Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Фев. 21, 2024

A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second-generation system, shed light onto observed stereochemical retention inversion pathways when performing late-stage S

Язык: Английский

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Electrifying P(V): Access to Polar and Radical Reactivity

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

Abstract Electrochemical, fully stereoselective P(V)‐radical hydrophosphorylation of olefins and carbonyl compounds using a P(V) reagent is disclosed. By strategically selecting the anode material, radical reactivity accessible for alkene whereas polar pathway operates ketone hydrophosphorylation. The mechanistic intricacies these chemoselective transformations were explored in‐depth.

Язык: Английский

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Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4741 - 4785

Опубликована: Янв. 1, 2024

The review summarizes advances in the radical chemistry of polyfluorinated arenes under photocatalytic conditions. fluoroaryl fragment serves as enabling motif for reaction design and efficient generation reactive intermediates.

Язык: Английский

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Photochemical halogen-bonding assisted carbothiophosphorylation reactions of alkenyl and 1,3-dienyl bromides

Chemical Science, Год журнала: 2023, Номер 14(44), С. 12767 - 12773

Опубликована: Янв. 1, 2023

Herein, we present a synthetic procedure for the facile and general preparation of novel S-alkenyl dienyl phosphoro(di)thioates first time. Extensive mechanistic investigations support that reactions rely on photochemical excitation halogen-bonding complex, formed with phosphorothioate salt an alkenyl or bromide, which light-induced fragmentation leads to formation desired products through radical-based pathway. The substrate scope is broad exhibits wide functional group tolerance in final compounds, including molecules derived from natural products, all unknown potentially interesting biological properties. Eventually, very efficient continuous flow protocol was developed upscale these reactions.

Язык: Английский

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Organocatalytic enantioselective construction of axially chiral phosphorodithiolated styrenes

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111219 - 111219

Опубликована: Апрель 1, 2025

Язык: Английский

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Nickel-Catalyzed Asymmetric Synthesis of Ambiphilic Secondary Phosphine Oxides

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

Опубликована: Апрель 16, 2025

The synthesis of ambiphilic compounds, which possess both strong nucleophilic and electrophilic functional groups, presents a significant challenge due to their propensity self-react, forming oligomers or polymers. We have successfully achieved the nickel-catalyzed asymmetric P-stereogenic alkenyl secondary phosphine oxides from tailored primary oxide by leveraging controversial stability reactivity. This method demonstrates remarkable tolerance toward wide range unactivated alkynes, including those derived natural products medicinally relevant molecules, thus providing universal synthon for phosphines with high enantioselectivity regioselectivity. product exhibits interesting orthogonal reactivities nucleophiles electrophiles can be easily converted variety compounds.

Язык: Английский

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Fe(III)-Triggered Radical Arylation of Arene Moieties from Cyclopropanols to Construct Dibenzocyclohepta/octanones: Synthesis of N-Acetylcolchinol-O-methyl ether

Organic Letters, Год журнала: 2024, Номер 26(33), С. 6950 - 6954

Опубликована: Июль 9, 2024

Tricyclic 6-7-6 and 6-8-6 carbon ring systems are present in numerous biologically active natural molecules. However, simple efficient synthetic approaches to these scaffolds remain challenging. Herein, we report a versatile strategy for constructing via Fe(NO

Язык: Английский

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Strain-Releasing Ring-Opening Diphosphinations for the Synthesis of Diphosphine Ligands with Cyclic Backbones

JACS Au, Год журнала: 2024, Номер 4(10), С. 3777 - 3787

Опубликована: Июль 29, 2024

Diphosphine ligands based on cyclobutane, bicyclo[3.1.1]heptane, and bicyclo[4.1.1]octane were synthesized from the corresponding highly strained, small, cyclic organic molecules, i.e., bicyclo[1.1.0]butane, [3.1.1]propellane, [4.1.1]propellane, employing a ring-opening diphosphination. Under photocatalytic conditions, three-component reaction of diarylphosphine oxide, one aforementioned strained diarylchlorophosphine results in smooth formation diphosphines high yield. The obtained can be expected to find applications functional molecules due their unique structural characteristics, which likely impart specific properties associated metal complexes coordination polymers (e.g., zigzag-type structure). feasibility initial radical addition estimated using density-functional-theory calculations artificial force induced (AFIR) method. This study focuses importance integrating experimental computational methods for design synthesis new diphosphination reactions that involve molecules.

Язык: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at P(V): Improved Generality, Efficiency and Modularity

Опубликована: Дек. 5, 2023

A second generation catalytic two-phase strategy for the enantioselective synthesis of chiral at P(V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched precursors. new catalyst/leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be converted an even greater distinct classes by displacement remaining leaving as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior leads generality in our second-generation system, shed light onto observed retention inversion pathways when performing late-stage SN2@P reactions with Grignard reagents.

Язык: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie, Год журнала: 2024, Номер 136(18)

Опубликована: Фев. 21, 2024

Abstract A broadly improved second generation catalytic two‐phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C ‐, N O ‐ S substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP‐catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second‐generation system, shed light onto observed stereochemical retention inversion pathways when performing late‐stage 2@P reactions with Grignard reagents.

Язык: Английский

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