Reactions between heteroaromatic halides and lithium dimethylcuprate; synthetic and mechanistic aspects

Babudri, Francesco; Nunno, Leonardo Di; Florio, Saverio; Marchese, Giuseppe; Naso, Francesco

doi:10.1016/s0022-328x(00)82543-7

Cited by 14 publications

(2 citation statements)

References 20 publications

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“…The other halides as well as 3-iodopyridine were found to be less reactive (Table ). Using Ph 2 CuLi instead of Me 2 CuLi with 2-iodobenzothiazole under similar reaction times led to a more rapid reaction; benzothiazole was obtained in high yield, together with iodobenzene and biphenyl …”

Section: Bimetallic Metal–copper Reagents (Metal = Lithium Magnesium)mentioning

confidence: 99%

“…Using Ph 2 CuLi instead of Me 2 CuLi with 2-iodobenzothiazole under similar reaction times led to a more rapid reaction; benzothiazole was obtained in high yield, together with iodobenzene and biphenyl. 133 With the aim of developing a new method to get arylcuprates, Sakamoto and co-workers investigated the halogen/metal exchange of aromatic halides using lithium cuprates. The group identified Me 2 Cu(CN)Li 2 as a reagent more efficient than Me 2 CuLi, Me 2 Cu(SCN)Li 2 , Me(PhC C)Cu(CN)Li 2 , and Me(2-thienyl)Cu(CN)Li 2 when used in THF toward iodobenzenes, as demonstrated by subsequent interception with various electrophiles (Table 108).…”

Section: Bimetallic Metal−copper Reagents (Metalmentioning

confidence: 99%

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Bimetallic Combinations for Dehalogenative Metalation Involving Organic Compounds

et al. 2013

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Section: Bimetallic Metal–copper Reagents (Metal = Lithium Magnesium)mentioning

confidence: 99%

Section: Bimetallic Metal−copper Reagents (Metalmentioning

confidence: 99%

Bimetallic Combinations for Dehalogenative Metalation Involving Organic Compounds

et al. 2013

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Organocopper Reagents: Substitution, Conjugate Addition, Carbo/Metallocupration, and Other Reactions

1992

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Well over a decade ago, two reviews were contributed to the Organic Reactions series covering substitution and conjugate addition reactions in organocopper chemistry. Their appearance, which highlighted most of the early work in this field, served not only as a source of invaluable references to original literature reports, but also stimulated a vast number of subsequent studies on the properties and uses of organocopper complexes. The work cited in this chapter, which dates from ca. 1975, concerns in large measure uses of organocopper complexes originating from either catalytic or stoichiometric quantities of a copper(I) halide together with a Grignard (RMgX) or organolithium (RLi) reagent. These combinations form either neutral organocopper reagents RCu ( 1 ) or copper(I) monoanionic salts R 2 CuM (M = Li or MgX), commonly referred to as “lower‐order” species. The latter ate complexes with lithium as gegenion ( 2 ) are also known as “Gilman reagents” in recognition of their origins. Copper(I) cyanide is also an excellent precursor, affording homogeneous mixtures of lower order cyanocuprates RCu(CN)Li, ( 3 ), upon treatment with an equivalent of an organolithium. The strength of the CuCN linkage presumably accounts for direct cuprate formation with 1 equivalent of the organolithium, rather than the metathesis that occurs with copper(I) chloride, bromide, or iodide. While use of reagents ( 1 ), ( 2 ) and ( 3 ) alone can be aptly classified as broad‐based and intense, their importance has further encouraged extensive development of variations on these themes (i.e., their composition and reactivity profiles). Reagents ( 1–3 ) have been found to be unexpectedly compatible with certain electrophilic additives at low temperatures, which substantially alter their reactivity. Rather than forming ( 2 ) from 2 equivalents of the same RLi, different organolithiums can be utilized to give R T R R CuLi, ( 4 ), conserving potentially valuable RLi. This scenario raises the question of controlling the selectivity of transfer of the desired ligand R T rather than the anticipated residual (or “dummy”) group R R from copper to electrophilic carbon. Fortunately, many solutions to this problem now exist. Admixture of 2RLi (or R T Li + R R Li) with copper(I) cyanide proceeds beyond the stage of ( 3 ) to ultimately arrive at copper(I) dianionic complexes 5 , the so‐called “higher‐order” cyanocuprates. Undoubtedly it is the cyano ligand, with its π‐acidic nature, which enables copper to accept a third negatively charged ligand. Although reagents ( 5 ) do not yet share in all of the benefits offered by time in comparison with their lower‐order counterparts, they nicely complement prior art. Moreover, as with species ( 1–4 ), they continue to evolve, providing the synthetic community with alternatives for highly selective and efficient means of making key carbon–carbon bonds.

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Selektive Metallierung von Halogenarenen mit Cupraten

et al. 1996

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Die Verzerrung des ClO,-Radikals in Richtung auf C,,-Symmetrie ist dynamisch (Jahn-Teller-Effekt), wobei ein Wechsel des Cl 142 pm freien Elektrons von dem antibindenden der nachsten erfolgt, so daD es zu einer Li-0 ' \ ' o o*-Orbital der einen C10-Bindung in das Abb. 3. Struktur nienverbreiterung der IR-Banden kommt. von C10,. Mit CIO, sind nun alle einkernigen binaren Chloroxide bekannt, aus denen sich formal die bekannten zweikernigen Chloroxide CI,O,, Cl,O,, Cl,O,, Cl,O,, C1,07 aufbauen lassen. Deren primarer thermischer Zerfall erfolgt, wie hier exemplarisch gezeigt, in die entsprechenden einkernigen Radikale, wobei die Bildung von OClO besonders bevorzugt ist. Analog sind die Verhaltnisse in der NO,-Chemie, in der bei Bildung und Zerfall von N,O,, N,O, und N,O, die Radikale NO, NO, und NO, beteiligt sind. 0 153 pm Eingegangeu am 26. Oktober 1995 [Z 84991 Stichworte: Chlorverbindungen . IR-Spektroskopie . Matrixisolierung [15] E. M. Suznki, J. W. Nihler, L Moiec. At-Komplexe wie Cuprate sind nutzliche Reagentien zur selektiven Bildung von C-C-Bindungen ; an Halogen-Metall-Austauschreaktionen mit At-Komplexen bestand dagegen bislang wenig Interesse"]. Um eine neue, einfache Methode zur Herstellung von Arylcupraten zu entwickeln, haben wir die Halogen-Kupfer-Austauschreaktion von Halogenarenen rnit Cupraten untersucht. Dabei stellte sich heraus, daD [Li,Cu(CN)Me,] ein ausgezeichnetes Metallierungsreagens ist. Die Methode wurde [*] Prof. 818 0 VCH Verlugsgesellschafi mbH, 0-69451 Weinheim,

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Reactions between heteroaromatic halides and lithium dimethylcuprate; synthetic and mechanistic aspects

Cited by 14 publications

References 20 publications

Bimetallic Combinations for Dehalogenative Metalation Involving Organic Compounds

Bimetallic Combinations for Dehalogenative Metalation Involving Organic Compounds

Organocopper Reagents: Substitution, Conjugate Addition, Carbo/Metallocupration, and Other Reactions

Selektive Metallierung von Halogenarenen mit Cupraten

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