3-硅烷基烯丙氧基硅烷的逆Brook重排反应形成罕见的3,3-双硅烷基烯醇.docVIP

  Discovery of the unusual 3,3-bissilyl enols in retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes# 5 10 15 20 25 Gao Lu, Song Zhenlei** (West China School of Pharmacy, Sichuan University) Abstract: In this paper, a detailed study on the retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes has been described. Based on control experiments and NMR studies, rationalizations of formation of the unusual 3,3-bissilyl enols, which is stable to acidic hydrolysis, but can be transformed into the aldehyde under the basic hydrolysis condition. Key words: bissilyl compound; retro-[1,4] Brook rearrangement; enol; 3-silyl allyloxysilane 0 Introduction Bissilyl compounds[1] are a special type of organosilane[2] that appear to be attractive synthons because of their great potential for bifunctional reactivity. However, investigations of these compounds have been limited because of the lack of practical method for their synthesis. Indeed, the installation of two large silyl groups into one carbon center is quite challenging. Solving this problem requires efficient formation of a carbon-silicon bond in a sterically bulky system. Our interest in these compounds led us to focus on the well-known retro-Brook rearrangement,[3] which involves an intramolecular silyl group migration from an oxygen to a carbon atom. The most appealing feature of this reaction is that functionalized organosilane can be rapidly constructed from more accessible silyl ethers. Recently, we communicated a facile retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes 1 promoted by organolithium (Scheme 1).[4] During the studies, we discovered that hydrolysis of the 3,3-bissilyl lithium enolate intermediate 2 gives the unusual enol 3, which is stable to acidic hydrolysis, but can be transformed into the aldehyde 4 under the basic hydrolysis condition. Here we report detailed studies and deeper understanding of this reaction.  Si  1  OSiM  s-BuLi THF/HMPA retro-[1,4] Brook rearrangement