Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17398 - 17404

Опубликована: Ноя. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Язык: Английский

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H₈‐BINOL‐Derived Chiral η⁶‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Апрель 29, 2024

Abstract Given the tremendous success of (p‐cymene)Ru II ‐catalyzed C−H activation over past 20 years, community has long been aware that development chiral η 6 ‐benzene (Ben) ligands should be a potent strategy for achieving attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric activation. However, it rarely achieved due to severe difficulty in developing proper Ben ligands. In particular, designing by connecting benzene fragment framework including rings remained an unsolved challenge until this effort. Here we present novel class axially derived from readily available ( S )‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐bi‐2‐naphthol (( )‐H 8 ‐BINOL) 4–8 steps. Notably, when coordinated with ruthenium, such ligand containing three only forms one possible isomeric BenRu complexes. The related catalysts could effectively catalyze N‐sulfonyl ketimines alkynes, affording range spirocyclic sultams up 99 % yield >99 ee. These are expected find broad applications future.

Язык: Английский

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Planar chiral arene ruthenium complexes derived from R-carvone

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Natural R -carvone was converted into ruthenium complexes with planar-chiral arene ligands. Similar to the classical [(cymene)RuCl 2 ] complex, they catalyse C–H activation reactions, albeit low stereoselectivity.

Язык: Английский

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H₈‐BINOL‐Derived Chiral η⁶‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation

Angewandte Chemie, Год журнала: 2024, Номер 136(31)

Опубликована: Апрель 29, 2024

Abstract Given the tremendous success of (p‐cymene)Ru II ‐catalyzed C−H activation over past 20 years, community has long been aware that development chiral η 6 ‐benzene (Ben) ligands should be a potent strategy for achieving attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric activation. However, it rarely achieved due to severe difficulty in developing proper Ben ligands. In particular, designing by connecting benzene fragment framework including rings remained an unsolved challenge until this effort. Here we present novel class axially derived from readily available ( S )‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐bi‐2‐naphthol (( )‐H 8 ‐BINOL) 4–8 steps. Notably, when coordinated with ruthenium, such ligand containing three only forms one possible isomeric BenRu complexes. The related catalysts could effectively catalyze N‐sulfonyl ketimines alkynes, affording range spirocyclic sultams up 99 % yield >99 ee. These are expected find broad applications future.

Язык: Английский

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Sulfoximine Aided Ru(II)-Catalyzed Asymmetric Double C(sp²)–H Hydroarylations of Olefins

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Presented here is a sulfoximine-directed Ru(II)-catalyzed asymmetric intramolecular double C(sp

Язык: Английский

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