Stereoselective Synthesis of <i>P</i>‐Stereogenic <i>N</i>‐Phosphinyl Compounds

Chelouan, Ahmed; Recio, Rocío; Álvarez, Eleuterio; Khiar, Noureddine; Fernández, Inmaculada

doi:10.1002/ejoc.201501260

Cited by 13 publications

(1 citation statement)

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“…Over the past decades, chemists have primarily focused on four methodologies for constructing optically pure phosphorus compounds. Firstly, the use of natural chiral auxiliaries like menthol [11] and D-glucose [12] necessitates pre-splicing of the auxiliaries. Recent advancements include transition metalcatalyzed intramolecular CÀ H functionalization of diphenyl phosphide oxides, offering a representative desymmetrization protocol for accessing enantioenriched phosphorus products, albeit requiring the introduction of directing groups.…”

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confidence: 99%

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Liu,

Deng,

Liang

et al. 2024

Angewandte Chemie

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Intermolecular pnictogen bonding (PnB) catalysis has received increased interest in non‐covalent organocatalysis. It has been demonstrated that organic electron‐deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre‐chiral phosphorus molecules bearing two electron‐withdrawing benzoyl groups, resulting in the formation of a σ‐hole at the P atom. X‐ray and non‐covalent interaction (NCI) analysis indicate that these phosphorus substrates exhibit intrinsic PnB interactions between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrates in a preferred conformation (P212121 chiral group). Under the catalysis of N–heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus products with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non‐polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.

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confidence: 99%

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Liu,

Deng,

Liang

et al. 2024

Angewandte Chemie

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Asymmetric Synthesis ofP‐Chirogenic Phosphorus Compounds

2016

Asymmetric Synthesis in Organophosphorus Chemistry

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Synthesis of Heteroatom Stereocenters by Enantioselective CH Functionalization

Cao

Tang

2022

Handbook of CH-Functionalization

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Enantioselective CH functionalization is one of the most straightforward and efficient approaches to access synthetically valuable chiral molecules. Only recently, transition metal‐catalyzed enantioselective CH functionalization has been explored to construct heteroatom stereocenters, providing molecules with heteroatom stereocenters that cannot be accessed otherwise. This article aims to provide a recent update toward the construction of heteroatom stereocenters through enantioselective CH functionalization including desymmetrization approach and resolution approach. The content is categorized according to the formed stereogenic atoms including P, Si, S‐stereocenters.

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Stereoselective Synthesis of P‐Stereogenic N‐Phosphinyl Compounds

Abstract: A number of P-stereogenic N-phosphinyl compounds were stereoselectively prepared in good yields by a straightforward approach, thanks to the diversified and, up until now, unexplored reactivity of (R)-and (S)-dicyclohexylidene-D-

Cited by 13 publications

References 74 publications

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Asymmetric Synthesis ofP‐Chirogenic Phosphorus Compounds

Synthesis of Heteroatom Stereocenters by Enantioselective CH Functionalization

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Stereoselective Synthesis of P‐Stereogenic N‐Phosphinyl Compounds

Abstract: A number of P-stereogenic N-phosphinyl compounds were stereoselectively prepared in good yields by a straightforward approach, thanks to the diversified and, up until now, unexplored reactivity of (R)-and (S)-dicyclohexylidene-D-

Cited by 13 publications

References 74 publications

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to PIII‐Stereogenic Compounds

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to PIII‐Stereogenic Compounds

Asymmetric Synthesis ofP‐Chirogenic Phosphorus Compounds

Synthesis of Heteroatom Stereocenters by Enantioselective CH Functionalization

Contact Info

Product

Resources

About

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds