The Power of Iron Catalysis in Diazo Chemistry

Carreras, Virginie; Tanbouza, Nour; Ollevier, Thierry

doi:10.1055/s-0040-1707272

Cited by 20 publications

(5 citation statements)

References 72 publications

(105 reference statements)

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“…Further reduction of intermediate D by another Fe(TPP) or Mn furnishes the active iron carbene E . 31 The subsequent fast concerted Si–H insertion yields the organosilicon product and regenerates Fe(TPP), completing the catalytic cycle. 32…”

Section: Resultsmentioning

confidence: 99%

Fe-catalyzed B–H and Si–H insertion reactions of gem-dihaloalkanes

Wang,

Wang

2024

Org. Chem. Front.

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Section: Resultsmentioning

confidence: 99%

Fe-catalyzed B–H and Si–H insertion reactions of gem-dihaloalkanes

Wang,

Wang

2024

Org. Chem. Front.

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“…Therefore, they are electrically neutral species that can simultaneously form two bonds. Metal–carbene complexes are species made up of carbenes that are covalently bonded to a metal, usually with expensive transition metals (M = Ru, Os, Co, Rh, Ir) [ 14 , 15 ]; however, there are several works with iron, an abundant metal, which is cheap, environmentally benign, and with low toxicity [ 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. The chemical behavior of carbenes and metal–carbene complexes differ in reactivity and selectivity.…”

Section: Introductionmentioning

confidence: 99%

Recent Synthetic Advances on the Use of Diazo Compounds Catalyzed by Metalloporphyrins

Simões,

Cavaleiro,

Ferreira

2023

Molecules

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Diazo compounds are organic substances that are often used as precursors in organic synthesis like cyclization reactions, olefinations, cyclopropanations, cyclopropenations, rearrangements, and carbene or metallocarbene insertions into C−H, N−H, O−H, S−H, and Si−H bonds. Typically, reactions from diazo compounds are catalyzed by transition metals with various ligands that modulate the capacity and selectivity of the catalyst. These ligands can modify and enhance chemoselectivity in the substrate, regioselectivity and enantioselectivity by reflecting these preferences in the products. Porphyrins have been used as catalysts in several important reactions for organic synthesis and also in several medicinal applications. In the chemistry of diazo compounds, porphyrins are very efficient as catalysts when complexed with low-cost metals (e.g., Fe and Co) and, therefore, in recent years, this has been the subject of significant research. This review will summarize the advances in the studies involving the field of diazo compounds catalyzed by metalloporphyrins (M−Porph, M = Fe, Ru, Os, Co, Rh, Ir) in the last five years to provide a clear overview and possible opportunities for future applications. Also, at the end of this review, the properties of artificial metalloenzymes and hemoproteins as biocatalysts for a broad range of applications, namely those concerning carbene-transfer reactions, will be considered.

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“…This status represents a distinct advantage compared to the ≤10 ppm prescribed for most other transition metals, including rhodium . These characteristics elevate iron as a sustainable catalyst for chemical synthesis, presenting economic benefits and enhanced safety features. , Another crucial factor contributing to cost-effective chemical synthesis involves adopting cascade reactions, which have garnered substantial research interest in recent years . These reactions offer remarkable advantages, encompassing atom economy, a substantial saving in time, labor, resources, and waste management .…”

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confidence: 99%

Iron-Carbene Initiated O–H Insertion/Aldol Cascade for the Stereoselective Synthesis of Functionalized Tetrahydrofurans

Kafle,

Ghosh,

Hunter

et al. 2024

ACS Catal.

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Given its earth abundance, cost-effectiveness, and ecofriendly qualities, iron serves as a promising alternative to precious metals in catalysis. This article presents an iron carbene-initiated cascade approach for synthesizing highly substituted tetrahydrofurans at the gram scale. This cascade reaction utilizes readily accessible β-hydroxyketones and diazo compounds and works with iron catalyst loading as low as 5 mol %. This reaction proceeds through an O−H insertion into diazo-derived iron carbenes, followed by an intramolecular aldol reaction to access functionalized tetrahydrofurans in high yields and diastereoselectivity. The versatile nature of this domino sequence accommodates diverse β-hydroxyketones and diazo compounds, streamlining access to synthetically challenging spiroethers. Furthermore, this cascade process offers a route to enantiopure tetrahydrofurans by utilizing a diazo ester bearing a chiral auxiliary, 8-phenylmenthol. Postmodifications of the tetrahydrofuran product provide access to various analogues, including a medicinally relevant oxetane motif. Density functional theory (DFT) calculations substantiate a stereospecific mechanism wherein the intramolecular aldol reaction proceeds via a fused six-and five-membered iron−oxygen transition-state complex, yielding the contrathermodynamic cis-aldol product.

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The Power of Iron Catalysis in Diazo Chemistry

Cited by 20 publications

References 72 publications

Fe-catalyzed B–H and Si–H insertion reactions of gem-dihaloalkanes

Fe-catalyzed B–H and Si–H insertion reactions of gem-dihaloalkanes

Recent Synthetic Advances on the Use of Diazo Compounds Catalyzed by Metalloporphyrins

Iron-Carbene Initiated O–H Insertion/Aldol Cascade for the Stereoselective Synthesis of Functionalized Tetrahydrofurans

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