Total Synthesis of (+)-Psymberin (Irciniastatin A): Catalytic Reagent Control as the Strategic Cornerstone

详细信息    查看全文

• 作者：Amos B. Smith ; ; Jon A. Jurica ; Shawn P. Walsh
• 刊名：Organic Letters
• 出版年：2008
• 出版时间：December 18, 2008
• 年：2008
• 卷：10
• 期：24
• 页码：5625-5628
• 全文大小：167K
• 年卷期：v.10,no.24(December 18, 2008)
• ISSN：1523-7052

文摘

An effective total synthesis of the marine sponge cytotoxin (+)-psymberin [irciniastatin A (1)] has been achieved. Highlights of the strategy include a Diels−Alder reaction between a bis-siloxy diene and an allene to construct the aromatic ring, a boron-mediated aldol reaction to elaborate the C(15−17) all syn stereotriad, catalytic reagent control to set the C(8, 9, 11 and 13) stereogenic centers of the tetrahydropyran core, and a late-stage Curtius rearrangement to install the sensitive N,O-aminal moiety. The synthesis proceeds with a longest linear sequence of 21 steps from commercially available 2,2-dimethyl-1,3-propanediol.