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Larsson, Michael
Publications (9 of 9) Show all publications
Larsson, M., Galandrin, E. & Högberg, H.-E. (2004). Diastereoselective Addition of Organozinc Reagents to 2-alkyl-3-(arylsulfanyl)propanals. Tetrahedron, 60(47), 10659-10669
Open this publication in new window or tab >>Diastereoselective Addition of Organozinc Reagents to 2-alkyl-3-(arylsulfanyl)propanals
2004 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 60, no 47, p. 10659-10669Article in journal (Refereed) Published
Abstract [en]

The preparation of compounds incorporating the 3-hydroxy-2-methyl-1-alkyl moiety of high diastereomeric purity is described. Such compounds can serve as potential building blocks for the preparation of several kinds of natural products. Diastereoselective synthesis of two potential pine sawfly pheromone components, one the pure racemic threo-isomer of 3-methylpentadecan-2-ol and the other the racemic erythro-isomer of 3-methyltridecan-2-ol are described. The diastereoselective addition of R2Zn (R = Me, Et and n-Bu) to several 2-alkyl-3-(arylsulfanyl)propanals in the presence of a Lewis acid and CH2Cl2 as solvent was studied. An excellent diastereomeric ratio (95/5 anti-Cram/Cram) was obtained with 2-[(phenylsulfanyl)methyl]pentanal, 2-[(phenylsulfanyl)methyl]decanal and 2-[(phenylsulfanyl)methyl]dodecanal and Me2Zn in the presence of TiCl4. (C) 2004 Elsevier Ltd. All rights reserved.

Keywords
Dialkylzinc addition, diastereoselection, racemic 2-alkyladehydes
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-2335 (URN)10.1016/j.tet.2004.09.005 (DOI)000224715100008 ()2-s2.0-5644248089 (Scopus ID)2196 (Local ID)2196 (Archive number)2196 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2017-12-12Bibliographically approved
Larsson, M., Andersson, J., Liu, R. & Högberg, H.-E. (2004). Enantiopure building blocks for the synthesis of 3-methyl-2-alkanols: Diastereoselective methylmetal addition to a chiral 2-methylaldehyde followed by lipase catalysed esterification. Tetrahedron: asymmetry, 15(18), 2907-2915
Open this publication in new window or tab >>Enantiopure building blocks for the synthesis of 3-methyl-2-alkanols: Diastereoselective methylmetal addition to a chiral 2-methylaldehyde followed by lipase catalysed esterification
2004 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 15, no 18, p. 2907-2915Article 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.

Keywords
3-methyl-2-alkanols, dimethylzinc, diastereoselectivity, kinetic resolution
National Category
Chemical Sciences Industrial Biotechnology
Identifiers
urn:nbn:se:miun:diva-873 (URN)10.1016/j.tetasy.2004.07.049 (DOI)000224333100032 ()2194 (Local ID)2194 (Archive number)2194 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2017-12-13Bibliographically approved
Larsson, M. & Högberg, H.-E. (2004). Totalsyntes av två attrahentkomponenter hos Microdiprion pallipes, via en anti-Cramselektiv addition av dimetylzink till en 2-metylaldehyd: Organikerdagarna 2004 i Linköping.
Open this publication in new window or tab >>Totalsyntes av två attrahentkomponenter hos Microdiprion pallipes, via en anti-Cramselektiv addition av dimetylzink till en 2-metylaldehyd: Organikerdagarna 2004 i Linköping
2004 (Swedish)Conference paper, Published paper (Other academic)
Keywords
asymmetry, chelation, total synthesis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-4814 (URN)2462 (Local ID)2462 (Archive number)2462 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2011-04-06Bibliographically approved
Högberg, H.-E. & Larsson, M. (2002). Diasteroselective Addition to Chiral Racemic 2-Methylaldehydes using Organozinc Reagents.: Poster och Abstrakt, 18:e Organikerdagarna, Mitthögskolan, Sundsvall..
Open this publication in new window or tab >>Diasteroselective Addition to Chiral Racemic 2-Methylaldehydes using Organozinc Reagents.: Poster och Abstrakt, 18:e Organikerdagarna, Mitthögskolan, Sundsvall.
2002 (English)Conference paper, Published paper (Other academic)
Keywords
Diastereoselective addition/Chelation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-4415 (URN)1247 (Local ID)1247 (Archive number)1247 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2011-04-06Bibliographically approved
Larsson, M. & Högberg, H.-E. (2001). Diastereoselective Addition of Methylmetallic Reagents to 2-Methylaldehydes. Tetrahedron, 57(35), 7541-7548
Open this publication in new window or tab >>Diastereoselective Addition of Methylmetallic Reagents to 2-Methylaldehydes
2001 (English)In: Tetrahedron, ISSN 0040-4020, Vol. 57, no 35, p. 7541-7548Article in journal (Refereed) Published
Abstract [en]

The preparation of compounds incorporating the 3-hydroxy-2-methyl-1-butyl moiety of high diastereomeric purity is described. These compounds can serve as potential building blocks for the preparation of several kinds of natural products. The diastereoselective addition of a number of methylmetal derivatives to three 3-substituted 2-methylaldehydes in various solvents was studied. An excellent diastereomeric ratio (95:5 anti-Cram/Cram) was obtained with 2-methyl-3-(phenylsulfanyl)propanal (5) and Me2Zn in the presence of TiCl4.

Keywords
asymmetric induction, diastereoselection, chelation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-2167 (URN)10.1016/S0040-4020(01)00713-X (DOI)000170631700013 ()2-s2.0-0035959454 (Scopus ID)1246 (Local ID)1246 (Archive number)1246 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2016-10-17Bibliographically approved
Larsson, M., Nguyen, B.-V., Högberg, H.-E. & Hedenström, E. (2001). Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine Sawfly Microdiprion pallipes (Hymenoptera: Diprionidae). European Journal of Organic Chemistry, 2001(2), 353-363
Open this publication in new window or tab >>Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine Sawfly Microdiprion pallipes (Hymenoptera: Diprionidae)
2001 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, Vol. 2001, no 2, p. 353-363Article in journal (Refereed) Published
Abstract [en]

All sixteen stereoisomers of 3,7,11-trimethyl-2-tridecanol were synthesised in high stereoisomerical purities (> 95%), for use in the identification of the stereoisomers present in females of the pine sawfly Microdiprion pallipes (Fallen) (Hymenoptera: Diprionidae) as the precursor of the actual sex pheromone (which is the propionate), and also for investigation of the biological activities of the esters. The key step in the syntheses was the coupling of each of the enantiomers of cis-3,4-dimethyl-gamma -butyrolactone with each of the four pure stereoisomers of 1-lithio-2,6-dimethyloctanes. The four corresponding alcohols were obtained by lipase-catalysed (Amano PS) kinetic separation, based on selective acylation of either (2R/S,6S)- or (2R/S,GR)-2,6-dimethyl-1-octanol (obtained from the optically pure enantiomers of citronellal). Additionally, a mixture of the 16 possible stereoisomers of 3,7,11-trimethyl-2-tridecanol was also prepared.

Keywords
Feromoner, syntes
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-2279 (URN)10.1002/1099-0690(200101)2001:2<353::AID-EJOC353>3.0.CO;2-Z (DOI)000166621900015 ()2-s2.0-0035139029 (Scopus ID)1859 (Local ID)1859 (Archive number)1859 (OAI)
Note

EUCHEM Conference on Ecological Chemistry: Chemical Communications, Aug 12-15, 1998, Sundsvall, Sweden

Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2017-12-12Bibliographically approved
Larsson, M. & Högberg, H.-E. (1999). Diasteroselective Addition to Chiral Racemic Aldehydes, via Methylmetallic Reagents.: Poster och Abstrakt, ESOC 11, Göteborgs Universitet, Göteborg.
Open this publication in new window or tab >>Diasteroselective Addition to Chiral Racemic Aldehydes, via Methylmetallic Reagents.: Poster och Abstrakt, ESOC 11, Göteborgs Universitet, Göteborg
1999 (English)Conference paper, Published paper (Other academic)
Keywords
Diastereoselective addition
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-4404 (URN)1244 (Local ID)1244 (Archive number)1244 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2011-04-06Bibliographically approved
Larsson, M., Ngyuen, B.-V., Hedenström, E. & Högberg, H.-E. (1998). Synthesis and Studies of the Stereoisomeric Composition in the Sex Pheromone of Microdiprion pallipes.: Poster och abstrakt. Euchem conference, Sundsvall..
Open this publication in new window or tab >>Synthesis and Studies of the Stereoisomeric Composition in the Sex Pheromone of Microdiprion pallipes.: Poster och abstrakt. Euchem conference, Sundsvall.
1998 (English)Conference paper, Published paper (Other academic)
Keywords
Asymmetric synthesis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-4393 (URN)1243 (Local ID)1243 (Archive number)1243 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2016-09-29Bibliographically approved
Högberg, H.-E. & Larsson, M. (1997). Pherodip: Third coordination meeting, Freising, Munchen, Germany, deltagande..
Open this publication in new window or tab >>Pherodip: Third coordination meeting, Freising, Munchen, Germany, deltagande.
1997 (English)Conference paper, Published paper (Other academic)
Keywords
Pheromones
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-5257 (URN)1245 (Local ID)1245 (Archive number)1245 (OAI)
Available from: 2008-09-30 Created: 2008-09-30 Last updated: 2011-04-06Bibliographically approved
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