Stereodivergent synthesis via iridium-catalyzed asymmetric double allylic alkylation of cyanoacetate.
Stereodivergent synthesis via iridium-catalyzed asymmetric double allylic alkylation of cyanoacetate.
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铱催化氰基乙酸酯的不对称双烯丙基烷基化立体发散合成
DOI：
10.1039/d1sc06115a
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发表时间：
2021-12-15
期刊：
影响因子：
8.4
通讯作者：
Wang CJ
中科院分区：
文献类型：
--
作者：
Shen C;Cheng X;Wei L;Wang RQ;Wang CJ
在有机合成中，能够使用具有高非对映体和对映体控制的单一催化剂快速构建多个C-C键的方法特别有价值。在这里，我们报告了一个Ir催化的双烯丙基烷基化反应中，双亲核氰基乙酸酯与亲电π-烯丙基-Ir物种连续反应，以高产率和良好的立体控制产生各种假C2-对称氰基乙酸酯衍生物。更具有挑战性的连续烯丙基烷基化/烯丙基烷基化与两个不同的烯丙基碳酸酯，可以提供相应的产品轴承三个连续的叔-季-叔立体中心也开发了通过使用改性的催化体系，这是揭示与最初形成的非对映体单烯丙基化中间体的准动态动力学分辨率。值得注意的是，这种顺序过程的立体分散性取决于一个单一的铱催化剂被成功地实现，和多达六个立体异构体可以预测通过结合适当的对映异构体的手性配体的铱催化剂和调整添加顺序的两个不同的烯丙基前体。研究了铱催化氰基乙酸酯的不对称双AAA反应，高产率地得到了具有良好立体控制的氰基乙酸酯衍生物。值得注意的是，准DKR涉及两个不同的烯丙基碳酸酯的顺序协议。
Methods that enable the rapid construction of multiple C–C bonds using a single catalyst with high diastereo- and enantio-control are particularly valuable in organic synthesis. Here, we report an Ir-catalyzed double allylic alkylation reaction in which bisnucleophilic cyanoacetate reacted successionally with electrophilic π-allyl-Ir species, producing various pseudo-C2-symmetrical cyanoacetate derivatives in high yield with excellent stereocontrol. More challenging sequential allylic alkylation/allylic alkylation with two distinct allylic carbonates that can deliver the corresponding products bearing three contiguous tertiary–quaternary–tertiary stereocenters was also developed by using a modified catalytic system, which is revealed to be associated with the quasi-dynamic kinetic resolution of the initially formed diastereomeric monoallylation intermediates. Notably, stereodivergence for this sequential process depending on a single iridium catalyst was successfully realized, and up to six stereoisomers could be predictably prepared by combining the appropriate enantiomer of the chiral ligand for the iridium catalyst and adjusting the adding sequence of two distinct allylic precursors. Ir-catalyzed asymmetric double AAA reaction of cyanoacetate was developed, affording cyanoacetate derivatives in high yield with excellent stereocontrol. Notably, quasi-DKR is involved in the sequential protocol with two distinct allylic carbonates.
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影响因子：
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