Chiral Symmetry Breaking of Monoacylated Anhydroerythritols and <i>meso</i>‐1,2‐Diols through Crystallization‐Induced Deracemization
Kazutaka Sanada, Aoi Washio, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Abstract
Abstract We developed a chiral symmetry breaking method for monoacylated meso diols. The X‐ray crystal structure analysis of monoacylated 1,4‐anhydroerythritols, meso cyclic diols with a cis configuration, revealed that the O‐( p ‐anisoyl) derivative crystallized as a racemic conglomerate of the P 2 1 2 1 2 1 crystal system. It was confirmed that the substrate racemized by intramolecular transfer of the acyl group in the presence of a catalytic amount of base. Evaporating the solvent gradually from the solution or Viedma ripening to promote crystallization‐induced deracemization efficiently led to enantiomer crystals. These results provide the first successful example of asymmetric expression and amplification by deracemization of sugar derivatives without an external chemical chiral source. Furthermore, we applied this methodology to acyclic meso ‐1,2‐diols. Three O‐monoacylated substrates were successfully deracemized to 99 % ee by Viedma ripening. We also developed asymmetric desymmetrization of meso ‐1,2‐diols by combining acylation and crystallization‐induced deracemization.