Carbene-Type Species in the Functionalization of Porphyrin Derivatives

Gomes, Ana T. P. C.; Forezi, Luana da S. M.; Simões, Mário M. Q.; Gonzaga, Daniel T. G.; Cardoso, Mariana F. C.; Silva, Fernando De C. Da; Ferreira, Vı́tor F.; Cavaleiro, José A. S.

doi:10.1055/s-0037-1609756

Cited by 7 publications

(4 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this sense, diazo compounds are excellent reactants for interacting with porphyrins in inter- or intramolecular reactions and structural modifications in the outer part of the macrocyclic ring. As metalloporphyrins have a metal ion in the center of each macrocycle, they can form metallocarbene intermediates (mainly from diazo compounds) that can catalyze various reactions, such as inter- or intramolecular cyclopropanations, cyclopropenation reactions, carbene carbonylation, olefination of carbonyl compounds, formation of C−C, C−N, C−O, C−Si, C−S bonds, intramolecular Buchner reaction, among others [ 10 , 11 , 17 , 28 , 29 , 30 , 31 , 32 ].…”

Section: Porphyrin-based Catalystsmentioning

confidence: 99%

“…It is crucial to emphasize that in the absence of the Co complex of meso-tetraphenyl porphyrin (CoTPP), only the diazo compound would be formed, and the cyclization product would not be obtained. [10,11,17,[28][29][30][31][32].…”

Section: Reactions Through Unusual Strategiesmentioning

confidence: 99%

“…For a long time, and up to the present day, these compounds continue to be of interest for organic synthesis and have been reviewed by many researchers in scientific journals and books, mainly in using more efficient and selective catalysts [5][6][7][8]. The scope of reactions involving carbenes and metallocarbenes represents a significantly broader and more versatile approach in organic synthesis compared to reactions with diazo compounds [9][10][11][12]. Carbenes are species containing only two groups covalently bonded to a carbon and two free nonbonding electrons that can be spin-paired in the same orbital (singlet state) or unpaired carbon and two free non-bonding electrons that can be spin-paired (singlet state) or unpaired in two separate orbitals (triplet state) [13].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Simões,

Cavaleiro,

Ferreira

2023

Molecules

View full text Add to dashboard Cite

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.

show abstract

Section: Porphyrin-based Catalystsmentioning

confidence: 99%

Section: Reactions Through Unusual Strategiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Simões,

Cavaleiro,

Ferreira

2023

Molecules

View full text Add to dashboard Cite

show abstract

“…N-Heterocyclic carbenes (NHCs), which are cyclic carbene species with at least one nitrogen atom, have attracted increasing attention because of their strong σ-donor capacity that makes them very useful ligands for various transition metals. − The first isolated iron porphyrin NHC complex [Fe III (TDCPP)(1,3-Me 2 Imd) 2 ]I has been applied as a catalyst in the C(sp3)–H amination of alkyl azides . However, controversies still exist concerning bonding in NHC-based transition-metal complexes, especially in the context of σ-donor/π-acceptor properties of NHC ligands and, in particular, regarding the importance of π-back-bonding. , NHC ligands were originally regarded basically as pure σ-donors .…”

Section: Introductionmentioning

confidence: 99%

Perspectives on Ligand Properties of N-Heterocyclic Carbenes in Iron Porphyrin Complexes

Wang

Liu

et al. 2021

Inorg. Chem.

View full text Add to dashboard Cite

There has been considerable research interest in the ligand nature of N-heterocyclic carbenes (NHCs). In this work, two six-coordinate NHC iron porphyrin complexes [FeII(TTP)(1,3-Me2Imd)2] (TTP = tetratolylporphyrin, 1,3-Me2Imd = 1,3-dimethylimidazol-2-ylidene) and [FeIII(TDCPP)(1,3-Me2Imd)2]ClO4 (TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin) are reported. Single-crystal X-ray characterizations demonstrate that both complexes have strongly ruffled conformations and relatively perpendicular ligand orientations which are forced by the sterically bulky 1,3-Me2Imd NHC ligands. Multitemperature (4.2–300 K) and high magnetic field (0–9 T) Mössbauer and low-temperature (4.0 K) EPR spectroscopies definitely confirmed the low-spin states of [FeII(TTP)(1,3-Me2Imd)2] (S = 0) and [FeIII(TDCPP)(1,3-Me2Imd)2]ClO4 (S = 1/2). The similarity of 1,3-Me2Imd and imidazole, as well as the well-established correlations between the ligand nature and spectroscopic characteristics of [FeII,III(Porph)(L)2]0,+ (Porph: porphyrin; L: planar base ligand) species, allowed direct comparisons between the pair of ligands which revealed for the first time that NHC has a stronger π-acceptor ability than imidazoles, in addition to its very strong σ-donation.

show abstract

Molecular Systems Combining Porphyrinoids and N‐Heterocyclic Carbenes

et al. 2021

View full text Add to dashboard Cite

Porphyrins and N‐heterocyclic carbenes (NHCs) are both relevant ligands in the fields of coordination and organometallic chemistry. Despite evident structural differences, porphyrins and NHCs have a lot in common such as their ability to form strong metal‐ligand bonds and their use in catalysis, materials science and biomedicine. During the last decade, several molecular systems combining porphyrins and NHC ligands were reported in the literature. The present review gathers relevant examples where NHC ligands are either axially bonded to metalloporphyrins or covalently attached to the porphyrin cores. Structural diversity, electronic interplay between porphyrins and NHCs and some relevant applications in catalysis and biomedicine are notably described. Finally, molecular systems combining NHCs with other original porphyrinoids such as N‐confused porphyrins, subporphyrins and norcorroles are also presented.

show abstract

Carbene-Type Species in the Functionalization of Porphyrin Derivatives

Cited by 7 publications

References 28 publications

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

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

Perspectives on Ligand Properties of N-Heterocyclic Carbenes in Iron Porphyrin Complexes

Molecular Systems Combining Porphyrinoids and N‐Heterocyclic Carbenes

Contact Info

Product

Resources

About