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    • Trenner 0
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Publications

Krohn, K.; Vidal, A.; Vitz, J.; Westermann, B.; Abbas, M.; Green, I.; First enantiospecific Baker–Venkataraman-rearrangements aiming at the total synthesis of chiral anthrapyran antibiotics Tetrahedron: Asymmetry 17 3051-3057 (2006) DOI: 10.1016/j.tetasy.2006.11.017
  • Abstract
  • BibText
  • RIS

The base-catalyzed acyl transfer (Baker–Venkataraman reaction) of chiral 2-acetyl-1-hydroxyanthraquionone esters 6 of 2-methylbutanoic acid or 11 of O-allyl lactic acid proceeds with virtually no racemization to ketides 7 and 12. The subsequent acid-catalyzed cyclization to the chiral anthra[1,2-b]pyran antibiotics such as (S)-1″-11-dideoxyespicufolin 8 or 13 also occurs with a very low racemization.

Publications

Scheid, G.; Ruijter, E.; Konarzycka-Bessler, M.; Bornscheuer, U. T.; Wessjohann, L. A.; Synthesis and resolution of a key building block for epothilones: a comparison of asymmetric synthesis, chemical and enzymatic resolution Tetrahedron: Asymmetry 15 2861-2869 (2004) DOI: 10.1016/j.tetasy.2004.06.048
  • Abstract
  • BibText
  • RIS

The asymmetric synthesis and kinetic resolution of a series of acyloins (α-hydroxy ketones) suitable as building blocks for the northern half of epothilones was studied. Three methods were applied to obtain nonracemic compounds at the eventual epothilone C15-position: asymmetric synthesis with Evans’ auxiliary, chemical resolution and enzymatic resolution. The success rate in small scale applications increased in the order given, and the enzymatic resolution was studied in more detail. Out of a set of nine lipases and esterases, lipases from Burkholderia cepacia, Pseudomonas sp., lipase B from Candida antarctica and recombinant esterases from Streptomyces diastatochromogenes exhibited the highest enantioselectivities with E-values ranging from 60 to >200. Pig liver esterase exhibited inverse enantiopreference and only with recombinant enzyme could a moderate selectivity (E = 50, commercial PLE: E = 8) be observed.

Publications

Micskei, K.; Hajdu, C.; Wessjohann, L. A.; Mercs, L.; Kiss-Szikszai, A.; Patonay, T.; Enantioselective reduction of prochiral ketones by chromium(II) amino acid complexes Tetrahedron: Asymmetry 15 1735-1744 (2004) DOI: 10.1016/j.tetasy.2004.04.017
  • Abstract
  • BibText
  • RIS

The reduction of prochiral ketones has been performed by Cr(II) L-amino acid complexes in aqueous DMF solution under mild conditions in good yields and moderate (up to 58%) ee values. The dependence of the yield and enantioselectivity on various factors such as the structure of the ligand, pH and the solvent has also been investigated. A mechanism based on SET from the Cr(II) ion followed by protonation by water and the formation of an organochromium intermediate is also proposed.

Publications

Braga, A. L.; Rubim, R. M.; Schrekker, H. S.; Wessjohann, L. A.; de Bolster, M. W.; Zeni, G.; Sehnem, J. A.; The facile synthesis of chiral oxazoline catalysts for the diethylzinc addition to aldehydes Tetrahedron: Asymmetry 14 3291-3295 (2003) DOI: 10.1016/j.tetasy.2003.08.029
  • Abstract
  • BibText
  • RIS

A range of chiral 4-(1′-hydroxyalkyl)oxazoline catalysts can be obtained in a straightforward two step synthesis, starting from β-hydroxy amino acids like l-serine or l-threonine. Catalyst 4c forms a complex with diethylzinc, effective for the enantioselective addition to aldehydes resulting in high yields and enantiomeric excesses up to >99% even with aliphatic aldehydes. In the latter case the enantiomeric excess showed a marked dependence of the aldehyde's chain length.

Publications

Braga, A. L.; Appelt, H. R.; Schneider, P. H.; Silveira, C. C.; Wessjohann, L. A.; A new functionalized, chiral disulfide derived from L-cysteine: (R,R)-bis[(3-benzyloxazolan-4-yl)-methane] disulfide as a catalyst in the diethylzinc addition to aldehydes Tetrahedron: Asymmetry 10 1733-1738 (1999) DOI: 10.1016/S0957-4166(99)00145-7
  • Abstract
  • BibText
  • RIS

A new, easily accessible, chiral disulfide 3 was prepared from l-cysteine in a short synthetic sequence (Scheme. 1) and applied successfully as a highly efficient catalyst for the enantioselective addition of diethyl zinc to aromatic and aliphatic aldehydes to afford the product alcohols in up to more than 99% ee. In contrast to the more common amino alcohols used in similar reactions, catalyst 3 does not have a protic hydrogen in the form of a free hydroxy group.

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