Enantiopure 1,5-Diols from Dynamic Kinetic Asymmetric Transformation. Useful Synthetic Intermediates for the Preparation of Chiral Heterocycles

Abstract

Dynamic kinetic asymmetric transformation (DYKAT) of a series of 1,5-diols has been performed in the presence of Candida antarctica lipase B (CALB), Pseudomonas cepacia lipase II (PS-C II), and ruthenium catalyst 4. The resulting optically pure 1,5-diacetates are useful synthetic intermediates, which was demonstrated by the syntheses of both an enantiopure 2,6-disubstituted piperidine and an enantiopure 3,5-disubstituted morpholine.

1,5-Polyols: Challenging motifs for configurational assignment and synthesis

“…22). Bäckvall has reported a dynamic kinetic asymmetric transformation which results in enantiopure 1,5-diols bearing additional functionality such as ester or nitrile (e.g., 70) [43]; this procedure combines kinetic resolution via enzymatic esterification with in situ Ru-catalyzed epimerization of secondary alcohols. Sequential dithiane-epoxide couplings can produce 1,5-diols with great versatility and efficiency, exploiting Brook rearrangement for in situ carbanion relay in a method first introduced by Smith and Boldi [44].…”

Dynamic kinetic asymmetric transformation of 1,4-diols and the preparation of trans-2,5-disubstituted pyrrolidines

“…2) as an epimerization catalyst. 7 We have now employed the previously optimized DYKAT conditions from that study for the 1,4-diols described here.…”

“…4 In a similar manner, enantiopure diols can be synthesized via dynamic kinetic asymmetric transformation (DYKAT). 5-7 Recently, we reported on an efficient procedure for DYKAT of 1,5-diols, 7 using a second generation Ru catalyst system. 2a,8 The enantiopure diacetates obtained were used in the synthesis of enantiopure heterocycles.…”

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

“…Monomeric ruthenium pentamethylcyclopentadiene complex 1 developed by Bäckvall and co-workers [17] has been widely used in tandem with different enzymes to deracemize a wide range of functionalized secondary alcohols, including aliphatic alcohols [18,19], allylic alcohols [20][21][22], chlorohydins [23], diols [24,25], homoallylic alcohols [26], and N-heterocyclic 1,2-aminos alcohols [27] with excellent yields and enantiomeric excess (ee). Recently, complex 1 has been employed to synthesize biologically active 5,6-dihydropyran-2-ones and the corresponding δ-lactones [26].…”