Enantiodivergent Synthesis of Allenes by Point-to-Axial Chirality Transfer
Enantiodivergent Synthesis of Allenes by Point-to-Axial Chirality Transfer
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通过点到轴手性转移对映异构合成丙二烯
DOI：
10.1002/ange.201804446
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发表时间：
2018
影响因子：
--
通讯作者：
Armstrong R
中科院分区：
文献类型：
--
作者：
Armstrong R
本文介绍了一种合成多取代联烯的对映体发散法。通过α-硒代烯基硼酸酯与锂化氨基甲酸酯的同系化反应合成了高度对映体富集的点手性硼酸酯，并消除以形成轴向手性丙二烯产物。通过采用氧化或烷基化条件，顺式和反式消除都可以实现完全的立体特异性。该方法能够从点手性前体的单一异构体合成MorPallenes，并且可以用于二取代、三取代和四取代的联烯的对映选择性组装。
An enantiodivergent method for the synthesis of multiply substituted allenes is described. Highly enantioenriched, point‐chiral boronic esters were synthesized by homologation of α‐seleno alkenyl boronic esters with lithiated carbamates and eliminated to form axially chiral allene products. By employing either oxidative or alkylative conditions, bothsynandantielimination could be achieved with complete stereospecificity. The process enables the synthesis of eitherMorPallenes from a single isomer of a point‐chiral precursor and can be employed for the enantioselective assembly of di‐, tri‐, and tetrasubstituted allenes.