LAUSR

For molecules with a singlet ground state, the population of triplet states is mainly possible (a) by direct excitation and subsequent intersystem crossing or (b) by energy transfer from an appropriate sensitizer. The latter scenario enables a catalytic photochemical reaction in which the sensitizer adopts the role of a catalyst undergoing several cycles of photon absorption and subsequent energy transfer to the substrate. If the product molecule of a triplet-sensitized process is chiral, this process can proceed enantioselectively upon judicious choice of a chiral triplet sensitizer. An enantioselective reaction can also occur in a dual catalytic approach in which, apart from an achiral sensitizer, a second chiral catalyst activates the substrate toward sensitization. Although the idea of enantioselective photochemical reactions via triplet intermediates has been pursued for more than 50 years, notable selectivities exceeding 90% enantiomeric excess (ee) have only been realized in the past decade. This review attempts to provide a comprehensive survey on the various photochemical reactions which were rendered enantioselective by triplet sensitization.