Concise Synthesis of (-)-Hodgkinsine, (-)-Calycosidine, (-)-Hodgkinsine B, (-)-Quadrigemine C, and (-)-Psycholeine via Convergent and Directed Modular Assembly of Cyclotryptamines.
Concise Synthesis of (-)-Hodgkinsine, (-)-Calycosidine, (-)-Hodgkinsine B, (-)-Quadrigemine C, and (-)-Psycholeine via Convergent and Directed Modular Assembly of Cyclotryptamines.
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DOI：
10.1021/jacs.7b09929
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发表时间：
2017-12-06
影响因子：
15
通讯作者：
Movassaghi M
中科院分区：
文献类型：
--
作者：
Lindovska P;Movassaghi M
描述了通过环色胺片段的二氮烯定向组装，对映选择性全合成 (-)-霍奇金素、(-)-毛萼苷、(-)-霍奇金素 B、(-)-四联胺 C 和 (-)-精神胆碱。我们的合成策略能够实现完整环色胺亚基的多重定向组装，以聚合合成高度复杂的双二氮烯和三二氮烯中间体。从这些中间体中光挤出二氮能够完全立体选择性地形成所有 C3a–C3a' 和 C3a–C7' 碳碳键以及所有相关的四元立构中心。在一个代表性的例子中，一步从高级中间体中光挤出三个二氮分子，导致四个四元立构中心的完全受控引入，并引导四个环色胺单体组装成(−)-四嗪C。通过使用电子衰减的肼亲核试剂进行银促进加成的芳基烷基二氮烯合成新方法，使这些复杂的二氮烯的合成成为可能。 C3a-溴环色胺。在复杂环境中应用 Rh 和 Ir 催化的 C-H 胺化反应分别快速获得 C3a 和 C7 官能化环色胺单体，用于二氮烯合成。这种完整环色胺的聚合和模块化组装提供了第一个解决方案，通过单体在具有挑战性的连接和相关的四元立构中心的完全立体选择性结合来获取这些生物碱，如我们对寡环色胺生物碱家族的五个成员的合成所示。
The enantioselective total synthesis of (−)-hodgkinsine, (−)-calycosidine, (−)-hodgkinsine B, (−)-quadrigemine C, and (−)-psycholeine through a diazene-directed assembly of cyclotryptamine fragments is described. Our synthetic strategy enables multiple and directed assembly of intact cyclotryptamine subunits for convergent synthesis of highly complex bis- and tris-diazene intermediates. Photoextrusion of dinitrogen from these intermediates enables completely stereoselective formation of all C3a–C3a' and C3a–C7' carbon–carbon bonds and all the associated quaternary stereogenic centers. In a representative example, photoextrusion of three dinitrogen molecules from an advanced intermediate in a single-step led to completely controlled introduction of four quaternary stereogenic centers and guided the assembly of four cyclotryptamine monomers en route to (−)-quadrigemine C. The synthesis of these complex diazenes was made possible through a new methodology for synthesis of aryl-alkyl diazenes using electronically attenuated hydrazine-nucleophiles for a silver-promoted addition to C3a-bromocyclotryptamines. The application of Rh- and Ir-catalyzed C–H amination reactions in complex settings were used to gain rapid access to C3a- and C7-functionalized cyclotryptamine monomers, respectively, used for diazene synthesis. This convergent and modular assembly of intact cyclotryptamines offers the first solution to access these alkaloids through completely stereoselective union of monomers at challenging linkages and the associated quaternary stereocenters as illustrated in our synthesis of five members of the oligocyclotryptamine family of alkaloids.
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影响因子：
16.6
作者：
Foo, Klement;Newhouse, Timothy;Mori, Ikue;Takayama, Hiromitsu;Baran, Phil S.
通讯作者：
Baran, Phil S.
影响因子：
5.1
作者：
GUERITTEVOEGELEIN, F;SEVENET, T;POTIER, P
通讯作者：
POTIER, P
DOI：
10.1002/anie.201507549
发表时间：
2016-03-18
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Büschleb M;Dorich S;Hanessian S;Tao D;Schenthal KB;Overman LE
通讯作者：
Overman LE
影响因子：
2.1
作者：
BALDWIN, JE;ADLINGTON, RM;PERRY, MWD
通讯作者：
PERRY, MWD
影响因子：
3.6
作者：
GUZIEC, FS;WEI, DC
通讯作者：
WEI, DC