Fig. 1: Background and concept.

a Selected pentavalent phosphoranes. b Pentavalent stereocentres. c Fourfold stereogenicity in pentavalent stereocentres. d Stereoisomerisation of pentavalent dioxophosphoranes32,33,34,35,36,37. e Auxiliary (Xc*) approaches & dehydrogenation of hydridophosphoranes. f Recent strategies to catalytically control tetravalent phosphorus stereocentres. g Catalyst control over pentavalent phosphorus stereocentres (this work).