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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 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

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6009 - 6015

Published: April 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Language: Английский

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Selenium Electrophilic Center Responsive to Biological Electron Donors for Efficient Chemotherapy

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Abstract Designing drugs to intelligently respond different ratio of biological electron donors/receptors in cancer cells and normal is a promising strategy achieve highly effective less toxic chemotherapy. Herein by employing metal center active the selenium‐containing electrophilic drug Ru(phtpy‐NO 2 )(phenSe)Cl ( RuSe ) with strongly polarization characteristics are synthesized which can efficiently shuttle electrons from donors convert oxidative stress. The rate transfer at selenium 1.81 times higher cell environments compared environments. This results being 14.98 more lethal than cells. Experimental demonstrate that transport process carried out via radicals intermediate positively correlated properties atoms. transports bioactive generate large number superoxide anions leading DNA damage decrease mitochondrial membrane potential further activates p53 signaling pathway amplifies cell‐killing effect after transporting electrons. work provides new avenue for design efficient chemotherapeutic agents.

Language: Английский

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

Language: Английский

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Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(4), P. 1846 - 1875

Published: Jan. 1, 2024

Organocatalytic enantioselective cross-dehydrogenative coupling reaction provides a great opportunity for the synthesis of highly enantioenriched molecules. In this review, recent progress in field is summarized.

Language: Английский

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Thiourea-Assisted Chiral Bicyclic Imidazole Organocatalysts: Design, Synthesis, and Application in Asymmetric Acylative Desymmetrization of Bisphenols for the Construction of P-Stereocenters

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16300 - 16306

Published: Dec. 6, 2023

Thiourea-assisted chiral bicyclic imidazole organocatalysts were designed, synthesized, and successfully applied in the asymmetric acylative desymmetrization of P-prochiral bisphenols. Under mild conditions, P-stereogenic products obtained high yields (up to 99% yield) with enantioselectivities ee). Most importantly, reaction could also achieve satisfactory results under 1 mol % catalyst loadings. Mechanistic studies showed that synergistic effect including covalent activation acyl group by nucleophilic noncovalent H-bonding π-interaction between substrate was crucial for efficient construction P-stereocenters.

Language: Английский

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Palladium-Catalyzed Asymmetric Desymmetrization for the Simultaneous Construction of Chiral Phosphorus and Quaternary Carbon Stereocenters

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5934 - 5939

Published: July 5, 2024

A palladium-catalyzed asymmetric tandem Heck and carbonylation of bisallyl-phosphine oxides has been developed. This desymmetrization process provided an efficient route to the simultaneous synthesis a chiral P-stereogenic center quaternary carbon stereocenter in good yields with diastereo- enantioselectivities.

Language: Английский

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Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14762 - 14768

Published: Sept. 20, 2024

Language: Английский

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Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 9, 2024

In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)-stereogenic molecules by utilizing the catalytic atroposelective Catellani-type C-H arylation/desymmetric intramolecular N-arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent-dictated inversion compounds.

Language: Английский

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Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13055 - 13064

Published: Aug. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Language: Английский

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