Rhodium-Catalyzed Dehydrogenative Annulation of N-Arylmethanimines with Vinylene Carbonate for Synthesizing Quinolines

Organic Letters, Journal Year: 2021, Volume and Issue: 23(21), P. 8527 - 8532

Published: Oct. 20, 2021

Here we report a novel Rh-catalyzed C−H/C−H alkenylation of N-arylmethanimines with vinylene carbonate acting as unit. Forty examples C3,C4-nonsubstituted quinolines were achieved from commercially available starting materials. This identified process features an exceedingly simple system, lower loading catalyst, and the capacity for postfunctionalization bioactive molecules.

Language: Английский

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Recent progress in rare-earth metal-catalyzed sp² and sp³ C–H functionalization to construct C–C and C–heteroelement bonds

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(11), P. 3102 - 3141

Published: Jan. 1, 2022

The review presents rare-earth metal-catalyzed C(sp 2 /sp 3 )–H functionalization accessing C–C/C–heteroatom bonds and olefin (co)polymerization, highlighting substrate scope, mechanistic realization, origin of site-, enantio-/diastereo-selectivity.

Language: Английский

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Recent Advances in Rare‐Earth Metal‐Catalyzed C−H Functionalization Reactions

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(23)

Published: Oct. 12, 2022

Abstract There has been a persistent impetus for the development of versatile C−H functionalization reactions, which represents powerful approach to wide variety valuable chemical compounds. Transition metal catalyzed attracted intense interest and witnessed considerable advances in this field owing its outstanding regioselectivity atom‐economy. In recent years, rare‐earth (RE) metal‐based catalysts have successfully employed flourished area, demonstrating unique selectivity complementary reactivity with respect late‐transition metal‐catalyzed functionalization. The by taking advantage these characteristic properties is great importance interest. Herein, panorama during last decade presented.

Language: Английский

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Yttrium‐Catalyzed ortho‐Selective C−H Borylation of Pyridines with Pinacolborane

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(21)

Published: March 9, 2022

This work reports a site-selective C-H borylation of pyridines at the ortho-position with pinacolborane enabled by an yttrocene catalyst. The reaction provides new family 2-pyridyl boronates broad substrate scope and high atom efficiency. resultant were able to undergo variety transformations, e.g., oxidation, Suzuki-Miyaura coupling, Chan-Lam amination etherification. Catalytic intermediates, including ortho-C-H metalated borylated complexes, isolated from stoichiometric experiments confirmed single-crystal X-ray diffraction.

Language: Английский

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Divergent Synthesis of Multi‐Substituted Aminotetralins via [4+2] Annulation of Aldimines with Alkenes by Rare‐Earth‐Catalyzed Benzylic C(sp³)−H Activation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 16, 2024

The search for efficient and selective methods the divergent synthesis of multi-substituted aminotetralins is much interest importance. We report herein first time diastereoselective [4+2] annulation 2-methyl aromatic aldimines with alkenes via benzylic C(sp

Language: Английский

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(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(39), P. 26766 - 26776

Published: Sept. 20, 2024

The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- stereoselectivity challenges, typically yielding

Language: Английский

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Solvent-Switched Manganese(I)-Catalyzed Regiodivergent Distal vs Proximal C–H Alkylation of Imidazopyridine with Maleimide

Organic Letters, Journal Year: 2021, Volume and Issue: 23(19), P. 7370 - 7375

Published: Sept. 20, 2021

A sustainable Mn(I)-catalyzed exclusive solvent-dependent functionalization of imidazopyridine with maleimide via an electrophilic metalation at the distal (in 2,2,2-trifluoroethanol (TFE)) and chelation assisted proximal tetrahydrofuran (THF)) has been developed. The strategy was successfully applied to drug Zolimidine a broad range substrates, thereby reflecting method's versatility.

Language: Английский

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Enantioselective Synthesis of 1-Aminoindanes via [3 + 2] Annulation of Aldimines with Alkenes by Scandium-Catalyzed C–H Activation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17468 - 17477

Published: July 28, 2023

Multisubstituted chiral 1-aminoindanes are important components in many pharmaceuticals and bioactive molecules. Therefore, the development of efficient selective methods for synthesis is great interest importance. In principle, asymmetric [3 + 2] annulation aldimines with alkenes through C–H activation most atom-efficient straightforward route construction 1-aminoindanes, but such a transformation has remained undeveloped to date probably due lack suitable catalysts. Herein, we report first time enantioselective wide range aromatic via ortho-C(sp2)–H by half-sandwich scandium catalysts, which provides multisubstituted 1-aminoindanes. This protocol features 100% atom-efficiency, broad functional group compatibility, high regio-, diastereo-, enantioselectivity (up >19:1 dr 99:1 er). Remarkably, fine-tuning sterics ligand around catalyst metal center, diastereodivergent styrenes been achieved level diastereo- enantioselectivity, offering an method both trans cis diastereomers novel class 1-aminoindane derivatives containing two contiguous stereocenters from same set starting materials. Moreover, aliphatic α-olefins, norbornene, 1,3-dienes also achieved.

Language: Английский

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Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(7), P. 3544 - 3559

Published: Feb. 3, 2024

The direct copolymerization of polar and nonpolar olefins is great interest significance, as it the most atom-economical straightforward strategy for synthesis functional polyolefin materials. Despite considerable efforts, precise control monomer-sequence their regio- stereochemistry full challenges, related mechanistic origins are still in infancy to date. Herein, studies on model reaction Sc-catalyzed co-syndiospecific alternating anisylpropylene (AP) styrene were performed by DFT calculations. results suggest that subtle balance between electronic steric factors plays an important role during monomer insertions, a new amino-dissociated mechanism was proposed AP insertion at chain initiation. follows 2,1-si-insertion pattern, which mainly controlled caused restricted MeO···Sc interaction. As insertion, prefers 2,1-re-insertion manner its stereoselectivities influenced repulsions inserting polymer or ligand. More interestingly, found determined "steric matching" principle, quantitatively expressed buried volume metal center preinserted species. concept pocket has been successfully applied explain different performances several catalysts other reactions. insightful findings quantitative present here expected promote rational design rare-earth developing regio-, stereo-, sequence-controlled specific olefins.

Language: Английский

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Iron-mediated divergent reductive coupling reactions of heteroarenes with alkenes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(9), P. 2318 - 2323

Published: Jan. 1, 2023

Divergent catalytic olefin-based Minisci alkylation and reductive of heteroarenes with alkenes using Fe(dibm) 3 as the catalyst promoter were developed.

Language: Английский

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