Wu Haiting, Xu Yougen, Lin An, Wang Zhi, Chen Huanjun, Zhu Xinwei, Gao Yadong, Su Lebin
Bioland Laboratory, Guangzhou, China.
State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing, China.
Nat Commun. 2024 Nov 25;15(1):10207. doi: 10.1038/s41467-024-54532-3.
α-Functionalized Si-, Ge-, B-, Se-, and S-amide moieties are present in many medicinally active molecules, but their synthesis remains challenging. Here, we demonstrate a high-throughput synthesis using amide-sulfoxonium ylides as carbene precursors in a Si-H, Ge-H, B-H, Se-H, and S-H insertion reactions to target a wide range of α-silyl, α-geryl, α-boryl, α-selenyl, and α-sulfur (hetero)amides. The process is featured as simple operation, mild conditions, broad substrate scope, high functional group compatibility, and excellent chemoselectivity. Both experimental and computational studies are conducted to explore the mechanisms underlying the formation of C-Si/Ge/B/Se/S bond. This research highlights the use of highly selective X-H insertion reactions with amide-sulfoxonium ylide-derived carbenes, paving the way for the preparation of diverse functional organosilane, organogermane, organoboron, organoselenium, and organosulfur compounds from accessible and bench-stable precursors.
α-官能化的硅、锗、硼、硒和硫酰胺部分存在于许多具有药用活性的分子中，但其合成仍然具有挑战性。在此，我们展示了一种高通量合成方法，该方法使用酰胺-锍叶立德作为卡宾前体，用于硅氢键、锗氢键、硼氢键、硒氢键和硫氢键插入反应，以合成多种α-硅基、α-锗基、α-硼基、α-硒基和α-硫（杂）酰胺。该过程具有操作简单、条件温和、底物范围广、官能团兼容性高和化学选择性优异等特点。我们进行了实验和计算研究，以探索形成碳-硅/锗/硼/硒/硫键的潜在机制。这项研究突出了酰胺-锍叶立德衍生的卡宾与高选择性X-H插入反应的应用，为从易得且稳定的前体中制备各种功能性有机硅、有机锗、有机硼、有机硒和有机硫化合物铺平了道路。
