Low-temperature method for enhancement of enantioselectivity in the lipase-catalyzed kinetic resolutions of solketal and some chiral alcohols

Tetrahedron Letters

Volumn 39, Issue 43, 1998, Pages 7881-7884

  Sakai, Takashi ^a   Kishimoto, Tetsuo ^a   Tanaka, Yukie ^a   Ema, Tadashi ^a   Utaka, Masanori ^a  

^a OKAYAMA UNIVERSITY   (Japan)

Author keywords

Acylation; Enantiospecificity; Enzymes and enzyme reactions; Resolution

Indexed keywords

ACETAL DERIVATIVE; ALCOHOL; TRIACYLGLYCEROL LIPASE;

ACYLATION; ARTICLE; CATALYSIS; CHIRALITY; ENANTIOMER; ENZYME ACTIVITY; ENZYME MECHANISM; ESTERIFICATION; KINETICS; LOW TEMPERATURE PROCEDURES;

EID: 0032558671     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01747-X     Document Type: Article

References (21)

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14. 14. General procedure for Table 1: To a cooled mixture of solketal, lipase, and diisopropyl ether (dried over benzophenone ketyl) was added freshly distilled vinyl butyrate through a syringe. Progress of the reaction was monitored by TLC analysis. After the reaction time indicated, the mixture was filtered as quickly as possible by suction through Celite pad to remove the lipase and the filtrate was concentrated under reduced pressure. The products without isolation were allowed to react with excess of propanoic anhydride (0.2 ml, 1.55 mmol) in pyridine (0.2 ml) overnight and then treated in the usual manner. Optical purities (% ee) of the obtained mixture of (S)-butyrate and (R)-propanoate were determined by GLC analysis with a chiral column (Tokyo Chemical Co. Ltd., CP-cyclodextrin-B-236-M-19, oven temp. 100 °C), compound (retention time): (R)-(26.3 min) and (S)-propanoates (27.7 min); (R)-(43.4 min) and (S)-butyrates (45.8 min). Reuse of these lipases (PS and AK) tends to reduce the selectivity. Reusable immobilized lipases are now under investigation.
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19. 19. Ee(s) of 2, its acetate and 3 were determined by HPLC analysis with Chiralcel OB-H (hexane - i-PrOH). Acetate of 3 was analyzed by HPLC after hydrolysis to alcohol 3. Ee(s) of acetate of 5 were determined by the GLC analysis in a similar way to that for 1 and those of 5 were determined after conversion to its acetate.
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