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Enantiopure building blocks for the synthesis of 3-methyl-2-alkanols: Diastereoselective methylmetal addition to a chiral 2-methylaldehyde followed by lipase catalysed esterification
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
2004 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 15, no 18, 2907-2915 p.Article in journal (Refereed) Published
Abstract [en]

The racemic synthetic building block (2R*,3R*)-3-methyl-4-(phenylsulfanyl)butan-2-ol (2R*,3R*)-2 was obtained in a high diastereomeric ratio [95:5, (2R*,3R*)/(2R*,3S*)-ratio] by Lewis acid catalysed dimethylzinc addition to racemic 2-methyl-3-(phenylsulfanyl)propanal (rac-1). Two consecutive acylations with vinyl acetate catalysed by Chirazyme L-2 (immobilised Candida antarctica lipase 13, CAL-B) led to preferential esterification of three of the four stereoisomers leaving (2S,3S)-3-methyl-4-(phenylsulfanyl)butan-2-ol (2S,3S)-2 of 98:2 dr and 98% ee. The stereoisomerically impure acetate of (2R,3R)-3-methyl-4-(phenyisulfanyl)butan-2-ol (2R,3R)-2, obtained in the first CAL-B-catalysed acylation step, was hydrolysed and reesterified using CAL-A (immobilised Novozyme SP 525) as the catalyst, which left (2R,3R)-3-methyl-4-(phenylsulfanyl)butan-2-ol (2R,3R)-2 of 98:2 dr and 99% ee as the remaining substrate. The individual enantiomers of 2-methyl-3-(phenylsulfanyl)propanal 1 were prepared from readily available (S)- and (R)-3-hydroxy-2-methylpropanoic acid methyl ester and reacted with dimethylzinc to give both enantiomers of (2R*,3R*)-3-methyl-4-(phenylsulfanyl)butan-2-ol (2R, 3R)- or (2S,3S)-2 of both high dr and ee. These products were purified by lipase catalysed acylation to give the enantiomerically and diastereomerically highly pure enantiomers (>99.5:0.5 dr, >99.9% ee). Pure (2S,3S)-3-methyl-4-(phenylsulfanyl)butan-2-ol (2S,3S)-2 was transformed into a potential pheromone precursor isolated from some pine sawflies of the genus Gilpinia, (2S,3R)-3-methylpentadecan-2-ol in 54% yield over eight steps.

Place, publisher, year, edition, pages
2004. Vol. 15, no 18, 2907-2915 p.
Keyword [en]
3-methyl-2-alkanols, dimethylzinc, diastereoselectivity, kinetic resolution
National Category
Chemical Sciences Industrial Biotechnology
Identifiers
URN: urn:nbn:se:miun:diva-873DOI: 10.1016/j.tetasy.2004.07.049ISI: 000224333100032Local ID: 2194OAI: oai:DiVA.org:miun-873DiVA: diva2:25905
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2011-05-29Bibliographically approved

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Larsson, MichaelAndersson, JimmyLiu, RongHögberg, Hans-Erik
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CiteExportLink to record
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