Acylative Desymmetrization of Cyclic meso-1,3-Diols by Chiral DMAP Derivatives

An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed by using a chiral DMAP derivative 1e having a 1,1'-binaphthyl unit. The reactions required only 0.5 mol % of the catalyst and showed good to excellent enantioselectivity. With this transformation, 5a, a key building block for the synthesis of natural products, was easily obtained in almost enantiomerically pure form after a single recrystallization. Control experiments revealed that tert-alcohol units on the catalyst were responsible for both the catalytic activity and enantioselectivity.

Automated summary

An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed using a chiral DMAP derivative with a 1,1'-binaphthyl unit, showing good to excellent enantioselectivity. The key building block obtained from this transformation can be easily obtained in almost enantiomerically pure form.