Total synthesis of (+)-asteltoxin
Total synthesis of (+)-asteltoxin
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DOI：
10.1021/ja034332q
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发表时间：
2003-05-07
影响因子：
15
通讯作者：
Cha, JK
中科院分区：
文献类型：
--
作者：
Eom, KD;Raman, JV;Cha, JK
通过双（四氢呋喃）醛53和α-吡喃酮膦酸酯5的Horner-Emmons烯化反应实现了（+）-asteltoxin（1）的收敛合成。一个关键步骤的特点是立体选择性建设的空间拥挤的季中心嵌入在密集的官能化双（四氢呋喃）亚基的刘易斯酸催化，频哪醇型重排的环氧甲硅烷基醚。这种关键的重排方法平行的生物合成途径1和成熟的立体控制合成结构复杂的天然产物的应用。
A convergent synthesis of (+)-asteltoxin (1) has been achieved by the Horner-Emmons olefination of bis(tetrahydrofuran) aldehyde 53 and alpha-pyrone phosphonate 5. A key step features the stereoselective construction of a sterically congested quaternary center embedded in the densely functionalized bis(tetrahydrofuran) subunit by a Lewis acid-catalyzed, pinacol-type rearrangement of an epoxy silyl ether. This pivotal rearrangement methodology parallels the proposed biosynthetic pathway of 1 and is ripe for applications to the stereocontrolled synthesis of structurally complex natural products.