Huber, Tanja and Espinosa-Jalapa, Noel Angel and Bauer, Jonathan O. (2022) Access to Enantiomerically Pure P-Stereogenic Primary Aminophosphine Sulfides under Reductive Conditions. CHEMISTRY-A EUROPEAN JOURNAL, 28 (72). ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Stereochemically pure phosphines with phosphorus-heteroatom bonds and P-centered chirality are a promising class of functional building blocks for the design of chiral ligands and organocatalysts. A route to enantiomerically pure primary aminophosphine sulfides was opened through stereospecific reductive C-N bond cleavage of phosphorus(V) precursors by lithium in liquid ammonia. The chemoselectivity of the reaction as a function of reaction time, substrate pattern, and chiral auxiliary was investigated. In the presence of exclusively aliphatic groups bound to the phosphorus atom, all competing reductive side reactions are totally prevented. The absolute configurations of all P-stereogenic compounds were determined by single-crystal X-ray diffraction analysis. Their use as synthetic building blocks was demonstrated. The lithium salt of (R)-BINOL-dithiophosphoric acid proved to be a useful stereochemical probe to determine the enantiomeric purity. Insights into the coordination mode of the lithium-based chiral complex formed in solution was provided by NMR spectroscopy and DFT calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CATALYTIC ASYMMETRIC DEPROTONATION; CHIRAL PHOSPHORUS LIGANDS; PHOSPHINE OXIDES; ENANTIOSELECTIVE SYNTHESIS; BRONSTED ACID; DIASTEREOSELECTIVE SYNTHESIS; ORGANOMETALLIC REAGENTS; BORANE COMPLEXES; ALDOL REACTIONS; HYDROGENATION; alkali metals; cleavage reactions; phosphorus; P-stereogenic compounds; structure elucidation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Jan 2024 06:45 |
| Last Modified: | 09 Jan 2024 06:45 |
| URI: | https://pred.uni-regensburg.de/id/eprint/57067 |
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