ENANTIOSELECTIVE TOTAL SYNTHESIS OF NOVEL DITERPENOID PYRONES (+)-SESQUICILLIN AND (-)-NALANTHALIDE FROM FUNGAL FERMENTATIONS

被引：11

作者：

Oguchi, Takamasa ^{[1
]}

Watanabe, Kazuhiro ^{[1
]}

Abe, Hideki ^{[1
]}

Katoh, Tadashi ^{[1
]}

机构：

[1] Tohoku Pharmaceut Univ, Dept Chem Pharmaceut Sci, Lab Med Synthet Chem, Aoba Ku, Sendai, Miyagi 9818558, Japan

来源：

HETEROCYCLES | 2010年 / 80卷 / 01期

关键词：

Sesquicillin; Glucocorticoid Antagonist; Nalanthalide; Kv1.3; Blocker; Total Synthesis; SECONDARY ALCOHOLS; REARRANGEMENT; INHIBITOR; SESQUICILLIN; POTENT; KV1.3; (+)-SCYPHOSTATIN; BLOCKERS;

D O I：

10.3987/COM-08-S(S)2

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We efficiently synthesized (+)-sesquicillin (a glucocorticoid antagonist) and (-)-nalanthalide (a potassium channel Kv1.3 blocker) in a convergent and unified manner starting from (+)-5-methyl-Wieland-Miescher ketone. The synthesis involved the following key steps: (i) a [2,3]-Wittig rearrangement of a stannylmethyl ether to install the stereogenic center at C9 and the exo-methylene functionality at C8 present in the trans-decalin portion, (ii) a coupling reaction of a trans-decalin portion with a gamma-pyrone moiety to assemble the requisite whole carbon framework, and (iii) a conversion of a gamma-pyrone moiety to an alpha-pyrone ring to produce (+)-sesquicillin. The present total synthesis has verified the absolute configuration of these natural products.

引用

页码：229 / 250

页数：22

共 30 条

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