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Updated: Apr 5, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
P-chiral 1-phosphanorbornenes: from asymmetric phospha-Diels-Alder reactions towards ligand design and
Tobias Möller1, Peter Wonneberger, Menyhárt B Sárosi
1Universität Leipzig, Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Johannisallee 29, D-04103 Leipzig, Germany. hey@uni-leipzig.de.
Abstract:
The principle of stereotopic face differentiation was successfully applied to 2H-phospholes which undergo a very efficient and highly stereoselective Diels-Alder reaction giving phosphorus-chiral 1-phosphanorbornenes with up to 87% yield. The observed reaction pathway has been supported by theoretical calculations showing that the cycloaddition reaction between 2H-phosphole 3a and the dienophile (5R)-(-)-menthyloxy-2(5H)-furanone (8) is of normal electron demand. Optically pure phosphanes were obtained by separation of the single diastereomers and subsequent desulfurisation of the sulfur-protected phosphorus atom. Finally, divergent ligand synthesis is feasible by reduction of the chiral auxiliary, subsequent stereospecific intramolecular Michael addition, and various functionalisations of the obtained key compound 13a. Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.
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