Convergent and Biomimetic Enantioselective Total Synthesis of (-)-Communesin F.
Convergent and Biomimetic Enantioselective Total Synthesis of (-)-Communesin F.
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(-)-Communesin F 的收敛和仿生对映选择性全合成。
DOI：
10.1021/jacs.6b04072
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发表时间：
2016-06-22
影响因子：
15
通讯作者：
Movassaghi M
中科院分区：
文献类型：
--
作者：
Lathrop SP;Pompeo M;Chang WT;Movassaghi M
首次基于后期异源二聚化和缩醛胺交换的仿生对映选择性全合成（-）-communesin F。我们的合成特点是两个先进的片段，以确保拥挤的C3 a-C3 a '连接在三个步骤中，由一个高效的生物启发的胺重组进入七环communesin核心，只有两个额外的步骤，方便的二氮烯定向组装。这两个片段的对映选择性合成，重点包括色胺衍生物的催化不对称卤环化和非对映选择性羟胺化反应，立体选择性亚磺亚胺烯丙基化，以及通过新的银促进的亲核胺化或铑催化的C-H胺化方案的有效的环色胺-C3 a-氨基磺酸酯合成。片段的多功能合成、它们的立体控制组装、以及由原位监测实验支持的有效的胺交换，以及公社蛋白核心的最后阶段N1′-酰化，提供了（−）-公社蛋白F的高度收敛合成。
The first biomimetic enantioselective total synthesis of (−)-communesin F based on a late-stage heterodimerization and aminal exchange is described. Our synthesis features the expedient diazene–directed assembly of two advanced fragments to secure the congested C3a–C3a′ linkage in three steps, followed by a highly efficient biogenetically inspired aminal reorganization to access the heptacyclic communesin core in only two additional steps. Enantioselective syntheses of the two fragments were developed, with highlights including the catalytic asymmetric halocyclization and diastereoselective oxyamination reactions of tryptamine derivatives, a stereoselective sulfinimine allylation, and an efficient cyclotryptamine–C3a-sulfamate synthesis by either a new silver–promoted nucleophilic amination or a rhodium–catalyzed C–H amination protocol. The versatile synthesis of the fragments, their stereocontrolled assembly, and the efficient aminal–exchange as supported by in situ monitoring experiments, in addition to the final stage N1′-acylation of the communesin core provide a highly convergent synthesis of (−)-communesin F.