研究室工作進展 May. 20th, 2018

楊琪  歐陽昆冰* 劉亮 席振峰*

Qi Yang, Kunbing Ouyang*, Liang Liu, and Zhenfeng Xi*

化學進展 2018, 30, 513-527.（綜述，黃志镗先生誕辰九十周年紀念專輯）

Prog. Chem. 2018, 30, 513-527. (Review)

三甲基矽基（TMS）廣泛存在于有機化合物中，并且在有機合成中有重要的應用。矽雜環化合物因其獨特的理化性質而被廣泛地應用于有機合成化學、材料化學和藥物化學中。因此，将含有TMS基團的化合物直接用于矽雜環化合物合成的研究具有重要的意義。在有機合成化學中，碳-矽鍵的切斷是一個非常重要的過程。通過化學計量的有機鎂或有機锂等金屬有機試劑對C(sp³)-Si鍵進行切斷是碳-矽鍵活化的經典方法，然而該方法的反應條件苛刻，應用有限。而過渡金屬催化的反應能夠在較溫和的條件下實現C(sp³)-Si鍵的切斷，這為進一步官能團化C(sp³)-Si鍵提供了一種新方向，同時也是一種高效構建矽雜環化合物的新方法。目前過渡金屬催化活化C(sp³)-Si鍵的研究主要集中在具有張力環或一些具有特定結構的底物中，對于催化活化惰性C(sp³)-Si鍵的研究仍然是一個具有挑戰性的課題。本文結合我們自己的工作綜述了近年來過渡金屬催化的TMS中C(sp³)-Si鍵的方法。

The C(sp³)-Si bond in trialkylsilyl groups such as SiMe₃ is among the most frequently encountered C-Si bonds, because many compounds are substituted with trialkylsilyl groups. Silacycles, particularly siloles, have been recognized and extensively studied for their potential applications in organic synthetic chemistry, material science, and medicinal chemistry. The cleavage and applications of the C-Si bond is important in organic synthetic chemistry. However, classic methods require a stoichiometric amount of either organo-magnesium or organolithium reagent. The harsh conditions in these methods do not tolerate many functional groups, thus limiting the synthetic application of these approaches. Transition-metal-catalyzed cleavage of the C(sp³)-Si bonds would be ideal for overcoming the limitation. The process not only shows a new and unique entry to functionalize the C(sp³)-Si bond, but also presents a powerful method to synthesize diverse organosilanes. Up to now, the majority of successful examples, in which the strategy of transition metal catalyzed reactions was applied into activation of C(sp³)-Si bonds, has concentrated on the strained cyclic compounds and functionalized substrates. Hence, the activation of unactivated C(sp³)-Si bonds remains a challenging issue. This review article summarizes recent reports on transition-metal-catalyzed cleavage and synthetic applications of the C(sp³)-Si bonds. In addition, the organometallic reagent-promoted cleavage of C(sp³)-Si bonds is also presented for comparison.