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Catalytic enantio- and diastereoselective domino halocyclization and spiroketalization
Nature Catalysis ( IF 42.8 ) Pub Date : 2020-11-09 , DOI: 10.1038/s41929-020-00530-9
Tianyu Zheng , Xinyan Wang , Wing-Hin Ng , Ying-Lung Steve Tse , Ying-Yeung Yeung

Asymmetric domino electrophilic halocyclizations are highly useful in the synthesis of structurally complex and pharmaceutically important compounds. Although some studies aimed at catalytic and enantioselective polyene cyclizations are documented, the chiral products have been limited to fused rings. Here, we report an efficient and highly enantio- and diastereoselective halocyclization and spiroketalization of olefinic keto-acids. Instead of electron-deficient thiourea, in this study electron-rich thiourea catalysts are crucial for high enantioselectivity. The resulting spiro compounds are privileged cores of many drugs and natural products. Our experimental and computational studies revealed that the reaction proceeded via a double dynamic–kinetic resolution mechanism. We anticipate that this work will stimulate the synthesis of other multifunctional compounds via electrophilic halocyclization.



中文翻译:

催化对映和非对映选择性的多米诺卤代化和螺缩酮化

不对称的多米诺亲电子卤代化在合成结构上复杂且具有药学重要性的化合物中非常有用。尽管已记录了一些针对催化和对映选择性多烯环化的研究,但手性产物仅限于稠环。在这里,我们报告了烯烃酮酸的高效,高度对映和非对映选择性的卤代环化和螺缩酮化。在这项研究中,代替缺乏电子的硫脲,富含电子的硫脲催化剂对于高对映选择性至关重要。产生的螺环化合物是许多药物和天然产物的特权核心。我们的实验和计算研究表明,反应是通过双重动力学动力学拆分机制进行的。

更新日期:2020-11-09
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