An Iron/Amine‐Catalyzed Cascade Process for the Enantioselective Functionalization of Allylic Alcohols

Quintard, Adrien; Constantieux, Thierry; Rodríguez, Jean

doi:10.1002/anie.201307295

Cited by 154 publications

(69 citation statements)

References 63 publications

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“…Iron cyclopentadienone complex Cat1 (refs 21-23) (Fig. 2b) has been recently used in C ¼ O transfer hydrogenation 24,25 as well as cooperative dual catalysis involving hydrogen autotransfer processes 26 . Given its unique reactivity, we considered Cat1 to be a promising candidate for the development of the desired iron-catalyzed hydrogen borrowing methodology.…”

Section: Resultsmentioning

confidence: 99%

Iron catalysed direct alkylation of amines with alcohols

2014

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The selective conversion of carbon-oxygen bonds into carbon-nitrogen bonds to form amines is one of the most important chemical transformations for the production of bulk and fine chemicals and pharma intermediates. An attractive atom-economic way of carrying out such C-N bond formations is the direct N-alkylation of simple amines with alcohols by the borrowing hydrogen strategy. Recently, transition metal complexes based on precious metals have emerged as suitable catalysts for this transformation; however, the crucial change towards the use of abundant, inexpensive and environmentally friendly metals, in particular iron, has not yet been accomplished. Here we describe the homogeneous, iron-catalysed, direct alkylation of amines with alcohols. The scope of this new methodology includes the monoalkylation of anilines and benzyl amines with a wide range of alcohols, and the use of diols in the formation of five, six-and seven-membered nitrogen heterocycles, which are privileged structures in numerous pharmaceuticals.

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Section: Resultsmentioning

confidence: 99%

Iron catalysed direct alkylation of amines with alcohols

2014

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“…(20);T MS = trimethylsilyl]. [77] Combining the two orthogonal catalytic cycles (BH catalysis by the iron complex 47 and iminium activation by the chiral amine 48) remarkably enhanced the hydrogen-transfer activity of the iron complex. This one-pot method features dual catalysis, thus enabling conversion of allylic alcohols into b-chiral alcohols under mild reaction conditions in an enantioselective fashion.…”

Section: Enantioselective Functionalization With Alcoholsmentioning

confidence: 99%

C‐Alkylation of Ketones and Related Compounds by Alcohols: Transition‐Metal‐Catalyzed Dehydrogenation

2015

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Transition-metal-catalyzed C-alkylation of ketones and secondary alcohols, with alcohols, avoids use of organometallic or environmentally unfriendly alkylating agents by means of borrowing hydrogen (BH) or hydrogen autotransfer (HA) activation of the alcohol substrates. Water is formed as the only by-product, thus making the BH process atom-economical and environmentally benign. Diverse homogeneous and heterogeneous transition-metal catalysts, ketones, and alcohols can be used for this transformation, thus rendering the BH process promising for replacing those procedures that use traditional alkylating agents. This Minireview summarizes the advances during the last five years in transition-metal-catalyzed BH α-alkylation of ketones, and β-alkylation of secondary alcohols with alcohols. A discussion on the application of the BH strategy for C-C bond formation is included.

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“…Recently, our group also reported an interesting dual catalytic transformation discovered thanks to iron cyclopentadienone complex Fe6. [44] This reaction takes full advantage of the ambivalent redox properties of this iron complex combined with an aminocatalyst 7, triggering the enantioselective functionalization of allylic alcohols (Scheme 25 a). The oxidation complex Fe8, formed in situ, is able to abstract hydrogen from the starting allylic alcohol leading to a reactive a,b-unsaturated aldehyde and generating Fe7.…”

Section: Angewandte Minireviewsmentioning

confidence: 99%

Iron Cyclopentadienone Complexes: Discovery, Properties, and Catalytic Reactivity

Quintard¹,

Rodríguez²

2014

Angew Chem Int Ed

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173

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Iron cyclopentadienone complexes have recently received particular attention in organic chemistry. This is due to their easy synthesis from simple and cheap materials, air-water stability, and most importantly for their unique catalytic features arising from the presence of a non-innocent ligand, triggering powerful redox properties. Herein we discuss the properties of such complexes from synthetic and mechanistic points of view, and their applications in original redox-neutral transformations in both racemic and enantioselective series.

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An Iron/Amine‐Catalyzed Cascade Process for the Enantioselective Functionalization of Allylic Alcohols

Cited by 154 publications

References 63 publications

Iron catalysed direct alkylation of amines with alcohols

Iron catalysed direct alkylation of amines with alcohols

C‐Alkylation of Ketones and Related Compounds by Alcohols: Transition‐Metal‐Catalyzed Dehydrogenation

Iron Cyclopentadienone Complexes: Discovery, Properties, and Catalytic Reactivity

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