Mechanistic Insights into the Palladium‐Catalysed Asymmetric Phosphination of Cyclohexenyl Triflate

Julienne, Delphine; Delacroix, Olivier; Lohier, Jean‐François; Oliveira‐Santos, Jana Sopkova de; Gaumont, Annie‐Claude

doi:10.1002/ejic.201000987

Cited by 10 publications

(1 citation statement)

References 25 publications

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“…Stereogenic phosphorus compounds can be generated via catalytic asymmetric reactions in high yields. However, the stereoselectivities are often not sufficient . Another strategy for forming P -chiral centers is the conversion of P -stereogenic starting materials .…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

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

et al. 2017

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Accelerated and Enantioselective Synthesis of a Library of P‐Stereogenic Urea Phosphines

2018

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Chiral phosphorus ligands play a central role in majority of the asymmetric transformations. However, access to chiral phosphorus ligands is limited due to their challenging synthesis. Reported here is a highly efficient and accelerated catalytic asymmetric synthesis of P‐stereogenic urea containing phosphines leading to a small library of 18 chiral phosphorus compounds. Characteristic two doublets in a 31P NMR spectrum, spectroscopic and analytical evidences authenticated the formation of [Pd‐{(S,S) Me‐FerroLANE}(m‐phenylurea)(I)] complex. Indeed, [Pd‐{(S,S) Me‐FerroLANE}(m‐phenylurea)(I)] was found to catalyze the C‐P coupling reaction and quantitative conversion was observed within 18 hours. Under optimized conditions, iodophenyl urea's (2a–2j) were treated with secondary phosphines (1a–1c) in presence of [Pd‐{(S,S) Me‐FerroLANE}(m‐phenylurea)(I)] to obtain P‐stereogenic urea phosphines 5a–5r. The identity of these urea derived phosphines was unambiguously ascertained using a combination of spectroscopic and analytical methods. The catalyst tolerated various functional groups and yielded corresponding urea containing phosphines with an enantiomeric excess in the range of 15–62 %.

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Phosphorus Ligands in Hydroformylation and Hydrogenation: A Personal Account

Tewari

Kumar

Chandanshive

et al. 2021

The Chemical Record

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Metal‐catalyzed hydroformylation and hydrogenation heavily rely on ligands, among which phosphorous ligands play a pivotal role. This personal account presents a selection of three distinct classes of phosphorous ligands, namely, monodentate meta‐substituted phosphinites, bis‐phosphites, and P‐chiral supramolecular phosphines, developed in our group. The synthesis of these ligands, isolation, characterization, and their performance in transition metal‐catalyzed hydroformylation, isomerizing hydroformylation, and asymmetric hydrogenation of olefins is summarized. The state of the art development in iron‐catalyzed hydroformylation of alkenes and our contributions to the field is discussed. Use of phosphines enabled iron‐catalyzed hydroformylation of alkenes under mild conditions. Thus, this account demonstrates the central role of phosphorus ligands in industrially relevant transformations such as hydrogenation and hydroformylation. The seemingly matured field of ligand discovery still holds significant potential and will steer the field of homogeneous catalysis.

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Mechanistic Insights into the Palladium‐Catalysed Asymmetric Phosphination of Cyclohexenyl Triflate

Cited by 10 publications

References 25 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

Accelerated and Enantioselective Synthesis of a Library of P‐Stereogenic Urea Phosphines

Phosphorus Ligands in Hydroformylation and Hydrogenation: A Personal Account

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