Photochemical Deracemization of Allenes and Subsequent Chirality Transfer
Manuel Plaza, Christian Jandl, Thorsten Bach
Abstract
Abstract Trisubstituted allenes with a 3‐(1′‐alkenylidene)‐pyrrolidin‐2‐one motif were successfully deracemized (13 examples, 86–98 % ee ) employing visible light ( λ =420 nm) and a chiral triplet sensitizer as the catalyst (2.5 mol %). The photocatalyst likely operates by selective recognition of one allene enantiomer via hydrogen bonds and by a triplet‐sensitized racemization process. Even a tetrasubstituted allene (45 % ee ) and a seven‐membered 3‐(1′‐alkenylidene)‐azepan‐2‐one (62 % ee ) could be enantiomerically enriched under the chosen conditions. It was shown that the axial chirality of the allenes can be converted into point chirality by a Diels–Alder (94–97 % ee ) or a bromination reaction (91 % ee ). Ring opening of the five‐membered pyrrolidin‐2‐one was achieved without significantly compromising the integrity of the chirality axis (92 % ee ).