Total synthesis of (+)-myriocin and (-)-sphingofungin E from aldohexoses using overman rearrangement as the key reaction

Takeshi Oishi, Koji Ando, Kenjin Inomiya, Hideyuki Sato, Masatoshi Iida, Noritaka Chida

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Abstract

Total synthesis starting from aldohexoses of naturally occurring α-substituted α-amino acids, (+)-myriocin (1) and (-)-sphingofungin E (2), is described. Overman rearrangement of allylic trichloroacetimidate 6E derived from D-mannose effectively generated the tetrasubstituted carbon with nitrogen, and subsequent Wittig olefination afforded the highly functionalized moiety 3 of myriocin stereoselectively. Sulfone-mediated coupling reaction of the allyl bromide 3 with C12 hydrophobic part 4 successfully constructed the carbon framework possessing E-olefin 28. Removal of the sulfone and protecting groups completed the chiral and stereoselective total synthesis of (+)-myriocin (1). A similar transformation starting from D-glucose also accomplished the total synthesis of (-)-sphingofungin E (2).

Original languageEnglish
Pages (from-to)1927-1947
Number of pages21
JournalBulletin of the Chemical Society of Japan
Volume75
Issue number9
DOIs
Publication statusPublished - 2002 Sep 1

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ASJC Scopus subject areas

  • Chemistry(all)

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