Cao Zhu, Sun Yuqian, Chen Yasu, Zhu Chen
Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China.
Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202408177. doi: 10.1002/anie.202408177. Epub 2024 Oct 16.
Given the pivotal role of β-(het)arylethylamine moiety in bioactive molecules, the direct amino(het)arylation of alkenes occupies a privileged position in the construction of (het)arylethylamine derivatives. Herein we devise chiral sulfoximines as novel bifunctional reagents which exhibit remarkable efficiency in the challenging asymmetric alkene aminohetarylation reaction, particularly in terms of reactivity and stereo-control. The chiral reagents can be conveniently accessed in gram scale, and efficiently generate N-centered radicals under mild photochemical conditions. The transformation proceeds through enantioselective 1,4-hetaryl migration, ensuring precise chirality transfer from sulfur- to carbon-centers, rendering wide applicability to both aromatic and aliphatic alkenes. Furthermore, the method is straightforward to operate and does not require transition metals or photosensitizers, making it an attractive and practical option.
鉴于β-（杂）芳基乙胺部分在生物活性分子中的关键作用，烯烃的直接氨基（杂）芳基化在（杂）芳基乙胺衍生物的构建中占据重要地位。在此，我们设计了手性亚砜亚胺作为新型双功能试剂，其在具有挑战性的不对称烯烃氨基杂芳基化反应中表现出显著的效率，特别是在反应性和立体控制方面。这种手性试剂可以方便地以克级规模制备，并在温和的光化学条件下有效地产生氮中心自由基。该转化过程通过对映选择性的1,4-杂芳基迁移进行，确保了从硫中心到碳中心的精确手性转移，使得该方法对芳香族和脂肪族烯烃都具有广泛的适用性。此外，该方法操作简便，不需要过渡金属或光敏剂，是一种有吸引力且实用的选择。
