54889-71-3Relevant academic research and scientific papers
Production of chiral hydroxy long chain fatty acids by whole cell biocatalysis of pentadecanoic acid with an E. coli recombinant containing cytochrome P450(BM-3) monooxygenase
Schneider, Silke,Wubbolts, Marcel G.,Sanglard, Dominique,Witholt, Bernard
, p. 2833 - 2844 (2007/10/03)
A multi-step product recovery process for 12-, 13- and 14- hydroxypentadecanoic acids was developed. Biotransformation of Pentadecanoic acid by whole-cells of recombinant E. coli K27 (pCYP102, pGEc47), synthesizing cytochrome P450(BM-3) monooxygenase [EC 1.14.14.1], led to the production of 12-, 13- and 14-hydroxypentadecanoic acids. To prevent further oxidation of these products, the conversion was performed under oxygen- limited conditions. After filtration and hexane extraction of culture supernatants, the hydroxy fatty acids were methylated. The purification process allowed us to separate the mixture of 12-, 13- and 14- hydroxypentadecanoic acid methyl esters into their single regioisomers by reversed-phase HPLC, followed by precipitation of the compounds as white crystals at 4°C and -20°C. The purified hydroxymethyl esters were characterized by GC-MS analysis. Chiral HPLC analysis of the ω-1 product. 14-hydroxypentadecanoic acid methyl ester, indicated that pentadecanoic acid is oxidized by cytochrome P450(BM-3) to optically pure (S)-(+)-14- hydroxypentadecanoic acid at an e.e. of over 95%. This result confirms recent observations by Capdevila that oxidation by cytochrome P450(BM-3) monooxygenase is highly stereoselective.
Orthocarbonsaeure-ester mit 2,4,10-Trioxaadamantanstruktur als Carboxylschutzgruppe; Verwendung zur Synthese von substituierten Carbonsaeuren mit Hilfe von Grignard-Reagenzien
Voss, Gundula,Gerlach, Hans
, p. 2294 - 2307 (2007/10/02)
The surprising stability of 2,4,10-trioxa-3-adamantyl derivatives 1 against nucleophilic substitution by organomagnesium compounds is discussed and shown to be caused by unfavourable stereoelectronic and steric factors governing the substitution of these cage compounds (Scheme 2).As a consequence, a number of Grignard reagents 2 containing the carboxyl group masked as 2,4,10-trioxa-3-adamantyl group could be prepared and have been reacted in a second step with various electrophiles (cf.Scheme 4).In the products 7-13 and 15b the carboxyl masking group is removed by mild ac id hydrolysis and saponification (cf.Scheme 3) to yield the corresponding acids 16a-21a, 22, and 23a.Acids 21a and 23a have been further transformed to give the macrocyclic lactones 24 and 26, isolated from Galbanum oleo-gum-resin, and acid 22 to give 12-methyl-13-tridecanolide (25), isolated from Angelica root oil.In addition 1-bromo-ω-(2,4,10-trioxa-3-adamantyl)alkanes 1c and 1b have been used to synthesize (+/-)-methyl recifeiolate (29b) and pure cis-ambrettolic acid ((Z)-32a).
