Stereoselective Synthesis of Biology-Oriented Pentacyclic Pyrrolo[2,1-a]isoquinoline Scaffolds by Photoredox-Induced Radical Annulations

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

We report a visible-light photoredox-induced stereoselective radical 1,3-dipolar cycloaddition between tetrahydroisoquinolines and coumarin derivatives, providing platform for the efficient synthesis of pseudo-natural-inspired fused pentacyclic scaffolds. Using this protocol, diverse range valuable pyrrolo[2,1-a]isoquinolines were efficiently obtained in moderate to good yields excellent diastereoselectivities. Mechanistic investigations including control experiments light on/off studies indicated that reaction underwent induced process. The insights gained from our are expected advance general efforts toward green biology-oriented pseudo-natural products heterocyclic skeletons.

Language: Английский

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Organocatalytic Asymmetric Synthesis of Pyran Derivatives with Adjacent F- and CF₃-Tetrasubstituted Centers

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Molecules containing fluorine atoms and trifluoromethyl groups are highly significant in medicinal chemistry. However, synthesizing compounds with adjacent F- CF3-substituted tetrasubstituted centers remains a formidable challenge. Herein, we report an organocatalytic asymmetric approach for pyran heterocycles bearing quaternary carbon stereocenters excellent diastereo- enantioselectivity (>20:1 dr, >99% ee). The process involves dehydration to generate fluorinated enolates, followed by trifluoroacetylation cyclization enones. This method is also applicable the functionalization of bioactive molecules drug derivatives, offering versatile platform constructing architectures.

Language: Английский

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Atherton–Todd Reaction-Guided Enantioselective Synthesis of Axially Chiral Olefins via Bifunctional Phosphonium Salt-Regulating Ketone-Enol Tautomerism

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 13077 - 13088

Published: Sept. 22, 2023

Atropisomerically enriched olefin scaffolds are of great importance in many fields chemistry. Although several synthetic routes to these axial molecules have been reported, alternative, powerful catalytic strategies still highly demanded this area. Here, we present an unprecedented organocatalytic method toward the atroposelective assembly axially chiral olefins with phosphorus unit via bifunctional phosphonium salt-catalyzed Atherton–Todd reaction ketones. This protocol provides a concise and efficient avenue allow access atropisomeric excellent stereoselectivities (up 99:1 e.r.). Moreover, experimental studies density functional theory (DFT) calculations revealed that coupling proceeded through dynamic kinetic resolution (DKR) process by phosphonium-controlled ketone-enol tautomerism also provided insights into origins formation axis. strategy offering convenient pragmatic route enantioenriched has never disclosed, providing platform for exploring potential applications olefin-containing molecules.

Language: Английский

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Novel Stereo‐Induction Pattern in Pudovik Addition/Phospha‐Brook Rearrangement Towards Chiral Trisubstituted Allenes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(22)

Published: March 23, 2024

Abstract Despite the significance of chiral allene skeletons in catalysis, organic synthesis and medicinal chemistry et al., there is a scarcity reports on axially allenyl phosphorus compounds. Here, we disclosed an efficient straightforward cascade reaction between ethynyl ketones phosphine oxides, resulting broad array trisubstituted allenes incorporating moiety high yields with excellent stereoselectivities facilitated by peptide‐mimic phosphonium salt (PPS) Additionally, comprehensive series mechanistic experiments have been conducted to elucidate that this proceeds via asymmetric Pudovik addition followed subsequent phospha ‐Brook rearrangement occurs concomitantly kinetic resolution, representing stereospecific protonation process facilitating central‐to‐axial chirality transfer manner. We anticipate our research will pave way for promising exploration novel stereo‐induction pattern addition/ reaction.

Language: Английский

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Organocatalytic Enantioselective Arylation to Access Densely Aryl-Substituted P-Stereogenic Centers

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Although methods for synthesizing chiral phosphorus scaffolds are available, the potential of this molecular chirality remains largely unexplored. Herein, we present a remote desymmetrization prochiral biaryl phosphine oxides through an organocatalytic asymmetric arylation. This metal-free approach enables efficient synthesis wide range densely functionalized P(V)-stereogenic compounds with good to excellent yields and satisfactory enantioselectivities. Mechanistic studies reveal that hydrogen bonding ion-pairing interactions crucial achieving precise stereocontrol in transformation.

Language: Английский

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Synergistic Catalysis between a Dipeptide Phosphonium Salt and a Metal‐Based Lewis Acid for Asymmetric Synthesis of N‐Bridged [3.2.1] Ring Systems

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(38)

Published: June 29, 2022

Abstract We present an unprecedented synergic catalytic route for the asymmetric construction of fluorinated N ‐bridged [3.2.1] cyclic members tropane family via a bifunctional phosphonium salt/silver co‐catalyzed cyclization process. A broad variety substrates bearing assortment functional groups are compatible with this method, providing targeted compounds seven‐membered ring and four contiguous stereocenters in high yields excellent stereoselectivities. The gram‐scale preparations, facile elaborations preliminary biological activities products demonstrate application potential. Moreover, both experimental computational mechanistic studies revealed that proceeded “sandwich” reaction model multiple weak‐bond cooperative activations. Insights gained from our expected to advance general efforts towards synthesis challenging chiral heterocyclic molecules.

Language: Английский

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Water-controlled skeletal editing or peripheral modification of ortho-chalcone-substituted organophosphines

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Skeletal editing of organophosphines is highly challenging owing to the high P-C bond dissociation energy. Herein, we report an efficient catalyst- and additive-free skeletal strategy transform easily accessible ortho-chalcone based into new complex phosphine oxides, that are unattainable by conventional methods. Water indispensable this transformation serves as oxygen source cleave bonds. Interestingly, it possible achieve peripheral modification phosphonium salts in absence water. This water-controlled or embedded with merits bond- ring-forming efficiency complete regio-, chemo- stereoselectivity.

Language: Английский

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Synergistically Activating Nucleophile Strategy Enabled Organocatalytic Asymmetric P-Addition of Cyclic Imines

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 12017 - 12025

Published: Jan. 1, 2024

An attractive organocatalytic asymmetric addition of P-nucleophiles with cyclic N -sulfonyl imines by phosphonium salt catalysis has been disclosed, offering a facile way to phosphorus-containing benzosultams in high yields and stereoselectivities.

Language: Английский

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Photoinduced Radical Annulations of Tetrahydroisoquinoline Derivatives with 2-Benzothiazolimines: Highly Diastereoselective Synthesis of Fused Hexahydroimidazo[2,1-a]isoquinolines

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13491 - 13500

Published: Sept. 6, 2024

We report herein a photoinduced radical 1,3-dipolar cycloaddition between the 2-benzothiazolimines and tetrahydroisoquinoline derivatives with an organo-photocatalyst. A variety of benzothiazole-based hexahydroimidazo[2,1-

Language: Английский

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Enantioselective Synthesis of Atropisomeric Biaryl Phosphorus Compounds by Chiral‐Phosphonium‐Salt‐Enabled Cascade Arene Formation

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(30)

Published: May 12, 2022

Abstract Axially chiral biaryl monophosphorus molecules, exemplified by atropisomeric 1,1′‐biaryl aminophosphines, are significant motifs in numerous ligands/catalysts. Developing efficient methods for preparing phosphorus compounds with these privileged is an important endeavor synthetic chemistry. Herein, we develop effective, modular method a chiral‐phosphonium‐salt‐catalyzed novel cascade between phosphorus‐containing nitroolefins and α,α‐dicyanoolefins, leading to great diversity of biaryls bearing groups high yields excellent stereoselectivities. The reaction features include Thorpe‐type cycloaddition/oxidative hydroxylation/aromatization pathway central‐to‐axial chirality transfer process. Insight gained from our studies expected advance general efforts towards the catalytic synthesis compounds, offering platform developing new ligands catalysts.

Language: Английский

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