanistic arguments, and then describe the most recent mechanistic pictures obtained through high‐level quantum mechanical calculations for three typical organocuprate reactions, carbocupration, conjugate addition, and SN2 alkylation. The unified view on the nucleophilic reactivities of metal organocuprate clusters thus obtained has indicated that organocuprate chemistry represents an intricate example of molecular recognition and supramolecular chemistry, which chemists have long exploited without knowing it. Reasoning about the uniqueness of the copper atom among neighboring metal elements in the periodic table will be presented.

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“…Polymeric structures are implied for insoluble compounds such as CuPh [60]. It has been proposed that the tetrameric aggregates are isostructural with [Cu 4 (C 6 H 4 CH 2 NMe 2 -2) 4 ], containing four copper atoms in a butterfly arrangement and with each of the aryl groups bridging between adjacent copper atoms (see Fig.…”

Section: Structures and Reactivities Of Organocopper Compoundsmentioning

confidence: 99%