Rapid Injection NMR in Mechanistic Organocopper Chemistry. Preparation of the Elusive Copper(III) Intermediate

Bertz, Steven H.; Cope, Stephen K.; Murphy, Michael; Ogle, Craig A.; Taylor, Brad J

doi:10.1021/ja067533d

Cited by 155 publications

(147 citation statements)

References 32 publications

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“…), neutral triorganocopper(III) complexes, e.g., Cu III EtMe 2 L, were also observed. 84 44 To finish, three examples of one alkylcopper(II) and two arylcopper(III) compounds are presented in Scheme 10. The copper(II) compound 22 has a trigonal-bipyramidal structure with one chloride and a σ-bonded alkyl grouping in the respective apical positions.…”

Section: ■ Mononuclear Organocopper(ii) and Copper(iii) Complexesmentioning

confidence: 99%

“…The organocuprate(III) species detected at low temperature (<100°C) are mononuclear copper compounds having a square-planar copper center. 44,84 Welldefined and thermally stable aryl-Cu III species are likewise mononuclear, square-planar copper species. The stabilization of the σ-(aryl)C ipso −copper(III) bond arises from three additional Cu−N interactions from amino-N atoms as present in, for example, the triaazaalkanediyl tether spanning the ortho positions of the aryl-Cu III unit (cf.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View

Koten

2012

Organometallics

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The first reports on copper-mediated organic reactions and speculations about the role of presumed organocopper compounds as intermediates or transient species date back to the early 20th century. Since that time, copper salt mediated and much later, copper-catalyzed C−X bond forming reactions (X = C, O, N) have been developed. Phenyl-and methylcopper(I) (highly explosive as a dry solid) were the first organocopper materials synthesized by Reich (1923) and Gilman (1952), respectively. However, it was not until the late 1960s and early 1970s that the first pure organocopper(I) compounds, which are also stable at room temperature, were isolated and structurally characterized. Recently, by the application of clever design and new synthetic approaches even organocopper(II) and -(III) compounds have been isolated, species that during the greater part of the last century were considered elusive. Significantly, these species had for some time been surmised, via kinetic and computational studies, to play a key role in copper-mediated and -catalyzed C−X bond forming reactions. In this personal account the various stages along which organocopper chemistry developed, with a steady pace, will be highlighted.

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Section: ■ Mononuclear Organocopper(ii) and Copper(iii) Complexesmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View

Koten

2012

Organometallics

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“…Experiments that probe for redox processes and the generation of free or caged aryl radicals provide strong evidence against these process to form such radical intermediates and argue in favor of an oxidative addition to form an arylCu III phenoxide complex that undergoes reductive elimination of ether. Although Cu III species are not common, alkylcopper(III) [31][32][33][34] and arylcopper(III) [11,35] species have been identified recently. Moreover, we have conducted computational studies by DFT on the energy of a phen-ligated arylcopper(III) halide phenoxide complex, and the ΔG for formation of this species from the [Cu(phen)(OPh)] and PhI is computed to be 22.1 kcalmol −1 [Eq.…”

Section: The Reaction Of O-(allyloxy)iodobenzene With the P-cresolatementioning

confidence: 99%

Copper(I) Phenoxide Complexes in the Etherification of Aryl Halides

et al. 2010

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Was ist der richtige Weg? Kupfer(I)‐Phenoxid‐Komplexe mit Chelatliganden (siehe Bild) sind mögliche Intermediate bei Kupfer‐katalysierten Veretherungen von Arylhalogeniden. Sie wurden nun synthetisiert und vollständig charakterisiert. Es wurde demonstriert, dass die isolierten Komplexe in kinetischer und chemischer Hinsicht plausible Zwischenstufen bei der Synthese von Arylphenylethern sind. Ein Verlauf über Radikale wurde experimentell ausgeschlossen.

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“…Recently, however, the debate was settled by researchers at the University of North Carolina, Charlotte who confirmed the existence of a predicted copper (III) intermediate by rapid-injection NMR spectroscopy. 32 Shown below in Figure 37 is the reaction of 2-cyclohexenone with lithium dimethylcuprate, which represents a general 1,4-conjugate addition mechanism.…”

Section: Conjugate Addition Mechanismmentioning

confidence: 99%

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

Moore¹

2008

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Rapid Injection NMR in Mechanistic Organocopper Chemistry. Preparation of the Elusive Copper(III) Intermediate

Cited by 155 publications

References 32 publications

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View

Copper(I) Phenoxide Complexes in the Etherification of Aryl Halides

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

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Rapid Injection NMR in Mechanistic Organocopper Chemistry. Preparation of the Elusive Copper(III) Intermediate

Cited by 155 publications

References 32 publications

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCuI Building Blocks to Mononuclear R2–nCuII and R3–mCuIII Compounds. A Personal View

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCuI Building Blocks to Mononuclear R2–nCuII and R3–mCuIII Compounds. A Personal View

Copper(I) Phenoxide Complexes in the Etherification of Aryl Halides

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

Contact Info

Product

Resources

About

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View

Organocopper Compounds: From Elusive to Isolable Species, from Early Supramolecular Chemistry with RCu^I Building Blocks to Mononuclear R_2–nCu^II and R_3–mCu^III Compounds. A Personal View