Catalytic enantioselective synthesis of key intermediates for triazole antifungal agents

Organic Letters

Volumn 7, Issue 13, 2005, Pages 2527-2530

  Suzuki, Masato ^a   Kato, Nobuki ^b   Kanaki, Motomu ^a,b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

2 (2,4 DIFLUOROPHENYL) 1 [3 [2 [4 (2,2,3,3 TETRAFLUOROPROPOXY)PHENYL]VINYL] 1,2,4 TRIAZOL 1 YL] 3 (1,2,4 TRIAZOL 1 YL) 2 PROPANOL; ANTIFUNGAL AGENT; SCH45450; TRIAZOLE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY; ELECTROSPRAY MASS SPECTROMETRY; STEREOISOMERISM; SYNTHESIS;

ANTIFUNGAL AGENTS; CATALYSIS; SPECTROMETRY, MASS, ELECTROSPRAY IONIZATION; STEREOISOMERISM; TRIAZOLES;

EID: 29844457404     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol050398+     Document Type: Article

References (33)

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22. Chiral ligands 4 and 5 are commercially available from Junsei Chemical Co., Ltd., Tokyo, Japan. Fax: +81-3-3270-5461.
23. Ligands 4 and 5 produced almost comparable enantioselectivity from simple ketones (e.g., acetophenone or 2-heptanone) as a substrate. Therefore, the significant difference in enantioselectivity between 4 and 5 is specific for the electron-deficient substrate 2a.
24. A marked advantage of 5 to 4 was observed in the Strecker reaction of ketoimines and the conjugate addition of cyanide: (a) Masumoto, S.; Usuda, H.; Suzuki, M.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 5634 (Strecker reaction).
25. (b) Mita, T.; Sasaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 514 (conjugate addition).
26. 3 (2 mol %) did not improve the enantioselectivity, which suggested that the improvement is not due to remaining trace amount HMDS.
27. 3 (0.17 M stock solution in THF, 1.3 mL, 0.22 mmol) was added to a solution of 5 (164 mg, 0.35 mmol) in THF (7 mL) in an ice bath, and the mixture was warmed to 45°C for 30 min. After cooling to room temperature, volatiles were evaporated, and the resulting white powder was dried under vacuum (2 mmHg) at 45°C for 3 h. Propionitrile (7 mL) was added, followed by the addition of TMSCN (2.1 mL, 15.8 mmol) at -30°C. After 10 min, substrate ketone 2a (2.00 g, 10.5 mmol) was added to start the reaction.
28. 3 as a gadolinium source (95 and 96% ee, respectively, using 2.5 mol catalyst at -40°C). The different tendency might be attributed to the susceptibility of the reactive ketones to the undesired reaction pathways promoted by the contaminating complex 8 (see text).
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30. + = 2831; see ESI-MS chart below).
31. (Figure Presented) (17) Rare earth metal isopropoxides can generate the μ-oxo complex even under strictly anhydrous conditions with liberation of diisopropyl ether at temperatures higher than the boiling point of 2-propanol. See: Bradley, D. C.; Chudzynska, H.; Frigo, D. M.; Hammond, M. E.; Hursthouse, M. B.; Mazid, M. A. Polyhedron 1990, 9, 719.
32. 3 and 5 in a 1:2 ratio, which excluded the possibility that generation of the μ-oxo 4:5 complex is due to the different metal/ligand ratio.
33. Studies to selectively generate the μ-oxo 4:5 complex and to elucidate the catalyst activity and enantioselectivity of this complex are ongoing.