Shi Yufeng, Qin Ying, Li Zhong-Qiu, Xu Yize, Chen Shuhan, Zhang Jinyu, Li Yu-An, Wu Yaxin, Meng Fei, Zhong Yu-Wu, Zhao Dongbing
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.
Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Angew Chem Int Ed Engl. 2024 Sep 2;63(36):e202405520. doi: 10.1002/anie.202405520. Epub 2024 Jul 30.
Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction of silicon-stereogenic architectures by functionalization of Si-bound methyl group has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed the enantioselective silylmethyl functionalization involving the aryl to alkyl 1,5-palladium migration to access diverse naphthalenes possessing an enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy to note that the realization of asymmetric induction at the step of metal migration itself remains challenging. Our study constitutes the first enantioselective aryl to alkyl 1,5-palladium migration reaction. The key to the success is the discovery and fine-tuning of the different substituents of α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, which ensure the enantioselectivity and desired reactivity.
硅键合甲基的官能团化提供了一种有效合成各种有机硅烷的方法。然而，尽管近期在手性硅的合成方面取得了显著进展，但通过硅键合甲基的官能团化来不对称构建含硅手性结构的方法尚未见报道。在此，我们报道了对映选择性硅甲基官能团化反应，该反应涉及芳基到烷基的1,5-钯迁移，以合成多种具有对映体富集的手性硅中心的萘类化合物，而这些化合物在此之前是无法获得的。值得注意的是，在金属迁移步骤实现不对称诱导仍然具有挑战性。我们的研究构成了首例对映选择性芳基到烷基的1,5-钯迁移反应。成功的关键在于发现并微调基于α,α,α,α-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）的亚磷酰胺的不同取代基，这些取代基确保了对映选择性和所需的反应活性。
