Enzymatic alcoholysis of alkoxymethyl alkanoates: A possible approach for the kinetic resolution of tertiary alcohols

Tetrahedron Letters

Volumn 39, Issue 45, 1998, Pages 8345-8348

  Franssen, Maurice C R ^a   Goetheer, Earl L V ^a   Jongejan, Hugo ^a   De Groot, Aede ^a  

^a WAGENINGEN UNIVERSITY   (Netherlands)

Author keywords

Esterase; Kinetic resolution; Lipase; Tertiary alcohols

Indexed keywords

HYDROLASE; LINALOOL; LINALOOL DERIVATIVE; TERT BUTYL ALCOHOL; UNCLASSIFIED DRUG;

ALCOHOL OXIDATION; ARTICLE; CANDIDA RUGOSA; CHEMICAL REACTION KINETICS; ENZYME BINDING; ENZYME KINETICS; HYDROLYSIS; STEREOCHEMISTRY;

EID: 0032487983     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01840-1     Document Type: Article

References (27)

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15. [7] This approach has been used succesfully for the resolution of hindered carboxylic acids (Ebiike H, Terao Y, Achiwa K. Tetrahedron Lett. 1991;41:5805-5808) and barbiturates ( Murata M, Achiwa K. Tetrahedron Lett. 1991;32:6763-6766 ).
16. [7] This approach has been used succesfully for the resolution of hindered carboxylic acids (Ebiike H, Terao Y, Achiwa K. Tetrahedron Lett. 1991;41:5805-5808) and barbiturates ( Murata M, Achiwa K. Tetrahedron Lett. 1991;32:6763-6766 ).
17. [8] See for a similar approach using a stable spacer: Brackenridge I, Mc.Cague R, Roberts SM, Turner NJ. J. Chem. Soc. Perkin Trans. I 1993:1093-1094.
18. [9] 1a Was prepared from potassium tert-butoxide and chloromethyl pivalate (Acros Organics) in THF, 47% yield [18]. 1b Was prepared by reaction of linalool with NaH in THF followed by treatment with chloromethyl pivalate, 40% yield [18].
19. [10] The enzymes were gifts from a) Biocatalysts Ltd.; b) Amano; c) Gist brocades; d) Novo Nordisk.
20. [11] Obtained from butyryl chloride and paraformaldehyde using zinc chloride as a catalyst (63% after distillation [18]): Rasmussen M, Leonard NJ. J. Am. Chem. Soc. 1967;89:5439-5445.
21. [12] Yields are 71 % for 4a and 61% for 4b, respectively [18].
22. [13] Established by retention time on chiral GC (Beta-DEX™ 120) through comparison to racemic linalool and oil of coriander, which contains (R)-linalool: Connolly JD, Hill RA. Dictionary of Terpenoids, Vol. I. London: Chapman & Hall, 1991:12.
23. [14] Standard procedure: 1 ml of a solution of 100 mM 4 in octane (unless indicated otherwise) containing 500 mM n-butanol and 45 mM hexadecane (internal standard) was mixed with enzyme and shaken at 45°C (unless indicated otherwise) and 250 rpm. The reaction was monitored by GC. Blanks showed no reaction.
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25. w=1) but had no effect on the E-value.
26. [17] Typical procedure: 6 ml of a solution of 100 mM 4b and 500 mM n-butanol in toluene was added to 100 mg Candida rugosa lipase. After 2 h of magnetic stirring at 0°C (conversion = 52%), the solution was filtered, concentrated and chromatographed to give 5.1 mg linalool [18] (c.e. = 68%;, detd. by GC).
27. [18] Numbers refer to isolated yields and are not optimised. NMR and HRMS data of all substrates and products are in full accordance with the depicted structures.