Phenanthrene cyclocarbonylation – core post-synthetic modification of phenanthriporphyrin

Kupietz, Kamil; Białek, Michał J.; Szyszko, Bartosz; Sarwa, Aleksandra; Latos‐Grażyński, Lechosław

doi:10.1039/d2qo00437b

Cited by 8 publications

(15 citation statements)

References 63 publications

(135 reference statements)

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“…Phenanthriporphyrin 493 reacted with Fe(CO) 5 and I 2 to give keto-derivative 501 . It was proposed that this reaction involved the intermediacy of an iron(II) organometallic complex [ 312 ].…”

Section: Contracted Carbaporphyrinoidsmentioning

confidence: 99%

Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems

Lash

2023

Molecules

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The unique environment within the core of carbaporphyrinoid systems provides a platform to explore unusual organometallic chemistry. The ability of these structures to form stable organometallic derivatives was first demonstrated for N-confused porphyrins but many other carbaporphyrin-type systems were subsequently shown to exhibit similar or complementary properties. Metalation commonly occurs with catalytically active transition metal cations and the resulting derivatives exhibit widely different physical, chemical and spectroscopic properties and range from strongly aromatic to nonaromatic and antiaromatic species. Metalation may trigger unusual, highly selective, oxidation reactions. Alkyl group migration has been observed within the cavity of metalated carbaporphyrins, and in some cases ring contraction of the carbocyclic subunit takes place. Over the past thirty years, studies in this area have led to multiple synthetic routes to carbaporphyrinoid ligands and remarkable organometallic chemistry has been reported. An overview of this important area is presented.

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Section: Contracted Carbaporphyrinoidsmentioning

confidence: 99%

Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems

Lash

2023

Molecules

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“…Ketophenanthriporphyrin 24 can be considered a borderline antiaromatic macrocycle [42] . In particular, the NH resonance position at 11.28 ppm indicated much less effective antiaromatic π‐conjugation than in 1 .…”

Section: Phenanthriporphyrin and Related Systemsmentioning

confidence: 99%

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

Szyszko

2022

Eur J Org Chem

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This Review discusses the recent developments in the field of synthetic chemistry of PAH–porphyrin hybrids, emphasizing phenanthrene‐embedded carbaporphyrinoids and related systems. The discussion covers various aspects of phenanthriporphyrin and its derivates chemistry, including their spectroscopic features, aromaticity, core reactivity, and coordination properties. The development of expanded phenanthriporphyrinoids is outlined, followed by the presentation of related carbaporphyrinoids incorporating hydrocarbon moieties such as fluorene, biphenyl, terphenyl, and dibenzo[g,p]chrysene. The exploitation of phenanthriporphyrinoids as a unique class of ligands for organometallic chemistry is discussed, altogether with their use for the construction of conformational and stereochemical switches. The perspective for using related macrocycles as building blocks for carbaporphyrinoid cages is also outlined.

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“…We therefore postulated that the reduction of the imide group (which stabilize the intermediates) to amine should be performed post‐macrocyclization. [ 36 , 37 ]…”

Section: Introductionmentioning

confidence: 99%

“…However, since the high HOMO level of furan intermediates renders them unstable throughout the synthetic procedure, we found that a previous strategy applied to macrocyclic thiophenes and pyrroles, namely, the macrocyclization of β‐alkyl‐monomers, [35] is not applicable for furan analogs. We therefore postulated that the reduction of the imide group (which stabilize the intermediates) to amine should be performed post‐macrocyclization [36,37] …”

Section: Introductionmentioning

confidence: 99%

“…We therefore postulated that the reduction of the imide group (which stabilize the intermediates) to amine should be performed postmacrocyclization. [36,37] Herein we apply a post-macrocyclization approach to introduce the first macrocyclic oligofuran with no electron withdrawing groups, by reducing four imide groups to amines in a single step to yield C 4 A (Scheme 1). We found that reducing the imide groups increases the global antiaromatic nature of the macrocycle in the neutral state.…”

Section: Introductionmentioning

confidence: 99%

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A Macrocyclic Furan with Accessible Oxidation States: Switching Between Aromatic and Antiaromatic Global Ring Currents

Dishi

Rahav

Carmieli

et al. 2022

Chemistry A European J

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Macrocyclic furans are predicted to switch between global aromaticity and antiaromaticity, depending on their oxidation states. However, the macrocyclic furans reported to date are stabilized by electron withdrawing groups, which result in inaccessible oxidation states. To circumvent this problem, a post-macrocyclization approach was applied to introduce methylene-substituted macrocyclic furans, which display an extremely low oxidation potential of À 0.23 vs. Fc/ Fc + , and are partially oxidized in ambient conditions. Addi-tional oxidation to the dication results in aromaticity switching to a global 30πe À aromatic state, as indicated by the formation of a strong diatropic current observed in the 1 H NMR spectrum. NICS and ACID calculations support this trend and provide evidence for a different pathway for the global current in the neutral and dicationic states. According to these findings, macrocyclic furans can be rendered as promising p-type materials with stable oxidation states.

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Phenanthrene cyclocarbonylation – core post-synthetic modification of phenanthriporphyrin

Abstract: The unique [Fe(CO)5]-induced cyclocarbonylation of the phenanthriporphyrin's core is an intriguing example of a post-synthetic core modification of the macrocycle. The reaction involves the activation of C(22)−H and C(25)−H bonds,...

Cited by 8 publications

References 63 publications

Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems

Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

A Macrocyclic Furan with Accessible Oxidation States: Switching Between Aromatic and Antiaromatic Global Ring Currents

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