Domino reaction of lithiated allenes with nitriles†

Langer, Peter; Döring, Manfred; Seyferth, Dietmar

doi:10.1039/a803040e

Cited by 21 publications

(5 citation statements)

References 8 publications

(4 reference statements)

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“…Although base‐catalysed polymerisation of benzonitrile has been known for quite some time, the recent publication of new domino reactions,19, 20 motivated us to react 1 also with excess benzonitrile. Reaction of 1 with three equivalents of benzonitrile at 60 °C was monitored by 1 H NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Hydrocarbon‐Soluble Calcium Hydride: A “Worker‐Bee” in Calcium Chemistry

Spielmann

Harder

2007

Chemistry A European J

134

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The reactivity of the hydrocarbon-soluble calcium hydride complex [{CaH(dipp-nacnac)(thf)}(2)] (1; dipp-nacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with a large variety of substrates has been investigated. Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes. Similarly, reduction of the C[triple chemical bond]N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)R}(dipp-nacnac)] and [Ca{C(H)=NR}(dipp-nacnac)], respectively. Complexation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs. In reaction with epoxides, nucleophilic ring-opening is observed as the major reaction. The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH(2), which is essentially inert and is used as a common drying agent. Crystal structures of the following products are presented: [{Ca{OC(H)Ph(2)}(dipp-nacnac)}(2)], [{Ca{N=C(H)Ph}(dipp-nacnac)}(2)], [{Ca{C(H)=NC(Me)(2)CH(2)C(Me)(3)}(dipp-nacnac)}(2)], [{Ca{C(H)=NCy}(dipp-nacnac)}(2)], [Ca(dipp-nacnac)(thf)](+)[H(2)BC(8)H(14)](-) and [{Ca(OCy)(dipp-nacnac)}(2)]. The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.

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Section: Resultsmentioning

confidence: 99%

Hydrocarbon‐Soluble Calcium Hydride: A “Worker‐Bee” in Calcium Chemistry

Spielmann

Harder

2007

Chemistry A European J

134

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“…in a reaction recently developed by us. [11,12] This reaction proceeds by lithiation of the silyl enol ether, elimination of lithium silanolate and lithiation of 1,1-diphenylallene (Scheme 2). The elimination either occurs directly (path A) or proceeds through a OǞC silyl migration/Peterson elimination sequence (path B).…”

Section: Resultsmentioning

confidence: 99%

“…[9] A domino reaction between Grignard reagents and a tris-nitrile has also been reported, [10] while we have recently reported that reactions between dilithiated allenes and benzonitrile resulted in the addition of up to four nitrile molecules. [11] This multiple anion-capture reaction involves the highest number so far of nitrile molecules added to an organolithium reagent to give an unambiguously characterized oligomer. Here we wish to report full details of this unusual reaction, which we believe also constitutes a new method for the synthesis of imidazoles.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Nitrile Oligomers through Multiple Anion Capture Reactions of Allene Dianions

Langer

Döring²,

Seyferth

et al. 2003

Eur J Org Chem

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Domino reactions between 1,1‐dilithio‐3,3‐diphenylallene and nitriles resulted in the formation of products containing up to four nitrile molecules, representing the highest number to date of nitrile molecules involved in the formation of unambiguously characterized oligomers. The unusual domino process reported constitutes a new method for the synthesis of imidazoles. The solid‐state structures of the sterically encumbered products were studied by crystal structure analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…The formation of the products can be explained by acid-mediated extrusion of water The reaction of 10c with 4.5 equivalents of benzonitrile afforded the unexpected product 25 in 51% yield (Scheme 15). 17,18 In the course of this reaction, four molecules of benzonitrile were consumed and incorporated into the final product. Therefore, the reaction represents a domino process and it is termed a 'multiple anion capture reaction'.…”

Section: Scheme 13 Synthesis Of Compounds 14a-ementioning

confidence: 99%

Adventures in 1,1-Diphenylacetone Dianion Chemistry

Langer

2023

Synlett

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The present personalized account highlights reactions of the dianion of 1,1-diphenylacetone and its applications. From a study directed towards the regioselectivity of such reactions a new allene synthesis via allene dianions was found by serendipity. In addition, reactions of allene dianions with various electrophiles have been studied.1 Introduction2 Cyclizations of the Dianion of 1,1-Diphenylacetone2.1 Reaction with Bis(cyclopentadienyl)zirconium Dichloride2.1 Reactions with Dichlorosilanes2.1 Reactions with Difluorosilanes2.1 Reactions with Ketones and Dielectrophiles3 Regioselectivity of Dianion Reactions4 Allene Dianions from Silyl Enol Ethers5 Scope of the Reactions of Allene Dianions6 Reactions of Allene Dianions with Ketones7 Reactions of Allene Dianions with Nitriles8 Conclusions

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Domino reaction of lithiated allenes with nitriles†

Cited by 21 publications

References 8 publications

Hydrocarbon‐Soluble Calcium Hydride: A “Worker‐Bee” in Calcium Chemistry

Hydrocarbon‐Soluble Calcium Hydride: A “Worker‐Bee” in Calcium Chemistry

Synthesis of Nitrile Oligomers through Multiple Anion Capture Reactions of Allene Dianions

Adventures in 1,1-Diphenylacetone Dianion Chemistry

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