Selective C(sp²)–P Cross-Coupling of Alkenylsulfonium Salts with P(O)H Compounds: Divergent Synthesis of Alkenylphosphorus Compounds

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Herein, we report a both regioselective and stereoselective method for the formation of C(sp2)–P bonds using alkenylsulfonium salts >P(O)–H compounds. By employing palladium catalyst or K2CO3, variety (E)-alkenylphosphorus compounds terminal alkenylphosphorus were successfully synthesized with high selectivity. Notably, trisubstituted (Z)-alkenylphosphorus first time under metal-free conditions. This protocol has wide substrate scope good functional group compatibility, providing direct highly selective approach preparation various

Язык: Английский

---

Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(15), С. 3354 - 3360

Опубликована: Июнь 7, 2024

Abstract An approach for the preparation and stabilization of primary phosphine oxides is presented complementing previous methods in situ generation. Specifically, RP(O)H 2 where R=benzyl (Bn), cyclohexyl (Cy), 2‐naphthyl (2‐Naph), phenyl (Ph), tert ‐butyl ( t ‐Bu) was prepared by controlled oxidation corresponding presence ferrocene as stabilizing reagent. The were characterized using NMR MS studied twofold hydrophosphorylation diketones. domino‐phospha‐aldol reaction catalysed with 5 mol% sodium methoxide yielded five‐, six‐ seven‐membered heterocyclic tertiary a high degree stereoselectivity, confirmed single X‐ray diffraction.

Язык: Английский

---

Metal‐Free Formation of Xanthenes and Xanthones from 2‐aryloxybenzaldehydes via Intramolecular Cyclization

ChemistrySelect, Год журнала: 2025, Номер 10(14)

Опубликована: Апрель 1, 2025

Abstract We herein report a metal‐free strategy for the selective synthesis of xanthenes and xanthones from 2‐aryloxybenzaldehydes. By employing phosphorous acid/iodine system, we achieved efficient preparation diverse via intramolecular reductive cyclization. In contrast, series were constructed same substrates through TBAI‐catalyzed direct This methodology offers notable advantages, including straightforward workup, absence metal involvement, low‐cost. A plausible reaction mechanism was also proposed.

Язык: Английский

---

Trivalent Phospha-Brook rearrangement enabled practical deoxygenative phosphonylation of carbonyls

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 16, 2025

Brønsted base-mediated [1,2]-phospha-Brook rearrangements have garnered considerable attention for developing new methodologies and efficiently constructing complex molecular structures. However, the strict reliance on pentavalent phosphonates imposes strong limitations reaction types, mechanistic constraint also excludes involvement of trivalent phosphine in same pathway. In this study, we employ Lewis acid rather than base to shift charge transfer from previous O-P-C direction a P-C-O process. This orthogonal approach can undergo unprecedented C-O bond cleavage instead traditional C-P splitting enables deoxygenative phosphorylation carbonyl compounds under metal-free conditions rapid access various tertiary oxides. The demonstrates excellent substrate scope, remarkable functional group compatibility, operational simplicity, offering significantly enhanced atom-economy compared strategies. Additionally, detailed studies reveal an unusual oxygen atom crossover clearly elucidate mechanism acid-mediated phospha-Brook rearrangement. These insights further deepen understanding phosphorus chemistry pave way design related reactions.

Язык: Английский

---

Lewis Acid-Mediated Deoxygenative Synthesis of Trivalent Sterically Hindered Phosphines from Aldehydes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 29, 2025

The efficient synthesis of trisubstituted trivalent phosphines remains challenging. Herein, we report a novel approach for rapid construction these compounds from aldehydes under Lewis acid-mediated conditions. By using sterically hindered disubstituted phosphines, can undergo deoxygenative reaction to afford phosphorus compounds. This modular and practical method is characterized by operational simplicity, broad substrate scope, excellent functional group tolerance, which holds great potential applications in organic synthesis.

Язык: Английский

---

Advances in Organic Reactions Using Phosphorus Acid as Reducing Agent

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(12), С. 3702 - 3702

Опубликована: Янв. 1, 2024

Язык: Английский

---