Trivalent Phospha-Brook rearrangement enabled practical deoxygenative phosphonylation of carbonyls

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 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.

Language: Английский

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Chiral Lewis Acid-Catalyzed Asymmetric Multicomponent Michael Reaction through [1,2]-Phospha-Brook Rearrangement

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6262 - 6266

Published: Aug. 21, 2023

The multicomponent catalytic asymmetric Pudovik addition/[1,2]-phospha-Brook rearrangement/Michael reaction sequence of isatins, phosphites, and 4-oxobutenoates was realized. A series oxindole derivatives containing two contiguous stereocenters obtained in high yields excellent stereoselectivities (up to >99% yield, >95:5 dr, ee) using a chiral Lewis acid catalyst. possible model is presented illustrate the stereocontrol.

Language: Английский

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Sequential In Situ-Formed Kukhtin–Ramirez Adduct and P(NMe₂)₃-Catalyzed O-Phosphination of α-Dicarbonyls with P(O)–H

Organic Letters, Journal Year: 2023, Volume and Issue: 25(42), P. 7595 - 7600

Published: Oct. 13, 2023

O-Phosphination of α-dicarbonyls via sequential in situ formation a Kukhtin-Ramirez adduct and P(NMe2)3-catalyzed process has been exploited for the synthesis α-phosphoryloxy carbonyls. A range P(O)-H derivatives, including diarylphosphine oxides, arylphosphinates, phosphinates, are competent candidates to be introduced into this transformation, various carbonyls obtained. This approach possesses advantages mild conditions, simple operations, atom economy, high efficiency, gram-scale synthesis, which make it promising toolbox.

Language: Английский

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Deciphering Asymmetric Brønsted Base-Aminocatalytic Mode in Pudovik/[1,2]-Phospha-Brook Rearrangement/Michael Cascade Reaction

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(19), P. 14177 - 14182

Published: Sept. 18, 2024

An approach involving the use of a bifunctional aminocatalyst containing Brønsted base and iminium activation sites for asymmetric multicomponent reactions [1,2]-phospha-Brook rearrangement has yet to be realized. Herein, we present an aminocatalytic enantioselective conjugate addition α-phosphonyloxy enolates formed

Language: Английский

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Catalytic Generation and Intermolecular Addition of Diarylmethyl Anions Utilizing [1,2]‐Phospha‐Brook Rearrangement Under Brønsted Base Catalysis

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1857 - 1862

Published: Feb. 21, 2024

Abstract An intermolecular addition reaction involving an unconventional combination of a diarylmethyl anion and electrophile, which is mediated by the [1,2]‐phospha‐Brook rearrangement under Brønsted base catalysis, was developed. Diarylmethyl anions having benzofuran moiety were generated through with aid catalytic amount phosphazene P2‐ t Bu. The resulting carbanion intermediates trapped various electrophiles, such as α,β‐unsaturated ketones, aryl aldehydes, α‐ketoesters, N ‐Boc imines, providing corresponding diarylalkane derivatives in good yields.

Language: Английский

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Organophosphates as Versatile Substrates in Organic Synthesis

Molecules, Journal Year: 2024, Volume and Issue: 29(7), P. 1593 - 1593

Published: April 2, 2024

This review summarizes the applications of organophosphates in organic synthesis. After a brief introduction, it discusses cross-coupling reactions, including both transition-metal-catalyzed and transition-metal-free substitution reactions. Subsequently, oxidation reduction reactions are described. In addition, this highlights synthesis natural compounds, demonstrating their versatility importance modern synthetic chemistry.

Language: Английский

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Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H2O)

Molecules, Journal Year: 2025, Volume and Issue: 30(6), P. 1367 - 1367

Published: March 18, 2025

It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in superbase suspension KOH/DMSO(H2O) at 85 °C 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates were earlier inaccessible a yield up 45%. The ESR data demonstrate unlike previously published phosphorylation elemental phosphorus, this new reaction proceeds via single electron transfer from polyphospide anions diaryl(hetaryl)ketones. This is example C-O-P bond generation during strongly basic media, which usually provides C-P formation.

Language: Английский

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Recent Developments in the [1,2]-Phospha-Brook Rearrangement Reaction

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(7), P. 3065 - 3065

Published: March 27, 2025

The [1,2]-phospha-Brook rearrangement serves as a powerful synthetic strategy that enables efficient carbonyl umpolung through phosphoryl group migration, providing direct access to α-hydroxyphosphoryl compounds-a privileged class of synthons with broad applications in organophosphorus chemistry, medicinal and materials science. This review provides comprehensive overview recent progress methodologies, possible mechanisms, asymmetric transformations, highlighting key breakthroughs future directions this rapidly evolving field.

Language: Английский

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Stereoselective [1,2]-Phospha-Brook Rearrangement of CAMDOL-Derived H-Phosphonate: Synthesis of α-Trifluoromethyl Alcohols

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

Published: May 1, 2025

A highly efficient and stereoselective [1,2]-phospha-Brook rearrangement of fluoromethyl ketones has been achieved by utilizing a new type P-chiral H-phosphonate derived from CAMDOL, designated as CAMDOL-PHO. library 38 secondary alcohols featuring an α-trifluoromethyl or trifluoroaryl motif were afforded in up to 97% yield with 99:1 dr. Compared other known chiral auxiliaries, bicyclic CAMDOL exhibits superior induction ability due its unique center-chiral scaffold.

Language: Английский

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Reductive Deuteration of Aldehydes/Ketones for the Synthesis of Monodeuterated Phosphinates and Derivatives Using D₂O as the Nucleophilic Deuterium Source

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

Published: May 14, 2025

The ideal deuteration, for organic synthetic chemists, might include the use of a cheap deuterium source, mild operating conditions, and diverse transformations. We developed an umpolung sequence reductive deuteration aldehydes/ketones, affording synthetically useful monodeuterated phosphinates. further one-pot transformation plausible mechanism this reaction were studied.

Language: Английский

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