Dai Rui-Han, Wang Qi, Chen Zhi-Xiong, Tian Shi-Kai
Hefei National Laboratory for Physical Sciences at the Microscale, Center for Excellence in Molecular Synthesis (CAS), and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
J Org Chem. 2021 Feb 5;86(3):3065-3073. doi: 10.1021/acs.joc.0c02721. Epub 2021 Jan 8.
An unprecedented asymmetric aza-Claisen rearrangement between enantioenriched α-chiral allylamines and allenones was found to proceed in the absence of catalysts and additives at room temperature. The rearrangement, followed by hydrolysis, provides convenient access to structurally diverse δ-chiral β-diketones in good to excellent yields with excellent retention of enantiopurity. This protocol proved powerful for the construction of an all-carbon quaternary stereocenter with high enantiopurity.
发现在室温下，对映体富集的α-手性烯丙胺与联烯酮之间能发生前所未有的不对称氮杂克莱森重排，且无需催化剂和添加剂。该重排反应随后经水解，能以良好至优异的产率方便地得到结构多样的δ-手性β-二酮，对映体纯度保持优异。该方法被证明对于构建具有高对映体纯度的全碳季立体中心非常有效。
