Photochemical Deracemization of Allenes and Subsequent Chirality Transfer

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).

Keywords: allenes; chiral resolution; enantioselectivity; hydrogen bonds; photochemistry; sensitizers.