Structure and reactivity of a planar chiral naphthylferrocenylcopper heteroaggregate

Venkatasubbaiah, Krishnan; Bolte, Michael; Jäkle, Frieder

doi:10.1016/j.jfluchem.2010.05.012

Cited by 4 publications

(1 citation statement)

References 45 publications

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“…In earlier work, we demonstrated that Kagan’s ferrocenyl p -tolyl sulfinate serves as a powerful precursor to ferrocene-based planar chiral and/or bidentate Lewis acids. Two complementary methods allow for stereoselective functionalization of ferrocene with main group Lewis acids: (1) lithiation of ferrocenyl p -tolyl sulfinate with LDA, followed by treatment with R 3 SnCl (R = Me, n -Bu), leads to stereoselective formation of ( p R)-1-stannyl-2-sulfinylferrocenes; (2) the sulfinyl group itself can be replaced by treatment with tert -butyl lithium at −78 °C and subsequent quenching with organometallic halides, such as R 3 SnCl . In both cases, the stannyl groups can then be further elaborated via highly selective transmetalation reactions to yield ferrocene-based organomercury, organocopper, or organoborane Lewis acids.…”

Section: Resultsmentioning

confidence: 99%

Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure

et al. 2011

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The boronic acid (pS)-1,2-NpFcB(OH)2 (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O i Pr)3, followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO]3 (2) in 49% isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a 1H, 1H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl3/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl3, followed by column chromatography on silica gel.

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Section: Resultsmentioning

confidence: 99%

Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure

et al. 2011

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An Axially Chiral, Electron‐Deficient Borane: Synthesis, Coordination Chemistry, Lewis Acidity, and Reactivity

Mewald

Fröhlich

Oestreich

2011

Chemistry A European J

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An axially chiral dihydroborepine with a binaphthyl backbone and a C(6)F(5) substituent at the boron atom was prepared by transmetalation from the corresponding tin precursor. This novel motif was structurally characterized by X-ray diffraction analysis as its THF and its PhCN Lewis acid/base complex. (1)H NMR measurements at variable temperatures of the former adduct revealed a remarkable dynamic behavior in solution. Several more Lewis pairs with oxygen, nitrogen, carbon, and phosphorus σ-donors were synthesized and analyzed by multinuclear NMR spectroscopy. The determination of the borane's Lewis acidity with the Gutmann-Beckett method attests its substantial Lewis acidity [85% with Et(3) PO as well as 74% with Ph(3) PO relative to the parent B(C(6)F(5))(3)]. Representative examples of Si-H bond activation (carbonyl reduction and dehydrogenative Si-O coupling) are included, demonstrating the chemical stability and the synthetic potential of the new chiral boron-based Lewis acid.

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Ferrocene: To Infinity and Back Again

Nataro

2021

Comprehensive Coordination Chemistry III

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Structure and reactivity of a planar chiral naphthylferrocenylcopper heteroaggregate

Cited by 4 publications

References 45 publications

Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure

Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure

An Axially Chiral, Electron‐Deficient Borane: Synthesis, Coordination Chemistry, Lewis Acidity, and Reactivity

Ferrocene: To Infinity and Back Again

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