Iron Porphyrin-Catalyzed Three-Component Reaction of Ethyl Diazoacetate with Aliphatic Amines and β,γ-Unsaturated α-Keto Esters

Ma, Chaoqun; Xing, Dong; Zhai, Changwei; Che, Jiuwei; Liu, Shunying; Wang, Jue; Hu, Wenhao

doi:10.1021/ol403011r

Cited by 47 publications

(15 citation statements)

References 35 publications

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“…Xing, Hu, and co-workers reported an iron porphyrin catalyzed three-component reaction of EDA with aliphatic amines and β,γ-unsaturated α-keto esters via a carbene insertion into the NÀH bond as a key step. 913 Insertion of carbenes generated from α-aryl α-diazo esters into the OÀH bond of alcohols and water has been reported by Zhou et al using catalytic amounts of iron(II) chloride tetrahydrate and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBAr F ) (Scheme 507). 914 In the presence of chiral spirobisoxazoline ligands the transformation is enantioselective.…”

Section: Insertion Of Carbene Nitrene and Related Speciesmentioning

confidence: 95%

Iron Catalysis in Organic Synthesis

2015

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Section: Insertion Of Carbene Nitrene and Related Speciesmentioning

confidence: 95%

Iron Catalysis in Organic Synthesis

2015

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“…56 Experimentally, the yield decreased with more electron-rich diazo derivatives. 15,16,[18][19][20] (d) The ylide formed by nucleophilic attack undergoes simultaneous rearrangement and dissociation from iron. Electron donation from iron to form the active species in the carbene system is reminiscent of the Cpd I formation pathway in P450s.…”

Section: C Comments On Hatmentioning

confidence: 99%

Computation Sheds Insight into Iron Porphyrin Carbenes’ Electronic Structure, Formation, and N–H Insertion Reactivity

et al. 2016

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Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential.

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“…Furthermore, Hu and co-workers were able to trap this metal-ylide intermediate with suitable electrophiles for developing a three-component reaction, thus providing further evidence for the existence of an ylide intermediate in iron porphyrin catalysed N-H insertion processes, along with the synthesis of β-hydroxy-α-amino esters starting from ethyl diazoacetate and aliphatic amines ( Scheme 35 ) [ 99 ].…”

Section: Carbene Insertion Into N-hmentioning

confidence: 99%

Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

et al. 2018

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Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn) as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

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Iron Porphyrin-Catalyzed Three-Component Reaction of Ethyl Diazoacetate with Aliphatic Amines and β,γ-Unsaturated α-Keto Esters

Cited by 47 publications

References 35 publications

Iron Catalysis in Organic Synthesis

Iron Catalysis in Organic Synthesis

Computation Sheds Insight into Iron Porphyrin Carbenes’ Electronic Structure, Formation, and N–H Insertion Reactivity

Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

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