Stereoselective synthesis and NMR characterization of C-24 epimeric pairs of 24-alkyl oxysterols.
作者： Shoujiro Ogawa , Hiroaki Kawamoto , Takashi Mitsuma , Hiroki Fujimori , Tatsuya Higashi
DOI: 10.1007/S11745-012-3739-1
关键词:
摘要: Two pairs of C-24 epimeric (24R)-/(24S)-24-hydroxy-24-methyl-5α-cholestan-3β-yl acetates and (24R)-/(24S)-25-hydroxy-24-methyl-5α-cholestan-3β-yl as well some related 24-ethyl oxysterol analogs were stereoselectively synthesized directly from the respective parent 24-alkyl sterols by a remote O-insertion reaction with 2,6-dichloropyridine N-oxide (DCP) in presence catalytic amount (5,10,15,20-tetramesitylporphrinate) ruthenium(II) carbonyl complex [Ru(TMP)CO] HBr. 1H- 13C-NMR signals serving to differentiate each two interpreted. The alkyl oxysterols at found be effectively characterized aromatic solvent-induced shift (ASIS) C5D5N, particularly for difference 13C resonances substituted cholestane side chain. A method differentiating 1H signal assignment terminal 26-/27-CH3 iso-octane chain was also discussed on basis combined use preferred conformational analysis HMQC HMBC techniques. present may useful determining stereochemical configuration this type oxysterols.
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