α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

Hodgson, David M.; Xu, Zhaoqing

doi:10.3762/bjoc.6.110

Cited by 11 publications

(5 citation statements)

References 41 publications

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“…Chiral phosphorylated aziridines and their derivatives have been demonstrated with pharmaceutical and other important synthetic applications. In addition to the fundamental and practical significance of the phosphorous-containing aziridines, the easy deprotection of phosphoryl groups makes them even more synthetically useful [ 24 – 27 ]. However very few catalytic systems are available for the direct asymmetric olefin aziridination with phosphoryl azides.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

Tao¹,

Jin²,

Zhang³

2014

Beilstein J. Org. Chem.

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SummaryThe Co(II) complex of a new D 2-symmetric chiral porphyrin 3,5-DiMes-QingPhyrin, [Co(P6)], can catalyze asymmetric aziridination of alkenes with bis(2,2,2-trichloroethyl)phosphoryl azide (TcepN3) as a nitrene source. This new Co(II)-based metalloradical aziridination is suitable for different aromatic olefins, producing the corresponding N-phosphorylaziridines in good to excellent yields (up to 99%) with moderate to high enantioselectivities (up to 85% ee). In addition to mild reaction conditions and generation of N2 as the only byproduct, this new metalloradical catalytic system is highlighted with a practical protocol that operates under neutral and non-oxidative conditions.

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Section: Introductionmentioning

confidence: 99%

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

Tao¹,

Jin²,

Zhang³

2014

Beilstein J. Org. Chem.

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“…Transferring this information to the N-phosphonylated aziridines, the optimized conditions were successfully applied to perform the phosphonate N-to-C migration in a stereocontrolled manner (exclusively trans product). To improve the yield (58–95%), the amount of LTMP was increased to 5 equiv, the reaction mixture was more diluted, and the reaction time was increased . The group further illustrated the utility of these compounds by synthesizing β-aminophosphonates and the natural antibiotic ( S )-azirinomycin.…”

Section: Three-membered Rings: Azirines and Aziridinesmentioning

confidence: 99%

“…To improve the yield (58−95%), the amount of LTMP was increased to 5 equiv, the reaction mixture was more diluted, and the reaction time was increased. 89 The group further illustrated the utility of these compounds by synthesizing β-aminophosphonates and the natural antibiotic (S)-azirinomycin.…”

Section: Transition-and Post-transition Metal Catalysismentioning

confidence: 99%

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

Mayorquín-Torres,

Simoens,

Bonneure

et al. 2024

Chem. Rev.

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The increasing importance of azaheterocyclic phosphonates in the agrochemical, synthetic, and medicinal field has provoked an intense search in the development of synthetic routes for obtaining novel members of this family of compounds. This updated review covers methodologies established since 2004, focusing on the synthesis of azaheterocyclic phosphonates, of which the phosphonate moiety is directly substituted onto to the azaheterocyclic structure. Emphasizing recent advances, this review classifies newly developed synthetic approaches according to the ring size and providing information on biological activities whenever available. Furthermore, this review summarizes information on various methods for the formation of C–P bonds, examining sustainable approaches such as the Michaelis–Arbuzov reaction, the Michaelis–Becker reaction, the Pudovik reaction, the Hirao coupling, and the Kabachnik–Fields reaction. After analyzing the biological activities and applications of azaheterocyclic phosphonates investigated in recent years, a predominant focus on the evaluation of these compounds as anticancer agents is evident. Furthermore, emerging applications underline the versatility and potential of these compounds, highlighting the need for continued research on synthetic methods to expand this interesting family.

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“…Besides OH and SH functionalities, ortho -NH substituents are also accessible by 1,2-N→C rearrangements to the α-position as it could be shown for pyrroles. , If the α-positions are blocked, then 1,3- or 1,5-migrations occurred . The less stable N–P bond, compared to O–P or C–P units, readily allows 1,2-migrations in the presence of aldehydes, , aziridines, oximes, and even pyrroles …”

Section: Introductionmentioning

confidence: 99%

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

2017

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The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(EAr) (Fc = Fe(η-CH)(η-CH); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of MeSO thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N→C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.

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α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

Cited by 11 publications

References 41 publications

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

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