P-chiral 1-phosphanorbornenes: from asymmetric phospha-Diels–Alder reactions towards ligand design and functionalisation12. Issue 5 (17th August 2015)

• Record Type: Journal Article
• Authors: Möller, Tobias; Wonneberger, Peter; Sárosi, Menyhárt B.; Coburger, Peter; Hey-Hawkins, Evamarie
• Is Part Of: Dalton transactions. Volume 45:Issue 5(2016)
• Page Start: 1904
• Page End: 1917
• Publication Date: 2015-08-17
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02564h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A building set for chiral phosphorus. The principle of stereotopic face differentiation is successfully applied to a PC bond. A divergent ligand synthesis is feasible after reduction of the chiral auxiliary. Abstract : The principle of stereotopic face differentiation was successfully applied to 2 H -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 2 H -phosphole3a and the dienophile (5 R )-(−)-menthyloxy-2(5 H )-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 compound13a . Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.