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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Access to Chiral Oxindoles via Ir-Catalyzed Asymmetric Pudovik Addition/[1,2]-Phospha-Brook Rearrangement/Allylation Cascade

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

Published: May 2, 2025

An asymmetric catalytic Pudovik addition/[1,2]-phospha-Brook rearrangement/allylation reaction of readily available isatins, phosphites, and vinyl ethylene carbonate enabled by a chiral iridium catalyst was developed in one-pot fashion. A wide range enantioenriched oxindole derivatives containing two adjacent stereocenters could be obtained good to high yields with excellent diastereoselectivity enantioselectivity (65-99% yield, 7:1 >20:1 dr, generally 99% ee). This cascade protocol owned the advantages starting materials, regio-/diastereo-/enantioselectivity, substrate scope generality.

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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