A Mesoporous‐Silica‐Immobilized Oxovanadium Cocatalyst for the Lipase‐Catalyzed Dynamic Kinetic Resolution of Racemic Alcohols

Abstract

V for resolution: A new oxovanadium catalyst (V‐MPS; see scheme) immobilized in the pores of mesoporous silica has been developed. The combined use of V‐MPS and lipases achieved the dynamic kinetic resolution of a wide range of racemic alcohols (1 or 2) to produce optically active esters 3 in high chemical and optical yields. The paired catalysts retained high catalytic activity when reused up to six times.

Lipases: Valuable catalysts for dynamic kinetic resolutions

“…The combination of oxovanadium catalysts and lipases have been reported to be useful for DKR of allylic alcohols (Akai, 2014;Akai et al, 2004Akai et al, , 2006Egi et al, 2013;Komaki et al, 2013). Akai et al described a method for the preparation of optically pure allylic alcohols by combining reactions of racemization and isomerization catalyzed by Fig.…”

“…In fact, there are few examples of heterogeneous and immobilized racemization catalysts compatible with lipases (Akai et al, 2010;Egi et al, 2013;Han et al, 2010a;Långvik et al, 2010;Nieguth et al, 2014;Wieczorek et al, 2011). The development of these catalysts, which are in general reusable and more suitable for industrial applications, is still a challenge.…”

“…The catalyst was applied in combination with immobilized B. cepacia lipase in the synthesis of (R)-imperanene (Fig. 18b) and has also been found to be useful for the DKR of benzyl, furyl and propargyl alcohols (Egi et al, 2013).…”

Algorithmic Discovery of Tactical Combinations for Advanced Organic Syntheses

“…As a case in point, we considered a platelet aggregation inhibitor called imperanene. 33,[37][38][39][40][41][42] To date, the syntheses allowing access to both the natural, (S) and unnatural (R) isomers entailed 8 to 11 steps 39,33 (see bottom portion of Figure 6D and Section S7). With the use of a previously unknown TC-that is, a previously Here, we consider an individual reaction to be popular if it has at least 300 literature precedents in the NOC.…”

Iridium-catalysed asymmetric hydrogenation of allylic alcohols via dynamic kinetic resolution

“…In these reactions an isomerization took place and the main products 1d and 11d were obtained in 89% and 87% respectively (Table 3, sulted from a redox mechanism in which the two enantiomeric alcohols are in equilibrium via the corresponding ketone or other type of racemization, 37,38 an experiment was attempted using the ketone 19 as starting material. In this reaction the ketone functionality remained in the product and in addition, the stereogenic centre formed had the opposite absolute configuration as observed in the dynamic kinetic resolution of the alcohol.…”