Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Abstract

Transition-metal-catalyzed sila-cycloaddition has been a promising tool for accessing silacarbocycle derivatives, but the approach has been limited to a selection of well-defined sila-synthons. Herein, we demonstrate the potential of chlorosilanes, which are industrial feedstock chemicals, for this type of reaction under reductive nickel catalysis. This work extends the scope of reductive coupling from carbocycle to silacarbocycle synthesis and from single C–Si bond formation to sila-cycloaddition reactions. The reaction proceeds under mild conditions and shows good substrate scope and functionality tolerance, and it offers new access to silacyclopent-3-enes and spiro silacarbocycles. The optical properties of several spiro dithienosiloles as well as structural variations of the products are demonstrated.

Nickel-Catalyzed C(sp3)–Sb Coupling of Chlorostibines with Unactivated Alkyl Chlorides and In Vitro Anticancer Activity of Products

“…Herein, we developed nickel-catalyzed C­(sp 3 )–Sb cross-coupling through chlorostibines with unactivated alkyl chlorides. Transition-metal-catalyzed reductive coupling of electrophiles has emerged as a powerful tool for constructing C–C and C–Z bonds. The relative works for C–metal bond formation include C­(sp 2 )–Ge and C­(sp 3 )–Ge bonds .…”

Nickel-Catalyzed Reductive [4＋1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes to Access Dihydrosiloles

“…近年来硅杂环化合物的催化合成及应用受到越来 越多的关注, 一些新的合成策略不断涌现 [1] , 其中过渡 金属催化硅基环加成反应已逐渐成为合成硅杂环化合 物的最重要工具之一, 在化学、药物和材料科学的许多 领域发挥着重要作用 [2][3][4] . 在各种硅基环加成反应中, 催 化合成五元硅碳杂环化合物的硅基环加成反应尤其备 受重视, 最近 Suginome 等 [5] 报道了(Et 最近, 兰州大学化学化工学院舒兴中课题组 [6] 报道 了以有机硅工业原料氯硅烷为反应物, 在镍金属的还原 催化下实现了其与 1,3-二烯的硅基[4＋1]环加成反应 (Scheme 1, c). 该工作将还原偶联反应从简单的碳环构 建反应扩展到硅杂环的合成, 并且从单个 C-Si 键的形 成扩展到硅基环加成反应, 反应条件温和, 具有良好的 底物范围和官能团兼容性, 为硅杂环戊烯即二氢噻咯和 螺环硅碳环化合物的合成提供了新方法, 同时还研究了 若干种螺二硫代噻咯化合物的光学性质以及构效关系.…”