Zhou Jun, Jiang Bingyao, Fujihira Yamato, Zhao Zhengyu, Imai Takanori, Shibata Norio
Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan.
Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan.
Nat Commun. 2021 Jun 18;12(1):3749. doi: 10.1038/s41467-021-24031-w.
A regioselective carbosilylation of alkenes has emerged as a powerful strategy to access molecules with functionalized silylated alkanes, by incorporating silyl and carbon groups across an alkene double bond. However, to the best of our knowledge, organic fluorides have never been used in this protocol. Here we disclose the catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides mediated by BuOK. The main feature of this transformation is the selective activation of the C-F bond of an organic fluoride by the silyl boronate without undergoing potential side-reactions involving C-O, C-Cl, heteroaryl-CH, and even CF groups. Various silylated alkanes with tertiary or quaternary carbon centers that have aromatic, hetero-aromatic, and/or aliphatic groups at the β-position are synthesized in a single step from substituted or non-substituted aryl alkenes. An intramolecular variant of this carbosilylation is also achieved via the reaction of a fluoroarene with a ω-alkenyl side chain and a silyl boronate.
通过在烯烃双键上引入硅基和碳基团，烯烃的区域选择性碳硅化反应已成为一种合成具有官能化硅烷化烷烃分子的有效策略。然而，据我们所知，有机氟化物从未用于该反应体系。在此，我们报道了在叔丁醇钾介导下，使用硼酸硅酯和有机氟化物实现烯烃的无催化剂碳硅化反应。该转化反应的主要特点是硼酸硅酯选择性活化有机氟化物的C-F键，而不发生涉及C-O、C-Cl、杂芳基-CH甚至CF基团的潜在副反应。从取代或未取代的芳基烯烃出发，一步合成了各种在β位具有芳香族、杂芳香族和/或脂肪族基团的含叔碳或季碳中心的硅烷化烷烃。通过氟代芳烃与ω-烯基侧链和硼酸硅酯的反应，还实现了该碳硅化反应的分子内变体。
