A phosphine free, inorganic base free, one-pot tandem Mizoroki–Heck olefination/direct arylation/hydrogenation sequence, to give multicyclic alkylated heteroarenes

Kehoe, Roberta A.; Light, Mark E.; Jones, David J.; McGlacken, Gerard P.

doi:10.1039/d3gc01403g

Cited by 6 publications

(1 citation statement)

References 69 publications

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“…[6] Due to their medicinal importance, [7,8] the synthesis of dihydrobenzofurans and dihydroindoles has been attracting increasing interest from the chemical community, which leads to the several distinct protocols available for their synthesis. [9,10,[19][20][21][22][23][24][25][11][12][13][14][15][16][17][18] However, in the case of dihydrobenzofurans and dihydroindoles bearing an estereogenic center at the C-3 position, there are only a few protocols available for their synthesis in an enantioselective manner. Arguably, the intramolecular radical synthesis of dihydrobenzofuran and dihydroindole derivatives is the most employed strategy, [26][27][28][29] but it leads to racemic products (Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Synthesis of Dihydrobenzofurans, Dihydrobenzosulfones, and Dihydroindoles by Merging One‐pot Intramolecular Heck‐Matsuda Reactions from Anilines with Redox‐Relay Process

Scarpa de Souza,

Gorbatov,

Pierozzi

et al. 2024

Chemistry A European J

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A one‐pot tandem process was developed aiming at the concise and expeditious enantioselective synthesis of dihydrobenzofuran, dihydrobenzosulfone, and dihydroindole scaffolds under mild, and open‐flask conditions. This process combines the in situ generation of aryldiazonium salt directly from the anilines in methanol telescoped to an intramolecular Heck‐Matsuda reaction linked to a redox relay process to provide the final products as the dimethyl acetals. These Heck products were smoothly converted into the corresponding primary alcohols or esters. The robustness and the efficiency of the protocol are demonstrated by the synthesis of 24 enantioenriched dihydrobenzofurans, dihydrobenzosulfones, and dihydroindoles in overall yields up to 78% in enantiomeric ratios up to 99:1 by a sequential 5‐step protocol..

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Section: Introductionmentioning

confidence: 99%

Enantioselective Synthesis of Dihydrobenzofurans, Dihydrobenzosulfones, and Dihydroindoles by Merging One‐pot Intramolecular Heck‐Matsuda Reactions from Anilines with Redox‐Relay Process

Scarpa de Souza,

Gorbatov,

Pierozzi

et al. 2024

Chemistry A European J

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Regioselective Partial Hydrogenation and Deuteration of Tetracyclic (Hetero)aromatic Systems Using a Simple Heterogeneous Catalyst

Kehoe,

Lowry,

Light

et al. 2024

Chemistry A European J

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The introduction of added ‘3‐dimensionality’ through late‐stage functionalization of extended (hetero)aromatic systems is a powerful synthetic approach. The abundance of starting materials and cross‐coupling methodologies to access the precursors allows for highly diverse products. Subsequent selective partial reduction can alter the core structure in a manner of interest to medicinal chemists. Herein, we describe the precise, partial reduction of multicyclic heteroaromatic systems using a simple heterogeneous catalyst. The approach can be extended to introduce deuterium (again at late‐stage). Excellent yields can be obtained using simple reaction conditions.

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Efficient N-Alkylation of Secondary Amines to Prepare N-Butyl-1,2-benzisothiazolin-3-one Based on Cs Ion Effect with Cs/LTA Zeolite Catalysts

Li,

Wu,

Jiang

et al. 2024

Ind. Eng. Chem. Res.

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is a safe and environmentally friendly new fungicide with wide application prospects in the field of industrial and medical antibacterial. The synthesis route of BBIT by introducing hydrocarbon groups through the N-alkylation reaction on the nitrogen atom of 1,2-benzisothiazolin-3-one (BIT) has been widely concerned. Herein, a series of Cs/ LTA zeolite catalysts were developed by an equal volume impregnation method with different cesium metal loadings to catalyze N-alkylation reactions of BIT instead of stoichiometric inorganic bases. The physicochemical properties of both prepared Cs/LTA catalysts and LTA zeolite supports were characterized by XRD, FT-IR, XPS, thermogravimetry (TG), N 2 -physisorption, and CO 2 -TPD, and the reaction mechanisms were discussed by DFT calculations. The characterization and DFT results show that the well-dispersed cesium metal on the LTA zeolite is the active site of the BIT reaction. The synergistic interaction of Cs + interacting with zeolite in the rate-control step of BIT and butyl bromide reduces the reaction barrier of C−N bond construction, thus prioritizing the dehydrogenation step of the product intermediate and improving the selectivity of N-alkylation. Compared with traditional inorganic bases, Cs/LTA catalysts have broad industrial application prospects because of their higher catalytic and environmental performance.

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A phosphine free, inorganic base free, one-pot tandem Mizoroki–Heck olefination/direct arylation/hydrogenation sequence, to give multicyclic alkylated heteroarenes

Abstract: One-pot processes which facilitate a number of tandem reactions, represent an environmentally friendly approach to building molecular complexity.

Cited by 6 publications

References 69 publications

Enantioselective Synthesis of Dihydrobenzofurans, Dihydrobenzosulfones, and Dihydroindoles by Merging One‐pot Intramolecular Heck‐Matsuda Reactions from Anilines with Redox‐Relay Process

Enantioselective Synthesis of Dihydrobenzofurans, Dihydrobenzosulfones, and Dihydroindoles by Merging One‐pot Intramolecular Heck‐Matsuda Reactions from Anilines with Redox‐Relay Process

Regioselective Partial Hydrogenation and Deuteration of Tetracyclic (Hetero)aromatic Systems Using a Simple Heterogeneous Catalyst

Efficient N-Alkylation of Secondary Amines to Prepare N-Butyl-1,2-benzisothiazolin-3-one Based on Cs Ion Effect with Cs/LTA Zeolite Catalysts

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