Formal total synthesis of fostriecin by 1,4-asymmetric induction with an alkyne-cobalt complex

Yujiro Hayashi, Hirofumi Yamaguchi, Maya Toyoshima, Kotaro Okado, Takumi Toyo, Mitsuru Shoji

研究成果: Article査読

32 被引用数 (Scopus)

抄録

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. The synthetic challenges were the construction of four stereogenic centers and the conformationally labile cis-cis-trans-triene moiety. Previous total syntheses have employed at least two asymmetric reactions that required the use of an external chiral auxiliary. Although remote stereoinduction in a 1,4-relationship is considered difficult, we have developed a notable 1,4-asymmetric induction that utilizes an alkyne-cobalt complex for the control of C5 stereochemistry by the C8 stereogenic center. The stereochemistry at C11 was established by 1,3-asymmetric induction with a higherorder alkynyl-zinc reagent. Thus, only one asymmetric reaction requiring an external chiral auxiliary was employed in this route. The labile cis-cis-transtriene unit was constructed at a late stage of the synthesis by diastereoselective coupling of a dienyne and an aldehyde unit, followed by reduction.

本文言語English
ページ(範囲)10150-10159
ページ数10
ジャーナルChemistry - A European Journal
16
33
DOI
出版ステータスPublished - 2010 9 3

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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