The Stereochemistry of P-N Bond Cleavage in the Staudinger -Wittig-type Reaction of 2-Anilido-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine-2-thiones

Lesiak, Krystyna; Stec, Wojciech J.

doi:10.1515/znb-1978-0719

Cited by 15 publications

(1 citation statement)

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“…The cycloaddition reaction was successfully extended to a variety of previously reported P-substituted 2H-phospholes [15][16][17] to give a range of diastereomeric α-substituted PANs (endo-1a-d, Scheme 1) via a sigmatropic shift of the substituent at higher temperatures [7,18]. The general formation and properties of compounds containing phosphorus-nitrogen bonds have been extensively studied [19][20][21][22][23][24][25][26][27], such as cleavage reactions [28][29][30][31][32]. Thus, the P-N bond of PAN endo-1b can be cleaved by achiral nucleophiles, namely H 2 O, H 2 S, and EtMgBr, to give 2,3-dihydrophosphole derivatives (5a,b or 3, Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies

Ramazanova,

Müller,

Lönnecke

et al. 2023

Molecules

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The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurization of the phosphorus atom, thus efficiently blocking the lone pair of electrons, as exemplified for 6b yielding structurally characterized 8b. Additionally, the influence of the substituent in the α position to the phosphorus atom (H, Ph, 2-py, CN) on the reversibility of the reaction was studied. Extensive theoretical calculations for understanding the ring-closing mechanism suggested that a multi-step reaction with one or more intermediates was most probable.

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Section: Introductionmentioning

confidence: 99%

Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies

Ramazanova,

Müller,

Lönnecke

et al. 2023

Molecules

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Oxygen Chiral Phosphate Esters

Gerlt

Coderre

Mehdi

1983

Advances in Enzymology - And Related Areas of Molecular Biology

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Stec Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The stereospecific synthesis of P‐chiral biophosphates from dialkyl (or aryl) phosphoramidate anions and carbonyl electrophiles, followed by the replacement of an amidate function by oxygen is generally referred to as the Stec reaction. This reaction not only provides a straightforward access to a variety of diastereomerically pure P‐chiral biophosphates and their analogues, but also retains the configuration at the phosphorus atom in these biophosphate analogues. This reaction is important for the synthesis of biophosphates and their analogues.

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The Stereochemistry of P-N Bond Cleavage in the Staudinger -Wittig-type Reaction of 2-Anilido-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine-2-thiones

Cited by 15 publications

References 3 publications

Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies

Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies

Oxygen Chiral Phosphate Esters

Stec Reaction

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