Trifluoromethyl vs. methyl ability to direct enantioselection in microbial reduction of carbonyl substrates

Tetrahedron

Volumn 54, Issue 12, 1998, Pages 2809-2818

  Arnone, Alberto ^a   Bernardi, Rosanna ^a   Blasco, Francesca ^a   Cardillo, Rosanna ^a   Resnati, Giuseppe ^a   Gerus, Igor I ^b   Kukhar, Valery P ^b  

^a POLITECNICO DI MILANO   (Italy)

^b INSTITUTE OF BIOORGANIC CHEMISTRY AND PETROCHEMISTRY   (Ukraine)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; CYCLOHEXANONE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; DIASTEREOISOMER; PRIORITY JOURNAL; REDUCTION; SACCHAROMYCES CEREVISIAE; STEREOSPECIFICITY;

SACCHAROMYCES CEREVISIAE; STAPHYLOCOCCUS PHAGE 3A; TRIFLUORO;

EID: 0032546281     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)83017-2     Document Type: Article

References (49)

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4. The trifluoromethyl has been suggested to posses physical properties intermediate between those of a methyl and a carbomethoxy (ref. 3). It has also been proposed to have a pseudo-π character (ref. 4) and the ability to coordinate metal ions (ref. 5).
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15. This transformation could be particularly well tailored to study the steric hindrance of the trifluoromethyl group as the kinetic resolution of racemic esters, or acids, by lipases and other hydrolytic enzymes is usually interpreted on the basis of steric interactions in enzyme-substrate adducts (ref. 13). However, it has to be observed that some lipases (from Candida cylindracea, Candida rugosa, Candida antarctica) have shown the same enantioselectivities (ref. 14) in the resolution of trifluoromethyl carbinols and their methyl analogues (ref. 15) while other lipases (PS, AK) showed opposite enantioselectivities (ref. 16). This suggests that several parameters besides steric hindrance play a role in determining enantioselectivities in lipase resolution of alcohols.
16. Faber, K. Biotranformations in Organic Chemistry, Springer, 2nd ed., 1995. Preparative Biotransformations: Whole cell and Isolated Enzymes in Organic Synthesis; Roberts, S.M. Ed.; Wiley, Chichester, 1993
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18. Alkyl(aryl) trifluoromethyl carbinols and their alkyl(aryl) methyl analogues which have the same geometry at the stereogenic centre are assigned to the opposite absolute configurations due to the CIP rules (e. g. (S)-4a and (R)-4b, or (S)-5a and (A)-5b).
19. Hamada, H.; Shiromoto, M.; Funahashi, M.; Itoh, T.; Nakamura, K. J. Org. Chem. 1996, 61, 2332-2336. Petschen, I.; Malo, E.A.; Bosch, M.P.; Guerrero, A. Tetrahedron: Asymm. 1996, 7, 2135. Gaspar, J.; Guerrero, A. Tetrahedron: Asymm. 1995, 6, 231-238.
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22. Opposite enantioselectivity means that the formed alcohols have opposite geometry at the stereogenic centre, but they are assigned the same absolute configuration due to CIP rules.
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30. It was not possible to establish the enantiomeric purity of unreduced ketones 1 as by GLC a partial overlap of one ketone enatiomer with one of the formed alcohols could not be avoided when 1a was used and we were unable to separate the enantiomers of 1b.
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32. Yamazaki, Y.; Kobayashi, H. Tetrahedron. Asymm. 1993, 4, 1287-1294. Goto, M.; Yamazaki, Y.; Uebayasi M. Bull. Chem. Soc. Jpn. 1993, 66, 666-669. Bucciarelli, M.; Forni, A.; Moretti, I.; Torre, G. Synthesis 1983, 897-899.
33. Yamazaki, Y.; Kobayashi, H. Tetrahedron. Asymm. 1993, 4, 1287-1294. Goto, M.; Yamazaki, Y.; Uebayasi M. Bull. Chem. Soc. Jpn. 1993, 66, 666-669. Bucciarelli, M.; Forni, A.; Moretti, I.; Torre, G. Synthesis 1983, 897-899.
34. 2O 80 : 20).
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37. (S)-trifluoromethyl alcohols have been obtained in good e.e. through reduction of corresponding ketones by the alcohol dehydrogenase from this microorganism: Nakamura, K.; Matsuda, T.; Itoh, T.; Ohno, A. Tetrahedron Lett. 1996, 37, 5727-5730.
38. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
39. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
40. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
41. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
42. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
43. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
44. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
45. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
46. These acids have been used to assign the absolute configuration of secondary alcohols (Raban, M.; Mislow, K Tetrahedron Lett. 1965, 4249-4253. Helmchen, G. Tetrahedron Lett. 1974, 1527-1530. Bravo, P.; Ganazzoli, F.; Resnati, G.; De Munari, S.; Albinati, A. J. Chem. Res., Synop. 1988, 216-217; Miniprint 1988, 1701-1739. Bravo, P.; Frigerio, M.; Resnati, G. Synthesis 1988, 955-959. Bravo, P.; Pregnolato, M.; Resnati, G. J. Org. Chem. 1992, 57, 2726-2731), amines (Helmchen, G.; Volter, H.; Schule, W. Tetrahedron Lett. 1977, 1417-1420), and thiols (Helmchen, G.; Schmierer, R. Angew. Chem. 1976, 88, 770-771; Angew. Chem., Int. Ed. Engl. 1976, 15, 703-704).
47. c ≤ 0.05 ppm) so that the preference for the eclipsed conformation described above and depicted in Scheme 3 is further supported.
48. c (0,06 ppm).
49. Lin, J.T.; Yamazaki, T.; Kitazume, T.J. Org. Chem. 1987, 52, 3211-3217.