Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Kahn, Bruce E.; Rieke, Reuben D.

doi:10.1021/cr00087a002

Cited by 205 publications

(75 citation statements)

References 30 publications

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“…[98] Imamoto et al reported a chemoselective pinacol coupling of ketones and aldehydes mediated by CeI 2 , which was prepared in situ from Ce metal and iodine (Scheme 33 A). [99] Although pinacol couplings can be accomplished using other reagents, [100] interesting features of this reaction include mild reaction conditions and good functional group compatibility. Recently, Groth and Jeske reported an attractive advancement in cerium-mediated pinacol couplings (Scheme 33 B).…”

Section: Other Lanthanide(ii) Reagentsmentioning

confidence: 99%

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

2012

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Reactions proceeding through open-shell, single-electron pathways offer attractive alternative outcomes to those proceeding through closed-shell, two-electron mechanisms. In this context, samarium diiodide (SmI(2)) has emerged as one of the most important and convenient-to-use electron-transfer reagents available in the laboratory. Recently, significant progress has been made in the reductive chemistry of other divalent lanthanides which for many years had been considered too reactive to be of value to synthetic chemists. Herein, we illustrate how new samarium(II) complexes and nonclassical lanthanide(II) reagents are changing the landscape of modern reductive chemistry.

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Section: Other Lanthanide(ii) Reagentsmentioning

confidence: 99%

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

2012

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“…60 Due to the oxophilicity of titanium, the most common reagents in the McMurry coupling are those prepared by the reduction of Ti(III) or Ti(IV) chlorides with a range of reducing agents (LiAlH 4 , Li, Na, Mg, K, Zn, Zn/Cu). Depending on the reducing agents, additives, and conditions, various low-valent titanium species with different oxidation states and reactivities are generated.…”

Section: Coupling Reagentsmentioning

confidence: 99%

The McMurry Coupling and Related Reactions

Takeda

Tsubouchi

2013

Organic Reactions

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The McMurry coupling reaction has been recognized as one of the most efficient methods for the synthesis of alkenes from carbonyl compounds. This reaction can be applied to the preparation of various alkenes that are otherwise difficult to prepare. For example, sterically congested tetrasubstituted alkenes as well as medium to large membered rings involving natural products may be accessed via this process. This coupling utilizes various low‐valent titanium reagents generated by the reduction of titanium (III or IV) chloride with K, Zn, LiAlH 4 , C 8 K, amongst others. Furthermore, a variety of low‐valent metal species other than titanium, including aluminum, zirconium, niobium, molybdenum, indium, tungsten, and samarium, have also been found to promote the reductive coupling of carbonyl compounds. The scope and limitations of these reagent systems are reviewed in this chapter, together with the stereochemistry and reaction mechanism. This reaction is categorized into four coupling modes: i) homocoupling giving symmetrical alkenes, ii) mixed coupling giving unsymmetrical alkenes, iii) intramolecular coupling giving cycloalkenes, and iv) tandem coupling giving cyclic polyenes. Characteristics of these reaction modes are described briefly. A selection of synthetic applications are reviewed, including examples of the preparation of sterically congested and strained alkenes, medium to large‐ring compounds, biologically active targets, as well as substrates applicable in material science. Experimental conditions used for this versatile process are summarized to assist the choice of suitable conditions.

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“…[96] nichtaktiviertes R-Cl [b] BirchReduktion (Schema 33 A). [99] Pinakolkupplungen kçnnen zwar auch mit anderen Reagentien durchgeführt werden, [100] allerdings handelt es sich bei den milden Reaktionsbedingungen und der hohen Kompatibilität funktioneller Gruppen um interessante Eigenschaften. Vor Kurzem beschrieben Groth und Jeske einen vielversprechenden Fortschritt bei Cer-vermittelten Pinakolkupplungen (Schema 33 B).…”

Section: Dysprosium(ii)-iodidunclassified

Jenseits von Samariumdiiodid: Perspektiven für Lanthanoid(II)‐vermittelte Reduktionen

Szostak

Procter

2012

Angewandte Chemie

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Reaktionen, die über offenschalige Einelektronenmechanismen ablaufen, führen zu interessanten alternativen Resultaten gegenüber solchen Reaktionen, die Zweielektronenmechanismen mit geschlossenen Schalen gehorchen. In diesem Zusammenhang entwickelte sich Samariumdiiodid zu einem der wichtigsten Elektronentransferreagentien. In letzter Zeit wurde ein signifikanter Fortschritt auf dem Gebiet der reduktiven Chemie anderer zweiwertiger Lanthanoide erzielt, die viele Jahre lang als zu reaktiv erachtet worden waren, um von Nutzen für Synthesechemiker zu sein. Wir beschreiben hier, wie neue Samarium(II)‐Komplexe und nichtklassische Lanthanoid(II)‐Reagentien die moderne reduktive Chemie verändern.

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Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Cited by 205 publications

References 30 publications

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

The McMurry Coupling and Related Reactions

Jenseits von Samariumdiiodid: Perspektiven für Lanthanoid(II)‐vermittelte Reduktionen

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