Variable mechanism of nucleophilic substitution of P-stereogenic phosphoryl chloride with alkynyl metallic reagents

Yao, Lan; Liu, Lijuan; Xu, Zhongyuan; Nie, Shao‐Zhen; Xiao, Xiao-Qing; Zhao, Chang‐Qiu

doi:10.1039/c5ob01871d

Cited by 4 publications

(2 citation statements)

References 45 publications

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“…In some cases in which 6a′ was formed significantly, l -(−)-menthol was detected by proton NMR spectroscopy. As seen in Scheme , other than in the BPR route B 1 to form 6a′ , 8 could be converted to l -(−)-menthol via direct P–O bond cleavage, which was assigned as route A 1 ′.…”

Section: Resultsmentioning

confidence: 99%

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

et al. 2017

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Nucleophilic substitutions at P centers are of high importance in biological processes and asymmetric synthesis. However, detailed studies on this topic are rare. P-Stereogenic compounds containing P-Cl, P-O, and P-S bonds were diastereoselectively prepared and then used to study the substitution of Cl, O, and S at phosphorus centers with organometallic reagents. It was proposed that with alkynyl metallic reagents an S2-like mechanism (route A) and a Berry pseudorotation (BPR) of pentacoordinated phosphorus intermediates (route B) were involved and afforded P-inverted and P-retained products, respectively. The P-inverted conversion of a P-Cl functionality to a P-C functionality can be controlled by either the temperature or the order of addition of the starting materials. The introduction of a P-Cl bond using an alkyl metallic reagent proceeded through routes A and A'. At higher temperatures, P-inverted products were predominantly afforded via S2-like route A. At lower temperatures, bis-substituted products were formed via route A' and cleavage of the P-O bond. The P-S bonds were accompanied by the epimerization of the starting materials, triggered by the alkylthio anion, via route C. The epimerization can be suppressed by the use of a poorly soluble magnesium alkylthiolate, and the P-retained compounds will be formed as the major products via route B and BPR of the intermediates.

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Section: Resultsmentioning

confidence: 99%

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

et al. 2017

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“…[66,67] In this context, Zhao, Han and co-workers reinvestigated the stereochemical outcome of the addition of nucleophiles such as alkynylmetals to chiral phosphonochloridates (Scheme 42). [68,69] Careful control of both the reaction conditions and the reagents Chemistry-A European Journal are required to predict the nature of the final products. For instance, when lithium phenylacetylide 109 was used at -45…”

Section: Nucleophilic Displacement Of P-cl Derivativesmentioning

confidence: 99%

New Approaches toward Building C_sp−P bond: A Two‐Decade Overview

Mele

Pirat

Ayad

et al. 2022

Chemistry A European J

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Since the review of Savignac, the past 20 years have seen significant progresses on the synthesis of alkynylphosphorus compounds considerably expanding the original and rather limited organic toolbox. This comprehensive review explores the latest and potentially greener methodologies using sustainable catalysis or direct metal‐free couplings from stable and easy to handle precursors. Recent progress and mechanistic insights for metal‐catalyzed reactions with a particular emphasis on copper, palladium, nickel and silver catalytic systems, photocatalytic and metal‐free reactions are detailed covering most of the publications related to this field since 2000 until March 2022.

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Carbanions and Electrophilic Aliphatic Substitution

Birsa¹

2020

Organic Reaction Mechanisms · 2016

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Variable mechanism of nucleophilic substitution of P-stereogenic phosphoryl chloride with alkynyl metallic reagents

Cited by 4 publications

References 45 publications

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

New Approaches toward Building C_sp−P bond: A Two‐Decade Overview

Carbanions and Electrophilic Aliphatic Substitution

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Variable mechanism of nucleophilic substitution of P-stereogenic phosphoryl chloride with alkynyl metallic reagents

Cited by 4 publications

References 45 publications

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

New Approaches toward Building Csp−P bond: A Two‐Decade Overview

Carbanions and Electrophilic Aliphatic Substitution

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Product

Resources

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New Approaches toward Building C_sp−P bond: A Two‐Decade Overview