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

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9713 - 9723

Опубликована: Июль 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.

Язык: Английский

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Synthesis of P‐Stereogenic Phosphine Oxides via Nickel‐Catalyzed Asymmetric Cross‐Coupling of Secondary Phosphine Oxides with Alkenyl and Aryl Bromides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 14, 2023

Abstract A general and mild nickel‐catalyzed enantioselective C(sp 2 )−P cross‐coupling for synthesizing P‐stereogenic phosphine oxides has been developed. The asymmetric alkenylation/arylation of racemic secondary with alkenyl/aryl bromides generated high yields enantioselectivities. Various functional groups were tolerated, the applications this method demonstrated through late‐stage functionalization product transformations.

Язык: Английский

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Copper-Catalyzed Dynamic Kinetic Resolution of Secondary Phosphine Oxides

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2178 - 2183

Опубликована: Фев. 10, 2023

Copper-catalyzed dynamic kinetic resolution of secondary phosphine oxides has been successfully developed, providing a general method for the gram-scale enantioselective synthesis P-stereogenic cyclic with high yields and enantioselectivities. The products could be easily reduced to corresponding useful P(III)-stereogenic phosphines. A mechanism involving unusual rapid racemization SPOs proposed.

Язык: Английский

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Palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts to access atropoisomeric phosphines

Chemical Science, Год журнала: 2024, Номер 15(18), С. 6943 - 6948

Опубликована: Янв. 1, 2024

A Pd-catalyzed atroposelective phosphination of cyclic biarylsulfonium salts with HPAr 3 Ar 4 for straightforward synthesis chiral phosphines bearing a stereogenic axis or both and P-stereogenic center is reported.

Язык: Английский

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A Ni-catalyzed asymmetric C(sp)–P cross-coupling reaction for the synthesis of P-stereogenic alkynylphosphines

Chemical Science, Год журнала: 2023, Номер 14(5), С. 1286 - 1290

Опубликована: Янв. 1, 2023

Due to the high reactivity of triple bond, P-stereogenic alkynylphosphines could be easily derivatized, serving as universal building blocks for structurally diverse phosphine compounds. However, synthesis via direct P-C bond formation was unprecedented. Here, we report an efficient method with enantioselectivity a Ni-catalyzed asymmetric cross-coupling reaction. The reaction tolerate variety functional groups, affording products that can converted into useful derivatives.

Язык: Английский

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Asymmetric Synthesis of Chiral‐at‐P Alkenylphosphonamidates through Nickel‐Catalyzed C−P Coupling of Phosphoramidites and Alkenyl Halides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(33)

Опубликована: Июнь 24, 2023

P-stereogenic compounds are widely used as ligands in asymmetric catalysis and present a myriad of bioactive pharmaceuticals. Yet, their stereocontrolled preparation remains challenging. Herein, we report novel strategy towards versatile chiral-at-P alkenylphosphonamidates through one-pot Ni-catalyzed C-P coupling/diastereoselective hydrolysis readily available phosphoramidites alkenyl halides. Remarkably, chemo- diastereodivergent behavior was observed upon subtle changes the reaction conditions. Additionally, selective derivatizations chiral demonstrate versatility building blocks for synthesis structurally diverse compounds.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Synthesis of P‐Stereogenic Phosphanyl Hydrazine Building Blocks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Сен. 29, 2023

Catalytic asymmetric methods for the synthesis of synthetically versatile P-stereogenic building blocks offer an efficient and practical approach diversity-oriented preparation P-chiral phosphorus compounds. Herein, we report first nickel-catalyzed secondary aminophosphine-boranes by addition primary phosphines to azo We further demonstrate that P-H P-N bonds on these phosphanyl hydrazine can be reacted sequentially stereospecifically access various compounds with structural diversity.

Язык: Английский

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Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 5, 2024

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio- enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.

Язык: Английский

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Copper-Catalyzed Dynamic Kinetic Asymmetric Arylation of Secondary Phosphine-Boranes for the Synthesis of P(III)-Stereogenic Centers

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 14, 2025

Transition-metal-catalyzed asymmetric C-P(III) bond formation is a direct method for the construction of P(III)-stereogenic centers; however, achieving high enantioselectivity remains challenge. Herein, an unprecedented Cu-catalyzed dynamic kinetic resolution secondary phosphine-boranes was successfully developed. This C-P(BH3) coupling reaction provided and highly enantioselective synthesis centers, enabling chiral medium-sized benzophosphine-boranes (7-10-membered cycles). A mechanism involving unusual rapid racemization has been proposed.

Язык: Английский

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Stereogenic P(V) Synthesis via Catalytic Continuous Substitutions

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 9, 2025

Phosphorus(V) stereocenters that are fully substituted by heteroatoms play important roles in bioactive molecules and organocatalysts. Existing methods to achieve such motifs rely almost entirely on resolution or diastereocontrol, prefunctionalized substrates usually required generate specific P(V) stereocenters. In contrast, related catalytic rare, no generally applicable method is described. Here, we report a modular strategy access broad variety of stereogenic-at-phosphorus skeletons, including ProTide analogs, alkoxylphosphoramidates, phosphates, phosphorothioates, phosphonamidates, through designed enantioselective continuous substitutions simple precursors. The nucleophilic substitution sequence readily determined the stereoconfiguration products. Concise synthesis analogs drug demonstrated practical value protocol. Experimental computational studies unveiled unique π-π stacking effect chalcogen bonding interaction between catalyst substrate as origin stereoselectivity.

Язык: Английский

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