Enzymatic synthesis of enantio- and diastereomerically enriched syn-3- nitro-2-pentanol

Tetrahedron Asymmetry

Volumn 10, Issue 19, 1999, Pages 3681-3690

  Morgan, Brian ^a   Sarikonda, Bhaskar R ^a   Dodds, David R ^a,b   Homann, Michael J ^a   Vail, Robert ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

^b BRISTOL MYERS SQUIBB COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

3 NITRO 2 PENTANOL; PENTANOL; POSACONAZOLE; UNCLASSIFIED DRUG;

ACYLATION; ANTIFUNGAL ACTIVITY; ARTICLE; DEACYLATION; DRUG SYNTHESIS; ENANTIOMER; ENZYME SYNTHESIS; HYDROXYLATION; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0033407116     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(99)00386-9     Document Type: Article

References (29)

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22. Novozyme 435 (Novo SP 435 from Novo Nordisk) is a lipase (lipase type B) whose gene coding has been transferred from a selected strain of Candida antarctica to a host organism, Aspergillus oryzae. The enzyme produced by the host organism is immobilized on a macroporous acrylic resin. ChiroCLEC™ BL (Alms Biologies, Inc.) is a cross-linked microcrystal of the serine endoprotease from Bacillus licheniformis. The dry powder form for reactions in organic solvents was used.
23. 3SnH/AIBN) and compared on chiral GC with the pentyl acetate prepared from commercial (R)-2-pentanol, establishing the reactive isomer as 2R (synlanti). Similarly, pure anti-nitroacetate 7a was reduced to (R)-pentyl acetate. This established the reactive isomers in the enzymatic acetylation as (2R,3R)-syn and (2R,3S)-anti. In addition, Novozyme 435 catalyzed deacylation of pure (±)-syn-7a provided (2R,3R)-2 whose structure was confirmed by X-ray crystallography of the corresponding brosylate 9 (Scheme 6). The assignments were also confirmed by examination of the corresponding Mosher esters using the model proposed by Kakisawa: Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092-4096.
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27. Amano lipase AK has been reported to acetylate the R-enantiomer of 1-nitro-2-propanol with high enantioselectivity: see Ref. 6b. Lipase AK was also highly selective for the acetylation of (±)-2 but was not as fast as Novozyme 435 under the conditions of the original screen.
28. The preparation of nitroalkenes from the acyloxynitro compounds has been reported previously, but we are unaware of any reports of preferential elimination. See (a) Barton, D. H. R.; Kervagoret, J.; Zard, S. Z. Tetrahedron 1990, 46, 7587-7598. (b) Denmark, S. E.; Senanayake, C. B. W. Tetrahedron 1996, 52, 11579-11600.
29. The preparation of nitroalkenes from the acyloxynitro compounds has been reported previously, but we are unaware of any reports of preferential elimination. See (a) Barton, D. H. R.; Kervagoret, J.; Zard, S. Z. Tetrahedron 1990, 46, 7587-7598. (b) Denmark, S. E.; Senanayake, C. B. W. Tetrahedron 1996, 52, 11579-11600.