Practical Iron‐Catalyzed Allylations of Aryl Grignard Reagents

Mayer, Michael; Czaplik, Waldemar Maximilian; Wangelin, Axel Jacobi von

doi:10.1002/adsc.201000228

Cited by 74 publications

(34 citation statements)

References 61 publications

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“…412 Most notably, the generation of the Grignard reagent and the coupling reaction was carried out in a one-pot procedure. Iron(III) acetylacetonate was employed as catalyst without any additive.…”

Section: -Catalyzed Vinylmentioning

confidence: 99%

Iron Catalysis in Organic Synthesis

2015

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Section: -Catalyzed Vinylmentioning

confidence: 99%

Iron Catalysis in Organic Synthesis

2015

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“…[54] This transformation proceeds efficiently at 0 8Cw ith [Fe(acac) 3 ] (5 mol %) as ac atalyst in THF in the absence of additional ligands.A llyl acetate was found to be the best coupling partner. [54] This transformation proceeds efficiently at 0 8Cw ith [Fe(acac) 3 ] (5 mol %) as ac atalyst in THF in the absence of additional ligands.A llyl acetate was found to be the best coupling partner.…”

Section: Cross-coupling Of Allylic and Propargylic Substratesmentioning

confidence: 99%

Iron‐Catalyzed C−O Bond Activation: Opportunity for Sustainable Catalysis

2017

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Oxygen-based electrophiles have emerged as some of the most valuable cross-coupling partners in organic synthesis due to several major strategic and environmental benefits, such as abundance and potential to avoid toxic halide waste. In this context, iron-catalyzed C-O activation/cross-coupling holds particular promise to achieve sustainable catalytic protocols due to its natural abundance, inherent low toxicity, and excellent economic and ecological profile. Recently, tremendous progress has been achieved in the development of new methods for functional-group-tolerant iron-catalyzed cross-coupling reactions by selective C-O cleavage. These methods establish highly attractive alternatives to traditional cross-coupling reactions by using halides as electrophilic partners. In particular, new easily accessible oxygen-based electrophiles have emerged as substrates in iron-catalyzed cross-coupling reactions, which significantly broaden the scope of this catalysis platform. New mechanistic manifolds involving iron catalysis have been established; thus opening up vistas for the development of a wide range of unprecedented reactions. The synthetic potential of this sustainable mode of reactivity has been highlighted by the development of new strategies in the construction of complex motifs, including in target synthesis. The most recent advances in sustainable iron-catalyzed cross-coupling of C-O-based electrophiles are reviewed, with a focus on both mechanistic aspects and synthetic utility. It should be noted that this catalytic manifold provides access to motifs that are often not easily available by other methods, such as the assembly of stereodefined dienes or C(sp )-C(sp ) cross-couplings, thus emphasizing the synthetic importance of this mode of reactivity.

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“…It is known that available iron(III) salts are effective catalysts in cross-coupling reactions of Grignard reagents with vinyl [9--12] and allyl halides [13,14]. Fe(acac) 3 the most commonly used in the synthesis of natural compounds [15,16] and drugs [17][18][19][20] is advantageously characterized by low hygroscopicity, good solubility, and ease of handling [21].…”

Section: Letters To the Editormentioning

confidence: 99%

A Simple Synthesis of 1,3-Diphenylpropene

et al. 2018

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Abstract-A simple approach to the synthesis of 1,3-diphenylpropene isomers was developed based on Fe(acac) 3 -catalyzed cross-coupling of (E)-and (Z)-1,3-dichloropropenes with phenylmagnesium bromide.Keywords: 1,3-diphenylpropene, cross-coupling, Fe-catalyzed cross-coupling, Fe(acac) 3 ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 2, pp. 342-344. © Pleiades Publishing, Ltd., 2018. Original Russian Text © R.N. Shakhmaev, A.Sh. Sunagatullina, A.N. Vasilyeva, V.V. Zorin, 2018, published in Zhurnal Obshchei Khimii, 2018 1,3-Diphenylpropene isomers are used in organic synthesis as the starting substrates and model compounds [1][2][3][4]. The specific reactivity of 1,3-diphenylpropene is due to the presence of methylene group, being simultaneously in the allyl and benzyl positions. (E)-1,3-Diphenylpropene is usually obtained by treating a not easily accessible phenylacetaldehyde with a KOH alcohol solution [5,6], while the synthesis of less thermodynamically stable (Z)-isomer with an acceptable stereochemical purity is very problematic [7,8]. LETTERS TO THE EDITORWe investigated the possibility of obtaining 1,3-diphenylpropene 2 by Fe(acac) 3 -catalyzed crosscoupling of 1,3-dichloropropene 1 with phenylmagnesium bromide. It is known that available iron(III) salts are effective catalysts in cross-coupling reactions of Grignard reagents with vinyl [9--12] and allyl halides [13,14]. Fe(acac) 3 the most commonly used in the synthesis of natural compounds [15,16] and drugs [17][18][19][20] is advantageously characterized by low hygroscopicity, good solubility, and ease of handling [21].The reaction of (E)-1,3-dichloropropene la with 3 equiv of PhMgBr in tetrahydrofuran in the presence of 3 mol % of Fe(acac) 3 afforded a mixture of (E)-and (Z)-isomers of 1,3-diphenylpropene 2a and 2b (E : Z = 92 : 8) in a 52% yield. The introduction of the most frequently used ligands like N,N,N,N-tetramethylethylenediamine (TMEDA) [22] or N-methylpyrrolidone (NMP) [10], the replacement of THF by diethyl ether and the use of FeCl 3 as the catalyst did not substantially increase the yield of the reaction product. However, a decrease in the reaction temperature to -35°C results in an increase in the yield of 1,3-diphenylpropene to 80% with the same isomeric composition.The cross-coupling with (Z)-1,3-dichloropropene under similar conditions resulted in an isomeric mixture of 1,3-diphenylpropene (E : Z = 55 : 45) with 72% yield, while at room temperature the reaction direction shifted toward the formation of (E)-isomer (E : Z = 76 : 24). (E)-and (Z)-isomers of 1,3-diphenylpropene and diphenyl formed by homocoupling reaction were separated by column chromatography (Scheme 1).Structure and purity of the obtained compounds was confirmed by high-performance GLC analysis, NMR spectroscopy and chromato-mass spectrometry. A reliable evidence of the stereochemical configuration of isomers 2a and 2b was the values of spin-spin coupling constant of vinyl hydrogen atoms (J = 15.6 and 11.3 Hz), characteristic of the E-and Z-con...

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Practical Iron‐Catalyzed Allylations of Aryl Grignard Reagents

Cited by 74 publications

References 61 publications

Iron Catalysis in Organic Synthesis

Iron Catalysis in Organic Synthesis

Iron‐Catalyzed C−O Bond Activation: Opportunity for Sustainable Catalysis

A Simple Synthesis of 1,3-Diphenylpropene

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