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Alkylation of in situ generated imines via photoactivation of strong aliphatic C-H bonds
Molecular Catalysis ( IF 3.9 ) Pub Date : 2021-09-09 , DOI: 10.1016/j.mcat.2021.111841
Serena Pillitteri 1 , Prabhat Ranjan 1 , Leonid G. Voskressensky 2 , Erik V. Van der Eycken 1, 2 , Upendra K. Sharma 1
Affiliation  

The ubiquity of non-activated aliphatic C-H bonds has been the object of evergreen attention for the advantages that the direct functionalization of these strong C-H bonds hold. The development of photoredox catalysis has brought evident advancement in this field, providing a wide array of solutions to overcome the challenges related to the inertness of unactivated C-H bonds. In this regard, the use of polyoxometalate tetrabutylammonium decatungstate (TBADT) provides a straightforward solution for the generation of C-sp3 centered radicals from aliphatic C-H bonds. Albeit the wide utilization of this photocatalyst, only a limited number of radical acceptors has been employed, and scarce reports on multicomponent reactions can be found, mainly due to chemoselectivity challenges and polarity match issues. Our study, therefore, focuses on the development of a broadly applicable strategy for the alkylation of in situ formed imines for the construction of functionalized secondary amines under mild reaction conditions. This atom economic transformation exploits the intrinsic electrophilicity of imines towards radical addition, and the fine-tuning of electronic properties of the starting materials allows the formation of a wide variety of products.



中文翻译:

通过光活化强脂肪族 CH 键使原位生成的亚胺烷基化

由于这些强 CH 键的直接功能化所具有的优势,非活化脂肪族 CH 键的普遍性一直是常青树关注的对象。光氧化还原催化的发展在该领域带来了明显的进步,为克服与未活化 CH 键的惰性相关的挑战提供了广泛的解决方案。在这方面,使用多金属氧酸四丁基十丁基铵 (TBADT) 为 C-sp 3的生成提供了直接的解决方案来自脂肪族 CH 键的中心自由基。尽管这种光催化剂得到了广泛应用,但仅使用了有限数量的自由基受体,而且很少有关于多组分反应的报道,这主要是由于化学选择性挑战和极性匹配问题。因此,我们的研究侧重于开发一种广泛适用的策略,用于原位形成的亚胺的烷基化,在温和的反应条件下构建官能化的仲胺。这种原子经济转化利用亚胺固有的亲电性进行自由基加成,并且对起始材料的电子特性进行微调,可以形成各种各样的产品。

更新日期:2021-09-09
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