Recent Advancements in Typical Friedel–Crafts Alkylation Reactions Focused on Targeting Arene Nucleophiles

Hazra, Chinmoy K.; Singh, Sanjay

doi:10.1055/s-0042-1751492

Cited by 10 publications

(3 citation statements)

References 320 publications

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“…Similar delocalization phenomenon of alkenes after oxidation has been reported previously . This is followed by a Friedel-Craft type alkylation from phenol 1 leading to a benzylic radical intermediate III . Pathway B commences with the oxidation of phenol ( 1a , E 1/2 = 1.70 V vs SCE in MeCN), forming radical species II followed by a strain-release event with BCB 2 .…”

Section: Resultssupporting

confidence: 80%

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Dutta,

Lee,

Ozols

et al. 2024

J. Am. Chem. Soc.

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Dearomative photocycloaddition of monocyclic arenes is an appealing strategy for comprehending the concept of “escape from flatland”. This brings the replacement of readily available planar aromatic hydrocarbon units with a 3D fused bicyclic core with sp 3-enriched carbon units. Herein, we outline an intermolecular approach for the dearomative photocycloaddition of phenols. In order to circumvent the ground-state aromaticity and to construct conformationally restrained building blocks, bicyclo[1.1.0]butanes were chosen as coupling partners. This dearomative approach renders straightforward access to a bicyclo[2.1.1]hexane unit fused to a cyclic enone moiety, which further contributed as a synthetic linchpin for postmodifications. Mechanistic experiment advocates for a plausible onset from both the reactants, depending on the redox potential.

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Section: Resultssupporting

confidence: 80%

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Dutta,

Lee,

Ozols

et al. 2024

J. Am. Chem. Soc.

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“…Moreover, based on previous studies, possible reaction mechanisms involving in situ generated Brønsted acid potentially played the role of the active catalyst …”

Section: Resultsmentioning

confidence: 99%

“…It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via the controllable construction of a heterogeneous catalyst containing defined active sites. The industrial production of unsymmetrical polyarylated alkanes involves the usage of precious metal complexes involving various cross-coupling reactions with prefunctionalized starting materials and demands Grignard conditions (Scheme A), and also includes homogeneous Lewis acid or Brønsted acid catalyzed FC reaction using electron-rich arenes, and high stoichiometry of corrosive acids such as sulfuric acid to afford polyarylated alkanes (Scheme A) . Consequently, several methods have also been reported using solid acidic catalysts, and ionic liquids have been employed to accomplish this typical FC reaction (Scheme B) .…”

mentioning

confidence: 99%

Sustainable Sulfonic Acid Functionalized Tubular Shape Mesoporous Silica as a Heterogeneous Catalyst for Selective Unsymmetrical Friedel–Crafts Alkylation in One Pot

Singh,

Kumar,

Nebhani

et al. 2023

JACS Au

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The development of general and more sustainable heterogeneous catalytic processes for Friedel–Crafts (FC) alkylation reactions is a key objective of interest for the synthesis of pharmaceuticals and commodity chemicals. Sustainable heterogeneous catalysis for the typical FC alkylation of an easily accessible carbonyl electrophile and arenes or with two different arene nucleophiles in one-pot is a prime challenge. Herein, we present a resolution to these issues through the design and utilization of a mesoporous silica catalyst that has been functionalized with sulfonic acid. For the synthesis of sulfonic acid-functionalized mesoporous silica (MSN-SO 3 H), thiol-functionalized mesoporous silica was first synthesized by the co-condensation method, followed by oxidation of the thiol functionality to the sulfonic acid group. Sulfonation of mesoporous silica was confirmed by 13 C CP MAS NMR spectroscopy. Further, the devised heterogeneous catalysis using MSN-SO 3 H has been successfully employed in the construction of diverse polyalkanes including various bioactive molecules, viz arundine, tatarinoid-C, and late-stage functionalization of natural products like menthol and Eugenol. Further, we have utilized this sustainable technique to facilitate the formation of unsymmetrical C–S bonds in a one-pot fashion. In addition, the catalyst was successfully recovered and recycled for eight cycles, demonstrating the high sustainability and cost-effectiveness of this protocol for both academic and industrial applications.

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Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters^†

Gao,

Hao,

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryCatalytic dehydrogenation, with its exceptional atom economy and chemoselectivity, offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules. Furthermore, the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications. The present study describes a practical Co‐catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters, facilitating the synthesis of a wide range of 3‐hydroxy‐prop‐2‐en‐1‐ones. We introduce a catalytic system based on novel and scalable indazole NNP‐ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols, and propose a plausible reaction mechanism supported by control experiments and labeling studies. Notably, it allows for the streamlined synthesis of multiple pharmaceuticals in one‐pot.

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Recent Advancements in Typical Friedel–Crafts Alkylation Reactions Focused on Targeting Arene Nucleophiles

Cited by 10 publications

References 320 publications

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Sustainable Sulfonic Acid Functionalized Tubular Shape Mesoporous Silica as a Heterogeneous Catalyst for Selective Unsymmetrical Friedel–Crafts Alkylation in One Pot

Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters^†

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Recent Advancements in Typical Friedel–Crafts Alkylation Reactions Focused on Targeting Arene Nucleophiles

Cited by 10 publications

References 320 publications

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols

Sustainable Sulfonic Acid Functionalized Tubular Shape Mesoporous Silica as a Heterogeneous Catalyst for Selective Unsymmetrical Friedel–Crafts Alkylation in One Pot

Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters†

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Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters^†