Highly Diastereoselective and Enantiospecific Allylation of Ketones and Imines Using Borinic Esters: Contiguous Quaternary Stereogenic Centers
Highly Diastereoselective and Enantiospecific Allylation of Ketones and Imines Using Borinic Esters: Contiguous Quaternary Stereogenic Centers
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DOI：
10.1002/anie.201407127
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发表时间：
2014-10-06
影响因子：
16.6
通讯作者：
Aggarwal, Varinder K.
中科院分区：
文献类型：
--
作者：
Chen, Jack L-Y.;Aggarwal, Varinder K.
3，3-二取代烯丙基硼酸酯的反应性不足以与酮和亚胺反应。然而，它们可以通过依次加入nBuLi和TFAA转化为相应的硼酸酯。这些反应性中间体具有反应性和构型稳定性之间的完美平衡。它们增强的反应性允许酮和酮亚胺的高度选择性烯丙基化，并且容易接近具有完全立体控制的相邻的季立体中心。该方法的多功能性证明在所有可能的立体异构体的季-季基序的建设和杂环，二氢异喹啉和吲哚的烯丙基化。
3,3-Disubstituted allylic boronic esters are not sufficiently reactive to react with ketones and imines. However, they can be converted into the corresponding borinic esters by the sequential addition of nBuLi and TFAA. These reactive intermediates possess the perfect balance between reactivity and configurational stability. Their enhanced reactivity allows the highly selective allylation of both ketones and ketimines, and facile access to adjacent quaternary stereocenters with full stereocontrol. The versatility of the methodology is demonstrated in the construction of all possible stereoisomers of a quaternary-quaternary motif and by the allylation of the heterocycles, dihydroisoquinoline and indole.