Photochemical deracemization of 2,3-allenoic acids mediated by a sensitizing chiral phosphoric acid catalyst

Photochemistry opens the possibility to convert a racemic mixture of a chiral compound into a distinct enantiomer in a single operation. Seven chiral phosphoric acids with a pendant thioxanthone chromophore were synthesized and evaluated as catalysts for the visible light-driven deracemization of 2,4-disubstituted 2,3-allenoic acids. A catalyst derived from 1,1'-spirobiindane-7,7'-diol (spinol) performed best and delivered 2-benzyl-4-tert-butyl-2,3-allenoic acids in 58-97% yield and with enantiomeric ratios (e.r.) varying between 71/29 and 85/15 depending on the benzyl substitution pattern. The major enantiomer was shown to be (R)-configured, and other 2,3-allenoic acids were also probed in the reaction. A mechanistic scenario for the observed enantioselectivity is provided that rests on experimental and quantum-chemical studies.