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

ACS Catalysis, Год журнала: 2022, Номер 12(22), С. 13876 - 13883

Опубликована: Окт. 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.

Язык: Английский

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Cobalt-catalyzed enantioselective C–H/N–H annulation of aryl sulfonamides with allenes or alkynes: facile access to C–N axially chiral sultams

Chemical Science, Год журнала: 2023, Номер 14(26), С. 7291 - 7303

Опубликована: Янв. 1, 2023

Herein we report a cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes and alkynes, using either chemical or electrochemical oxidation. By O2 as the oxidant, proceeds efficiently low catalyst/ligand loading 5 mol% tolerates wide range allenes, including 2,3-butadienoate, allenylphosphonate, phenylallene, resulting in C-N axially chiral sultams high enantio-, regio-, position selectivities. The alkynes also exhibits excellent enantiocontrol (up to >99% ee) variety functional sulfonamides, internal terminal alkynes. Furthermore, oxidative is achieved simple undivided cell, demonstrating versatility robustness cobalt/Salox system. gram-scale synthesis asymmetric catalysis further highlight practical utility this method.

Язык: Английский

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N,O-Auxiliary Enabled Cobaltaelectro-Catalyzed Atroposelective C–H Annulation

ACS Catalysis, Год журнала: 2023, Номер 14(1), С. 1 - 9

Опубликована: Дек. 7, 2023

Herein, we disclosed an efficient synthesis of C–N axially chiral pyridine-N-oxides through cobalt-catalyzed enantioselective C–H activation and annulation under electro-oxidative conditions. This protocol is accomplished by using a readily available cobalt(II) catalyst salicyloxazoline (Salox) ligand in undivided cell. The combination electrochemical simple Co/Salox system enabled effective control over the chemo- enantioselectivity process. A broad range benzamides alkynes bearing diverse functional groups are well compatible to deliver products with high yields enantioselectivities (up 97% yield 99% ee). scalability, asymmetric application, transformations demonstrated synthetic practicality. Moreover, photoluminescence properties further highlight potential applications this strategy material development performance enhancement.

Язык: Английский

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Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO₂

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 26, 2024

Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.

Язык: Английский

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Enantioselective C–H bond functionalization under Co(iii)-catalysis

Chemical Communications, Год журнала: 2024, Номер 60(25), С. 3354 - 3369

Опубликована: Янв. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Язык: Английский

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