Progress toward a Convergent, Asymmetric Synthesis of Jervine
Progress toward a Convergent, Asymmetric Synthesis of Jervine
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Jervine 的收敛、不对称合成取得进展
DOI：
10.1021/acs.orglett.0c00972
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发表时间：
2020
期刊：
影响因子：
5.2
通讯作者：
Johnson, Jeffrey S.
中科院分区：
文献类型：
--
作者：
Zavesky, Blane P.;De Jesús Cruz, Pedro;Johnson, Jeffrey S.
提出了对映选择性合成藜芦生物碱jervine的聚合方法的进展。这两个必需的片段是由经济且容易获得的试剂立体选择性且有效地形成的。关键反应包括（a）高度非对映选择性的爱尔兰-克莱森重排，以在四氢呋喃 E 环上的胺和甲基之间建立必要的顺式关系； (b) 非对映选择性硒醚化反应，使 D/E oxaspiro[4.5]癸烯能够组装成所需的构型； (c) 丰富的非手性二醇在生成关键四碳结构单元的过程中进行酶促去对称化，作为受保护的罗氏酯还原的实用替代方案。
Progress toward a convergent approach for the enantioselective synthesis of theVeratrumalkaloid jervine is presented. The two requisite fragments were stereoselectively and efficiently fashioned from economical and readily available reagents. Key reactions include (a) a highly diastereoselective Ireland−Claisen rearrangement to establish the necessarycis-relationship between the amine and methyl group on the tetrahydrofuran E-ring; (b) a diastereoselective selenoetherification reaction that enabled the assembly of the D/E oxaspiro[4.5]decene in the needed configuration; and (c) an enzymatic desymmetrization of an abundant achiral diol en route to a key four-carbon building block as a practical alternative to a protected Roche ester reduction.