Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals

Reed-Berendt, Benjamin G.; Polidano, Kurt; Morrill, Louis C.

doi:10.1039/c8ob01895b

Cited by 318 publications

(138 citation statements)

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“…[12] On the contrary, β-hydrogen elimination is relatively frequent for alkoxides and constitutes the basis for a number of catalytic applications mentioned in the Introduction. [17][18][19][20] Mechanistic studies have shown that βhydrogen elimination may, in fact, involve different pathways, summarized in Scheme 10. Mechanism A is analogous to typical β-elimination in alkyl complexes, and requires a vacant coordination site in cis to the β-hydrogen donor ligand.…”

Section: Methodsmentioning

confidence: 99%

“…[65] Our ability to synthesize a range of nickel alkoxide and amide complexes prompted us to examine the thermal stability of these complexes, in order to gain some insight in their decomposition mechanisms. In one of our studies (Scheme 12) we compared the thermal stability of some methylnickel alkoxides and amides (18)(19)(20)(21), available through the fluoride exchange route described in the precedent section. [66] To complete this study, we included a mixed methylnickel alkyl, 22, also obtained through fluoride exchange method.…”

Section: Methodsmentioning

confidence: 99%

“…[11] The number of applications of the special "organometallic-like" reactivity of transition metal compounds with MÀ N or MÀ O bonds has experienced a continuous growth. Some prominent examples of these are the Buchwald-Hartwig aryl amination [12] (now celebrating its 25th anniversary) and the analogous etherification reaction, [13] the Suzuki-Miyaura reaction, [14] reductive couplings of carbonyl and unsaturated compounds, [15] reduction of carbonyl compounds, [16] aerobic [17] or acceptorless [18] alcohol oxidation, hydrogen borrowing alkylation, [19] or various dehydrogenative coupling reactions, [20] just to cite a few of them (see Chart 1). In parallel, an intense effort has been deployed to understand the fundamental aspects of reactive metal-heteroatom bonds, either as catalytic intermediates or as stoichiometric reagents.…”

Section: Introductionmentioning

confidence: 99%

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Nickel and Palladium Complexes with Reactive σ‐Metal‐Oxygen Covalent Bonds

Martínez‐Prieto

Cámpora

2020

Israel Journal of Chemistry

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This article reviews the chemistry of nickel and palladium complexes with terminally bound hydroxide and alkoxide ligands. The research carried out in our group is discussed in the context of the general literature. It is shown that suitable methods of synthesis, combined with the choice of adequate ligands allow the isolation of a range of stable complexes. This has enabled a detailed investigation of the chemical reactivity of the MÀ O bonds, once believed to be intrinsically weak. The elucidation of trends in thermodynam-ic stability and kinetic lability is the key for a better understanding of the reactivity of this class of compounds, that combines basic and nucleophilic properties with typical organometallic patterns, like β-hydrogen elimination. Based on reversible acid-base exchange and CO 2 insertion reactions, we discuss how the polarity of the M-OR bonds influence their relative stability, their hydrolytic sensitivity and their tendency to react with electrophiles. Scheme 3. Precedents in the chemistry of Ni(II) alkoxide and hydroxide complexes.Scheme 4. Self-aldol reaction of nickel enolates promoted by bridging alkoxide interactions. Figures in brackets stand for isolated yields of pure products. ReviewIsr. J. Chem. 2020, 60, 373 -393 Scheme 5. Dimerization-driven mechanism of the self-aldol reaction. Scheme 6. Syntheses of some of group 10 hydroxide complexes with iPr PCP pincer ligands. Figures in brackets stand for isolated yields of pure products.Review Isr. J. Chem. 2020, 60, 373 -393 Scheme 14. Proposed mechanism for the decomposition of Ni(II) alkoxides catalyzed by Ni(I) species. Scheme 15. Mechanism of decomposition and activation parameters for β-hydrogen elimination from methoxide in Ni and Pd pincer complexes. Scheme 23. Carboxylation and reversible hydrolysis of iPr PCP-based alkoxides of Ni and Pd. Scheme 24. Kinetic lability of alkylcarbonate complexes. Scheme 25. Use of reversible water-alcohol exchange to probe the thermodynamics of CO 2 into different MÀ OR bonds.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Nickel and Palladium Complexes with Reactive σ‐Metal‐Oxygen Covalent Bonds

Martínez‐Prieto

Cámpora

2020

Israel Journal of Chemistry

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“…These examples show that the iron‐catalysed borrowing methodology exhibits similar efficiency to that with other 3d transition metals, but they are not yet as competitive as the classical noble metal‐catalysed ones, mainly in terms of catalytic loadings …”

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

confidence: 97%

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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“…The borrowing hydrogen strategy has been widely applied in organic transformations to construct various C-X (X = C, N, S) compounds in the last decade [17][18][19]. In this context, of particular importance is the N-alkylation of amines with alcohols to synthesize structurally complex primary and/or secondary amine compounds, which represents one of the most straightforward, efficient and eco-friendly methodologies for amine synthesis.…”

Section: Introductionmentioning

confidence: 99%

Switchable Access to Amines and Imines from Reductive Coupling of Nitroarenes with Alcohols Catalyzed by Biomass-Derived Cobalt Nanoparticles

et al. 2019

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Cobalt nanoparticles modified with N-doped hierarchical porous carbon derived from biomass are found to be a highly efficient, reusable heterogeneous catalyst for the coupling of nitroarenes with alcohols, selectively affording imines and amines via the borrowing hydrogen strategy for the first time. The product selectivity between imine and amine may be precisely tuned by simple alteration of the reaction conditions without changing the catalyst in one reaction system. In this study, a broad set of complex imines and amines was successfully synthesized in good to high yields with various functional groups tolerated for both nitroarenes and alcohols, highlighting the potentially practical utility of the protocol. This heterogeneous catalyst can be easily removed from the reaction medium by external magnet and can be reused at least four times without significant loss in activity and selectivity.Catalysts 2019, 9, 116 2 of 11 achievements, direct synthesis of imines by the coupling of nitroarenes and alcohols with high activity and selectivity via the borrowing hydrogen strategy remains challenging. To date, only a handful of examples enabled by noble metal catalysts (e.g., Pd [46,47], Ru [48], Ir [49], and Au [50,51]) have been reported; however, their catalytic activities and selectivities are rather low and accompanied by limited substrate scopes (Scheme 1b). In addition, the high cost and limited reserve on earth of noble metal catalysts significantly impedes their large-scale industrial application. Notably, no successful direct imine formation from nitroarenes and alcohols catalyzed by heterogeneous base metal catalysts has been described, to the best of our knowledge.

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Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals

Cited by 318 publications

References 50 publications

Nickel and Palladium Complexes with Reactive σ‐Metal‐Oxygen Covalent Bonds

Nickel and Palladium Complexes with Reactive σ‐Metal‐Oxygen Covalent Bonds

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

Switchable Access to Amines and Imines from Reductive Coupling of Nitroarenes with Alcohols Catalyzed by Biomass-Derived Cobalt Nanoparticles

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