A versatile synthesis of chiral β-aminophosphines. Issue 24 (4th January 2016)

• Record Type: Journal Article
• Authors: Su, Hsin Y.; Song, Yixiong; Taylor, Mark S.
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 24(2016)
• Page Start: 5665
• Page End: 5672
• Publication Date: 2016-01-04
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c5ob02439k
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : A protocol for the synthesis of chiral β-aminophosphines by ring-opening of cyclic sulfamidates with metallated secondary phosphine oxides is described. It allows access to previously unknown derivatives having electron-deficient, electron-rich and sterically hindered P -aryl substituents. Abstract : A method for the preparation of chiral β-aminophosphines having substituted P -aryl groups is described. Ring-opening of cyclic sulfamidates with metal diarylphosphinites yields β-aminophosphine oxides, which are then reduced to the corresponding phosphines. Effects of the diarylphosphinite countercation on the regioselectivity of the ring-opening reaction ( P - versus O -alkylation) are discussed. This method enables the introduction of electron-deficient, electron-rich and sterically hindered diarylphosphino groups, as demonstrated by the synthesis of a series of novel, P -aryl-substituted β-aminophosphines derived from tert -leucinol, valinol and phenylglycinol. Access to these derivatives will create new opportunities for steric and electronic tuning of β-aminophosphine-derived chiral ligands and organocatalysts.