152896-89-4Relevant academic research and scientific papers
Total synthesis of patulolide C and its homo, nor, and iso analogs
Leemhuis,Thijs,Zwanenburg
, p. 7170 - 7179 (2007/10/02)
The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to γ-hydroxy α,β-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into amixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are noteworthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.
AN ENANTIOSELECTIVE TOTAL SYNTHESIS OF THE MACROLIDE PATULOLIDE C
Thijs, L.,Egenberger, D. M.,Zwanenburg, B.
, p. 2153 - 2156 (2007/10/02)
A total synthesis of the twelve-membered ring lactone Patulolide C is described.The essentials of this synthesis are: nucleophilic ring opening of R-methyloxirane with a lithium acetylide, a Sharpless epoxidation, strategic use of the photochemical rearra
