Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: May 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Language: Английский

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Synthesis of Sulfur-Stereogenic Sulfoximines via Co(III)/Chiral Carboxylic Acid-Catalyzed Enantioselective C–H Amidation

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9806 - 9811

Published: July 27, 2022

Sulfoximines bearing stereogenic sulfur atoms are ubiquitous motifs in pharmaceuticals, agricultural chemicals, and bioactive compounds. Herein, we report the synthesis of sulfur-stereogenic sulfoximines via Co(III)/chiral carboxylic acid-catalyzed enantioselective C–H amidation. A broad range cyclic acyclic were isolated good yields enantioselectivities (up to an 86% yield 1.5:98.5 er). The amidation products can be reduced potential N,S-chiral sulfoxide ligands, which could further transformed into recyclable chiral auxiliaries Pd-catalyzed diastereoselective C(sp3)–H activation aliphatic acids.

Language: Английский

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Ir(III)-Catalyzed Asymmetric C–H Activation/Annulation of Sulfoximines Assisted by the Hydrogen-Bonding Interaction

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9083 - 9091

Published: July 14, 2022

Transition-metal-catalyzed asymmetric C–H activation reactions generally rely on the design of ligands with sterically bulky groups to create a chiral environment for enantioinduction through steric repulsion. Here we describe an Ir(III)-catalyzed enabled by noncovalent interactions. A broad range sulfur-stereogenic sulfoximines was prepared in high yields excellent enantioselectivities via activation/annulation diazo compounds. Desymmetrization, kinetic resolution, and parallel resolution are compatible this protocol. Detailed DFT calculations suggested that N–H···O hydrogen bonding interaction between sulfoximine carboxylic acid ligand crucial enantiocontrol. Moreover, iridacycle intermediates were isolated, characterized, subjected stoichiometric reactions. Computational experimental studies cleavage step rate- enantio-determining step.

Language: Английский

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Ru(II)/Chiral Carboxylic Acid-Catalyzed Asymmetric [4 + 3] Annulation of Sulfoximines with α,β-Unsaturated Ketones

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 13876 - 13883

Published: Oct. 27, 2022

Sulfur-stereogenic containing benzo-fused heterocycles have gained much attention in drug discovery. However, the asymmetric synthesis of these chiral molecules with structural diversity is very challenging. Herein, we report benzothiadiazine-1-oxides a seven-membered ring via achiral Ru(II)-catalyzed [4 + 3] annulation sulfoximines α,β-unsaturated ketones assisted by carboxylic acid (CCA). A broad range benzothiadiazepine-1-oxides bearing various functional groups could be prepared up to 90% yield >99% ee, expanding chemical space sulfoximines. Notably, oxidative cleavage double bonds products gave N-benzoyl C–S axis.

Language: Английский

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Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9713 - 9723

Published: July 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Language: Английский

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Synthesis of S(IV)‐Stereogenic Chiral Thio‐Oxazolidinones via Palladium‐Catalyzed Asymmetric [3+2] Annulations

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

Published: Jan. 29, 2024

Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, drugs, materials. Compared with acyclic ones, the catalytic synthesis of thio-heterocycles has largely lagged behind due to lack efficient synthetic strategies. Here we establish first modular platform access thio-oxazolidinones via Pd-catalyzed [3+2] annulations vinylethylene carbonates sulfinylanilines. This protocol is featured by readily available starting materials, high enantio- diastereoselectivity. In particular, an unusual effect non-chiral supporting ligand diastereoselectivity was observed. Possible reaction mechanisms stereocontrol models were proposed.

Language: Английский

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Construction of boron-stereogenic compounds via enantioselective Cu-catalyzed desymmetric B–H bond insertion reaction

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 12, 2022

Abstract Compared with the well-developed carbon-stereogenic chemistry, construction of boron-stereogenic compounds remains undeveloped and challenging. Herein, previously elusive catalytic enantioselective has been achieved through desymmetric B–H bond insertion reaction. The reaction 2-arylpyridine-boranes versatile diazo under chiral copper catalyst can afford good to excellent enantioselectivity. Moreover, synthetic utility this is demonstrated by scalability downstream transformations. DFT calculations provide insights into mechanism origin stereoselectivity.

Language: Английский

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Enantioselective Synthesis of 1,2‐Benzothiazine 1‐Imines via Ru^II/Chiral Carboxylic Acid‐Catalyzed C−H Alkylation/Cyclization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 17, 2023

Sulfondiimines are diaza-analogues of sulfones with a chiral sulfur center. Compared to and sulfoximines, their synthesis transformations have so far been studied lesser extent. Here, we report the enantioselective 1,2-benzothiazine 1-imines, i.e., cyclic sulfondiimine derivatives from sulfondiimines sulfoxonium ylides via C-H alkylation/cyclization reactions. The combination [Ru(p-cymene)Cl2 ]2 newly developed spiro carboxylic acid is key achieving high enantioselectivity.

Language: Английский

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Rh(III)-Catalyzed Atroposelective C–H Iodination of 1-Aryl Isoquinolines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(8), P. 5127 - 5134

Published: March 30, 2023

The rhodium-catalyzed enantioselective C–H iodination of 1-aryl isoquinolines under mild conditions is disclosed. Direct with N-iodosuccinimide (NIS) catalyzed by chiral CpRh(III) complexes afforded a series axially biaryl iodides in excellent yields and enantioselectivity (up to 99% yield 97% ee). Furthermore, the atroposelective bromination chlorination reactions were also compatible. Notably, could be easily transformed QUINAP-type N,N-type ligands.

Language: Английский

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Access to S-Stereogenic Free Sulfoximines via Bifunctional Phosphonium Salt-Catalyzed Desymmetrization of Bisphenols

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 13902 - 13912

Published: Nov. 1, 2021

Sulfur-stereogenic sulfoximines particularly with a free N-H unit exhibit intriguing chemical and biological activities, thus have received continuous attention from chemists. However, there are currently no examples of guiding catalytic asymmetric strategies available to directly access these molecules. Herein, we disclose an efficient practical protocol for the direct enantioenrichment sulfoximines, via bifunctional phosphonium salt-catalyzed desymmetrization triggered by Atherton–Todd reaction together further extended nucleophilic acyl substitution-type reaction. A series bearing assortment aromatic groups (70 examples) tolerated in this incidentally involving minority kinetic resolution (KR). The desymmetrized products can be easily transformed into chiral sulfoxides other classes active sulfur-stereogenic compounds. Mechanistic studies provided insights pathway suggesting desymmetrization/KR synergic process, also offered support on hydrogen-bonding interactions as key elements successful stereocontrol.

Language: Английский

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