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Desymmetrization of meso-1,2-Diols by a Chiral N,N‑4-Dimethylaminopyridine Derivative Containing a 1,1′-Binaphthyl Unit: Importance of the Hydroxy Groups

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journal contribution
posted on 31.05.2017, 00:00 by Hiroki Mandai, Hiroshi Yasuhara, Kazuki Fujii, Yukihito Shimomura, Koichi Mitsudo, Seiji Suga
We developed an acylative desymmetrization of meso-1,2-diols using a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1h with tert-alcohol substituents. The reaction proceeds with a wide range of acyclic meso-1,2-diols and six-membered-ring meso-1,2-diols to provide a monoacylate selectively with a high enantiomeric ratio (er). Only 0.1 mol % of the catalyst facilitated the reaction within a short reaction time (3 h) to afford enantio-enriched monoacylated products in moderate to good yield. Several control experiments revealed that the tert-alcohol units of catalyst 1h play a significant role in achieving high catalytic activity, chemoselectivity of monoacylation, and enantioselectivity.