Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

Sar, Dinabandhu; Yin, Shuai; Grygus, Jacob; Rentería-Gómez, Ángel; Garcia, Melanie; Gutierrez, Osvaldo

doi:10.1039/d3sc04549h

Chem. Sci.

2023

DOI: 10.1039/d3sc04549h

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Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

Dinabandhu Sar,

Shuai Yin,

Jacob Grygus

et al.

Abstract: Enol silyl ethers are versatile, robust, and readily accessible substrates widely used in chemical synthesis. However, conventional reactivity of these motifs has been limited to classical two electron (2-e) enolate-type...

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2024

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Cited by 2 publications

References 66 publications

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Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Guerrero,

Rentería-Gómez,

Das

et al. 2024

Org. Lett.

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In contrast to transition-metal-catalyzed difunctionalization of activated alkenes, selective alkylarylation of vinyl azaarenes is underdeveloped. Consequently, the lack of modular and rapid syntheses of 1,1-bis(hetero)arylalkanes limits their exploration in medicinal chemistry. Herein we report a protocol using commercially available iron salts, bisphosphine ligands, fluoroalkyl halides, and Grignard reagents that enables the selective 1,2-fluoroalkyl(hetero)arylation of vinyl azaarenes. We demonstrate the versatility and robustness of the method through the selective synthesis of a range of unsymmetrical 1,1-bis(hetero)arylalkenes, including pyridine N-oxides, triazoles, pyrazines, carbazoles, indazoles, and 1,2-azaborines. Mechanistic insights from experimental and computational investigations support a radical pathway and provide insights into the role of non-covalent interactions in iron catalysis.

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Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Guerrero,

Rentería-Gómez,

Das

et al. 2024

Org. Lett.

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Stereoselective Fe-Catalyzed Decoupled Cross-Couplings: Chiral Vinyl Oxazolidinones as Effective Radical Lynchpins for Diastereoselective C(sp²)–C(sp³) Bond Formation

Maity,

Rentería-Gómez,

Gutierrez

2024

ACS Catal.

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Modular, catalytic, and stereoselective methods for the dicarbofunctionalization of alkenes can streamline the synthesis of chiral active pharmaceutical ingredients (APIs) and agrochemicals. However, despite the inherent attractive properties of iron as catalysts for practical pharmaceutical synthesis (i.e., less expensive, more abundant, less toxic, and lower carbon footprint in comparison to other transition metals), iron-based catalytic methods that enable highly stereoselective dicarbofunctionalization of alkenes are lacking. Herein, we report the use of readily available chiral vinyl oxazolidinones as effective chiral radical lynchpins to enable practical and diastereoselective (up to 1:78 dr) Fe-catalyzed dicarbofunctionalization with fluoroalkyl halides and hetero(aryl) Grignard reagents. Experimental and computational mechanistic studies are carried out to elucidate the origin of stereoinduction and to build a stereochemical model for the rational reaction design.

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Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

Abstract: Enol silyl ethers are versatile, robust, and readily accessible substrates widely used in chemical synthesis. However, conventional reactivity of these motifs has been limited to classical two electron (2-e) enolate-type...

Cited by 2 publications

References 66 publications

Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Stereoselective Fe-Catalyzed Decoupled Cross-Couplings: Chiral Vinyl Oxazolidinones as Effective Radical Lynchpins for Diastereoselective C(sp²)–C(sp³) Bond Formation

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Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

Abstract: Enol silyl ethers are versatile, robust, and readily accessible substrates widely used in chemical synthesis. However, conventional reactivity of these motifs has been limited to classical two electron (2-e) enolate-type...

Cited by 2 publications

References 66 publications

Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Fe-Catalyzed Fluoroalkyl(hetero)arylation of Vinyl Azaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

Stereoselective Fe-Catalyzed Decoupled Cross-Couplings: Chiral Vinyl Oxazolidinones as Effective Radical Lynchpins for Diastereoselective C(sp2)–C(sp3) Bond Formation

Contact Info

Product

Resources

About

Stereoselective Fe-Catalyzed Decoupled Cross-Couplings: Chiral Vinyl Oxazolidinones as Effective Radical Lynchpins for Diastereoselective C(sp²)–C(sp³) Bond Formation