The ex-chiral pool synthesis of the Theodorakis C3-C11 fragment of borrelidin (I) by a chemoenzymic approach in nine steps and 12 \% overall yield starting from enantiopure methyl-branched preen gland wax esters is described. In the initial reaction, the wax ester II was (ω-1)-hydroxylated regioselectively by using a mutant of the cytochrome P 450 monooxygenase CYP102A1 as biocatalyst. The fourth stereocenter in the C3-C11 fragment III was generated by chiral auxiliary mediated alkylation. In order to explain the exptl. results of the alternative epimerization of an all-syn polypropionate, quantum chem. calcns. were performed at the B3LYP/cc-pVDZ level. ［on SciFinder(R)］
%0 Journal Article
%1 ISI:000293497900020
%A Theurer, Matthias
%A El Baz, Yana
%A Koschorreck, Katja
%A Urlacher, Vlada B.
%A Rauhut, Guntram
%A Baro, Angelika
%A Laschat, Sabine
%D 2011
%J European J. Org. Chem.
%K chemie products,Polyketides,Total Biocatalysis,Computational chemistry,Natural from:alexanderdenzel rauhut synthesis theoretische stuttgart theochem
%N 22
%P 4241–4249
%R 10.1002/ejoc.201100412
%T Chemoenzymatic synthesis of the C3-C11-fragment of borrelidin
%U http://dx.doi.org/10.1002/ejoc.201100412
%X The ex-chiral pool synthesis of the Theodorakis C3-C11 fragment of borrelidin (I) by a chemoenzymic approach in nine steps and 12 \% overall yield starting from enantiopure methyl-branched preen gland wax esters is described. In the initial reaction, the wax ester II was (ω-1)-hydroxylated regioselectively by using a mutant of the cytochrome P 450 monooxygenase CYP102A1 as biocatalyst. The fourth stereocenter in the C3-C11 fragment III was generated by chiral auxiliary mediated alkylation. In order to explain the exptl. results of the alternative epimerization of an all-syn polypropionate, quantum chem. calcns. were performed at the B3LYP/cc-pVDZ level. ［on SciFinder(R)］
%@ 1099-0690
@article{ISI:000293497900020,
abstract = {The ex-chiral pool synthesis of the Theodorakis C3-C11 fragment of borrelidin (I) by a chemoenzymic approach in nine steps and 12 {\%} overall yield starting from enantiopure methyl-branched preen gland wax esters is described. In the initial reaction, the wax ester II was (ω-1)-hydroxylated regioselectively by using a mutant of the cytochrome P 450 monooxygenase CYP102A1 as biocatalyst. The fourth stereocenter in the C3-C11 fragment III was generated by chiral auxiliary mediated alkylation. In order to explain the exptl. results of the alternative epimerization of an all-syn polypropionate, quantum chem. calcns. were performed at the B3LYP/cc-pVDZ level. ［on SciFinder(R)］},
added-at = {2019-02-15T17:47:57.000+0100},
author = {Theurer, Matthias and {El Baz}, Yana and Koschorreck, Katja and Urlacher, Vlada B. and Rauhut, Guntram and Baro, Angelika and Laschat, Sabine},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c0f013f62805aec60030f9553413dfa7/theochem},
doi = {10.1002/ejoc.201100412},
interhash = {42f2925da9d726760679f64c49eaa7ae},
intrahash = {c0f013f62805aec60030f9553413dfa7},
isbn = {1099-0690},
issn = {1434193X},
journal = {European J. Org. Chem.},
keywords = {chemie products,Polyketides,Total Biocatalysis,Computational chemistry,Natural from:alexanderdenzel rauhut synthesis theoretische stuttgart theochem},
month = aug,
number = 22,
pages = {4241–4249},
timestamp = {2019-02-15T16:47:57.000+0100},
title = {{Chemoenzymatic synthesis of the C3-C11-fragment of borrelidin}},
url = {http://dx.doi.org/10.1002/ejoc.201100412},
year = 2011
}
