Enantioselective transesterification of a propargyl tertiary alcohol by Candida antarctica lipase A: A reaction medium engineering approach

Neto, Luiz Biondi; Milagre, Cíntia D. F.; Milagre, Humberto M. S.

doi:10.1016/j.rechem.2023.100966

Cited by 2 publications

(2 citation statements)

References 24 publications

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“…Thus far, only a few commercial lipases, such as lipase A from Candida antarctica (CAL-A), lipase from Candida rugosa, and lipase from Burkholderia cepacia, are applicable. [6][7][8][9] In detail, the KR of (�)-1 a containing a tetralin skeleton reported by Özdemirhan et al reached 20 % conversion in 144 h, producing ester (R)-3 aa (99 % ee) with very high enantioselectivity (E [10] : > 100). In contrast, the KR of (�)-4 containing the less bulky dihydroindene moiety reached 20 % conversion in 72 h, but the enantiomeric purity of ester (R)-5 a (71 % ee) and the enantioselectivity (E: 7) were low (Scheme 1A).…”

Section: Introductionmentioning

confidence: 95%

“…[8] In 2023, another approach for improving the KR reaction rate of (�)-6 via reaction engineering, such as the selection of better immobilization carriers for commercial CAL-A, was reported to give (R)-7 b (33 % conv., 95 % ee, E: 62) in 48 h at 30 °C (Scheme 1D). [9] Although the enzymatic KR of esters derived from racemic tertiary alcohols via enantioselective hydrolysis has also been reported, most of the substrates are limited to esters of 1-arylpropargylic alcohols. [11] We recently reported the first enzymatic DKR of (�)-1 a affording the optically active ester (R)-3 aa in 77 % yield and with 99 % ee, [12] in which enantioselective acylation with CAL-A proceeded simultaneously with the racemization of remaining (S)-1 a by our original racemization catalyst V-MPS4 [13] (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

Horino,

Wagner,

Hummel

et al. 2024

Eur J Org Chem

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Enzyme‐catalyzed acylative kinetic resolution (KR) and dynamic kinetic resolution (DKR) of racemic primary and secondary alcohols have been widely reported to produce esters with high enantiomeric purity. In contrast, similar KRs of tertiary alcohols have been reported for only a limited range of substrates and require prolonged reaction times of several days. To gain deeper insight into the substrate scope and increase the process efficiency, we examined the reaction conditions using commercially available immobilized lipase A from Candida antarctica and found that the addition of the heterogeneous, inorganic base sodium carbonate significantly increased the reaction rate while maintaining high enantioselectivity. The use of vinyl hexanoate as the acyl donor provided esters that were stable during chromatography purification. The optimized reaction conditions were then successfully applied to a range of cyclic tertiary alcohols containing tetralin, dihydroindene, chromane, and thiochromane skeletons having, in part, a substituent on the aromatic ring. In this study on the structure–reactivity relationship of enzymatic KR‐type reactions, we achieved >30% conversion for various tertiary alcohols in 24 h at 25 °C, producing optically active esters with 88–99% ee.

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Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

Horino,

Wagner,

Hummel

et al. 2024

Eur J Org Chem

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Strategies to Design Chemocatalytic Racemization of Tertiary Alcohols: State of the Art & Utilization for Dynamic Kinetic Resolution

Gröger,

Horino,

Kanomata

et al. 2024

Chemistry A European J

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In this "Concepts"‐article, the difficulties in racemizing tertiary alcohols are described as well as a summary of the different chemocatalytic concepts to overcome these hurdles and to pave a way for efficiently racemizing of tertiary alcohols. When combined with the enantioselective enzymatic esterification of tertiary alcohols, the racemization protocols enable a DKR to convert the racemates into enantiomerically pure esters of tertiary alcohols, which are of high interest in the field of pharmaceutically active products. Very recently, various research groups have succeeded in solving the challenging task of identifying suitable chemocatalysts for an efficient racemization of tertiary alcohols and simultaneously suppressing unwanted dehydration side‐reactions. It is noteworthy that such methods are based on different, complementary catalysis concepts. Besides Brønsted acids, oxovanadium catalysts as well as piperidine as a representative of an organocatalyst have been found to be useful for the racemization of each type of alcohols. The latter two types of catalysts also turned out to be compatible with lipase‐catalyzed kinetic resolution, thus leading to the first two examples of a proof‐of‐concept for chemoenzymatic DKR of tertiary alcohols.

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Enantioselective transesterification of a propargyl tertiary alcohol by Candida antarctica lipase A: A reaction medium engineering approach

Cited by 2 publications

References 24 publications

Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

Strategies to Design Chemocatalytic Racemization of Tertiary Alcohols: State of the Art & Utilization for Dynamic Kinetic Resolution

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