Copper-decorated covalent organic framework as a heterogeneous photocatalyst for phosphorylation of terminal alkynes

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(10), P. 4071 - 4081

Published: Jan. 1, 2022

A copper decorated covalent organic framework has been prepared and identified as an efficient heterogeneous photocatalyst for the phosphorylation of terminal alkynes.

Language: Английский

---

Photocatalytic Hydrogen Atom Transfer-Induced Arbuzov-Type α-C(sp³)–H Phosphonylation of Aliphatic Amines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16105 - 16113

Published: Dec. 5, 2023

Despite remarkable progress in photocatalytic hydrogen atom transfer (HAT)-induced C(sp3)–H functionalization, achieving to C(sp3)–P transformation by the HAT process remains highly challenging due P-reagents' compatibility issues. α-Aminophosphonic acids have shown great potential medicinal chemistry, yet their synthesis is hindered limited substrate scopes, poor functional group tolerance, and reliance on prefunctionalized substrates, restricting broad applications. Herein, we report HAT-induced α-C(sp3)–H phosphonylation of aliphatic amines, providing rapid access structurally diverse α-aminophosphonates from abundant amines. Leveraging intramolecular HAT, radical polar crossover, an Arbuzov-type cascade, challenges associated with were overcome. This protocol features base-free, redox-neutral, mild conditions employing amines as limiting reagents, allows for late-stage complex drug molecules possessing amine moieties.

Language: Английский

---

Photoinduced Remote C(sp³)−H Phosphonylation of Amides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 4, 2024

The present study reports an unprecedented protocol for the phosphonylation of unactivated C(sp

Language: Английский

---

Synthesis of Chromone‐3‐phosphonates via Arbuzov‐Type C−P Cross Coupling from o‐Hydroxyphenyl Enaminones and Phosphites

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3670 - 3675

Published: July 2, 2024

Abstract With an in situ C−H iodination tactic, a method for the synthesis of chromone‐3‐phosphonates was developed with trialkyl/triaryl phosphites as reaction partners o ‐hydroxyphenyl enaminones by palladium catalysis. The product formation consists cascade iodination, chromone annulation, and Arbuzov‐type C−P cross coupling major transformations. In addition to providing enaminone‐based synthetic chromone‐3‐phosphonates, work shows advantage step economy skipping separate operation preparing iodo‐functionalized intermediate.

Language: Английский

---

Visible-Light-Promoted Phosphorylation/Cyclization of 1-Acryloyl-2-cyanoindoles in Green Solvent

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 14433 - 14442

Published: Oct. 18, 2022

A visible-light-induced persulfate-promoted cascade phosphorylation/cyclization reaction to access various phosphorylated pyrrolo[1,2-a]indolediones under mild conditions was developed. Notably, the transformation carried out with diethyl carbonate/H2O as a green medium at room temperature. More impressively, traditional metal catalysts and photocatalysts could be effectively avoided. The reactions are simple operate, easy scale up, have good functional group tolerance.

Language: Английский

---

TEMPO/PhI(OAc)₂ promotes the α-aminophosphinoylation of alcohols with amines and H-phosphine oxides in aqueous medium

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(19), P. 3860 - 3865

Published: Jan. 1, 2024

The aminophosphinoylation of alcohols with amines and H-phosphine oxides provides an efficient mild approach to access various α-aminoalkylphosphine in good yields tolerance functional groups using H 2 O as a clean solvent.

Language: Английский

---

Tuning the Photocatalytic Performance of Ruthenium(II) Polypyridine Complexes Via Ligand Modification for Visible‐Light‐Induced Phosphorylation of Tertiary Aliphatic Amines

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(1)

Published: Oct. 17, 2022

Tuning the redox potential of commonly available photocatalyst to improve catalytic performance or expand its scope for challenging synthetic conversions is an ongoing demand in chemistry. Herein, excited state properties and commercially [Ru(bpy)3 ]2+ were tuned by modifying structure bipyridine ligands with electron-donating/withdrawing units. The visible-light-mediated photoredox phosphorylation tertiary aliphatic amines was demonstrated under mild conditions. A series cross-dehydrogenative coupling reactions performed employing RuII complexes as giving corresponding α-aminophosphinoxides α-aminophosphonates via carbon-phosphorus (C-P) bond formation.

Language: Английский

---

Photocatalytic Oxidative C(sp³)-H/N–H Cross-Dehydrogenative Coupling of Tertiary Anilines with Amides/Imides: Synthesis of N-Mannich Bases

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

A photocatalytic method for the synthesis of N-Mannich bases has been developed through C(sp3)-H/N-H cross-dehydrogenative coupling N,N-dimethylanilines with amides/imides. This process utilizes 2,4,6-triphenylpyrylium tetrafluoroborate (TPT) as photocatalyst and is conducted at ambient temperature atmospheric air. Various aromatic, heteroaromatic aliphatic (cyclic) amides, well imides were successfully employed, yielding moderate to good results. Preliminary mechanistic isotope-labeling studies indicate that reaction likely proceeds via a single electron transfer pathway involves an α-aminoalkyl radical intermediate.

Language: Английский

---

Light-Induced Decarboxylative Phosphinylation

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

A visible light-induced decarboxylative radical coupling between N-hydroxyphthalimide esters and phosphonites or phosphinites has been developed. The corresponding phosphinates phosphine oxides could be obtained under mild conditions. No transition metals toxic reagents were involved. This method provides a low-cost practical alternative for synthesizing functionalized oxides.

Language: Английский

---

Phospha-Mannich reactions of phosphinous acids R ₂ P–OH and their derivatives

Phosphorus, sulfur, and silicon and the related elements, Journal Year: 2023, Volume and Issue: 198(11), P. 867 - 923

Published: July 20, 2023

Secondary phosphine oxides R2P(O)H are a relatively stable tautomeric form of secondary phosphinous acids R2P–OH that with imine/iminium species, or their donors, compounds P(O)–Csp3–N linkage (the phospha-Mannich reaction). These can be referred to as (α-aminoalkyl)phosphine oxides, (α-phosphinoylalkyl)amines, P(O),N-acetals. Compared P–Csp3–N linkages P,N-acetals, products reactions involving phosphines R2PH, the is significantly more allows for many examples α-functionalized P(O),N-acetals and α-phosphinoylated N-heterocycles, whereas such P,N-acetals rare. Trivalent derivatives halides R2P–Hal, esters R2P–OR' (phosphinites), amides R2P–NR'2 (aminophosphines), phosphides R2P–PR'2 (biphosphines) also participate in Mannich-type mechanisms depending on reactants. The react (α-alkoxyalkyl)amines (N,O-acetals) (α-haloalkyl)amines (N,Hal-acetals), respectively, via Arbuzov-type intermediates rearranged into alkyl (Arbuzov rearrangement). Furthermore, unlike phosphines, less sensitive oxidation, imines/iminium species generated not only under conventional Mannich conditions, i.e., from N,E-acetals (E = OH, O, N, halogen, etc.), but also, example, by oxidation α-C-atom amines, alcohols aldehydes than amines.

Language: Английский

---