Use of (Cyclopentadienone)iron Tricarbonyl Complexes for C–N Bond Formation Reactions between Amines and Alcohols

Brown, Thomas J.; Cumbes, Madeleine; Diorazio, Louis J.; Clarkson, Guy J.; Wills, Martin

doi:10.1021/acs.joc.7b01990

Cited by 74 publications

(34 citation statements)

References 74 publications

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“…Following this breakthrough, the scope of CIC‐catalyzed amination was expanded to the less reactive benzylic alcohols: Barta and co‐workers achieved this goal optimizing the reaction conditions with CIC 1a (Scheme A), whereas Wills and co‐workers employed the tetraphenyl‐substituted CIC 1g (Scheme B) . The Wills' group later developed a series of new CICs ( 1h–m , Scheme C) and used them in the amination of several substrates, including a few secondary alcohols …”

Section: Applications In Reactions Involving Ht Stepsmentioning

confidence: 99%

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Recent Catalytic Applications of (Cyclopentadienone)iron Complexes

Pignataro

Gennari

2020

Eur J Org Chem

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(Cyclopentadienone)iron complexes (CICs) are attractive pre‐catalysts due to their easy preparation and robustness, which are uncommon features in homogeneous iron catalysis. They represent a striking example of how deeply a non‐innocent ligand may affect the catalytic properties of the metal. Swinging between the cyclopentadienone and the hydroxycyclopentadienyl form, the ligand induces iron to engage in H2 heterolytic cleavage and transfer. The latter represents the basis for numerous applications of CICs in redox chemistry (multiple bond reduction, alcohol oxidation) and “hydrogen borrowing” processes (e.g., alcohol amination) that have been reported over the last few years. Moreover, very recently catalytic applications of CICs in different types of reactivity (where again the non‐innocent ligand plays a key role), have appeared in the literature. This minireview summarizes the advancements that have been made in the field of CICs and their catalytic applications in the period 2014–2019.

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Section: Applications In Reactions Involving Ht Stepsmentioning

confidence: 99%

“…HB amination of benzylic alcohols promoted by pre‐catalyst 1a (A) and 1g (B) . The CIC series developed by Wills and co‐workers and its application to the HB amination (C) …”

Section: Applications In Reactions Involving Ht Stepsmentioning

confidence: 99%

Recent Catalytic Applications of (Cyclopentadienone)iron Complexes

Pignataro

Gennari

2020

Eur J Org Chem

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“…Modifying the structure of the cyclopentadienone moiety, Wills has shown that a catalytic system generated in situ from the modified Knölker complex bearing a tetraphenyl‐pentadienone ligand ( 29 , 10 mol‐%) and Me 3 NO (10 mol‐%) exhibited similar activity when performing the reaction in toluene at 110 °C for 48 h or xylene at 140 °C for 24 h . He also designed a family of (cyclopentadienone)iron tricarbonyl complexes by modulating the electronic properties of the aromatic groups in α ‐positions to the C=O of the cyclopentadienone, and identified the complex 30 as the most active catalyst precursor for the series for BH of alcohols with various amines (10 mol‐% of 30 , 9 mol‐% of Me 3 NO, xylene, 140 °C) . Zhao reported that the complex 31 bearing a benzonitrile ligand instead of a CO (10 mol‐%) in combination with 40 mol‐% of AgF was efficient for the reaction of primary anilines with 5 equiv.…”

Section: Multi‐step Reactions Involving Iron‐catalysed Hydrogen Bomentioning

confidence: 99%

Multi‐Step Reactions Involving Iron‐Catalysed Reduction and Hydrogen Borrowing Reactions

2019

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Iron catalysis has seen an impressive breakthrough during the last two decades, and iron can now be considered as a valuable alternative transition metal for organic synthetic transformations. More precisely, in the reduction area, it became an efficient player for the selective reduction of olefins, alkynes, carbonyl and carboxylic derivatives, imines and nitro [a] Sortais. His work focuses on the homogeneous iron, manganese and rhenium-catalysed reduction and dehydrogenation reactions. Chakkrit Netkaew (left) was born in Nakhon Sawan, Thailand, in 1992. He completed his Bachelor's degree in Chemistry in 2017 from Mahidol University in Bangkok, Thailand, under the supervision of Assoc. Prof. Pasit Pakawatpanurut. After his graduation, he received a Franco-Thai scholarship 2018 from the French Embassy to attend the International Master's Program (Catalysis, Molecules and Green Chemistry) at the University of Rennes 1. Currently, he is carrying out research on the homogeneous iron-catalysed reduction reactions in Prof. C. Darcel's team. Prof. Christophe Darcel (centre) grew up in the north coast of Britany and studied chemistry at the University of Rennes 1, where he obtained his PhD in 1995 under the joint-supervision of Dr. Christian Bruneau and Prof. Pierre H. Dixneuf on Ru-and Pd-catalysed transformations of functional alkynes. After a year's postdoctoral stay with Prof. Wolfgang Oppolzer (Switzerland) working on sultam stereoselective chemistry and application in natural products synthesis, he then joined the group of Prof. Paul Knochel in Marburg (Germany) as an Alexander von Humboldt postdoctoral fellow and worked on the development of chiral zinc derivatives. In 1997, he was then appointed at the University of Cergy-Pontoise as assistant professor, and at the University of Burgundy as associate professor developing in collaboration with Prof. Sylvain Jugé P-chirogenic ligands for asymmetric catalysis. In 2007, he became full professor at the University of Rennes 1. His current research interests concentrate on homogeneous catalysis with particular emphasis on well-defined iron complexes in catalysis. 2474Scheme 12. Proposed mechanism for the selective formation of the secondary imines.Scheme 13. Selective reductive cross-coupling of nitriles and amines to form secondary aldimines. 2475Scheme 49. Iridium-iron-catalysed tandem conversion of alkanes to alkylsilanes. 2485 the use of CO 2 as a C1 building block, (ii) a step devoted to reduction of carboxylic derivatives, (iii) an enantioselective reduction step, and (iv) the use of biomass derivatives as starting materials.These achievements in iron-catalysed multi-step processes have already led to very impressive and promising results and will without any doubt stimulate their development in the near future.

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“…Therefore, application of Fe-based catalysts in organic synthesis attract significant attention [34][35][36][37][38][39][40]. Interestingly, iron catalysts were extensively used in cross-coupling reactions, [41][42][43][44][45] hydrogenations and transfer hydrogenations, [46][47][48][49], hydrosilylations [50][51][52], as well as in hydroboration processes [53,54]. However, the application of a Knölker-type complex for the alkylation and methylation of ketones and alcohols is noteworthy [55][56][57][58][59].…”

Section: Introductionmentioning

confidence: 99%

A Simple Iron-Catalyst for Alkenylation of Ketones Using Primary Alcohols

Kumar

Das

et al. 2020

Molecules

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Herein, we developed a simple iron-catalyzed system for the α-alkenylation of ketones using primary alcohols. Such acceptor-less dehydrogenative coupling (ADC) of alcohols resulted in the synthesis of a series of important α,β-unsaturated functionalized ketones, having aryl, heteroaryl, alkyl, nitro, nitrile and trifluoro-methyl, as well as halogen moieties, with excellent yields and selectivity. Initial mechanistic studies, including deuterium labeling experiments, determination of rate and order of the reaction, and quantitative determination of H2 gas, were performed. The overall transformations produce water and dihydrogen as byproducts.

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Use of (Cyclopentadienone)iron Tricarbonyl Complexes for C–N Bond Formation Reactions between Amines and Alcohols

Cited by 74 publications

References 74 publications

Recent Catalytic Applications of (Cyclopentadienone)iron Complexes

Recent Catalytic Applications of (Cyclopentadienone)iron Complexes

Multi‐Step Reactions Involving Iron‐Catalysed Reduction and Hydrogen Borrowing Reactions

A Simple Iron-Catalyst for Alkenylation of Ketones Using Primary Alcohols

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