[2,3]-Wittig重排不同于传统的[3,3]-Claisen重排,自发现起得到了合成化学家的广泛关注,并得到了充分的研究。由于其能实现化学键高效简洁的转化,且能得到具有高度衍生化的含烯丙基的产物,[2,3]-Wittig重排在全合成领域具有重要的地位。本文旨在从该反应的最初发现、重排前体的构建、不对成重排的实现等方面,全面系统的介绍有别于传统[3,3]-Claisen重排的[2,3]-Wittig重排反应。
[2,3]-Wittig rearrangement is an attractive reaction, which is extremely different from the traditional [3,3]-claisen rearrangement, and has received extensive attention from chemists since its initial discovery. Due to its efficient and concise transformation of chemical bonds and the ability to obtain highly derivatized allyl-containing products, [2,3]-Wittig rearrangement plays an important role in total synthesis. This review attempts to provide comprehensive knowledge about [2,3]-Wittig rearrangement, including initial discovery, construction of substrates, asymmetrical rearrangements, and so on.
[23]-Wittig重排,重排前体,烯丙基化, [23]-Wittig Rearrangement Substrates of Rearrangement Allylation摘要
[2,3]-Wittig rearrangement is an attractive reaction, which is extremely different from the traditional [3,3]-claisen rearrangement, and has received extensive attention from chemists since its initial discovery. Due to its efficient and concise transformation of chemical bonds and the ability to obtain highly derivatized allyl-containing products, [2,3]-Wittig rearrangement plays an important role in total synthesis. This review attempts to provide comprehensive knowledge about [2,3]-Wittig rearrangement, including initial discovery, construction of substrates, asymmetrical rearrangements, and so on.
Keywords:[2,3]-Wittig Rearrangement, Substrates of Rearrangement, Allylation
该反应还第一次以锡-锂交换的方式生成碳负离子,有别于传统的拔质子的方式,使底物兼容性有了大幅提高。因此,Still-Wittig 重排反应广泛应用于天然产物全合成中,如Pre-schisanartanin C [10]、(±)-Maoecrystal V [11]、(−)-Candelalide A [12] (图3)等。
1972年,M. J. LeBelle课题组 [13] 发现l-苄基-4-乙烯基-2-氮杂环丁烷在LDA作用下,发生[2,3]-重排,扩环得到五元内酰胺,但是同时有较高比例的[1,2]-重排产物(比例为3:2,总产率90%) (图4)。1995年,Iain Coldham [14] 发现乙烯基氮丙啶在LDA作用下,可以发生[2,3]-重排,以中等收率得到扩环的氨基酸衍生物。由于三元环和四元环都具有较大的张力,[2,3]-重排不适用于无张力环和链状底物中,反应不具备普适性。同年,Martin E. Swarbrick [15] 发现将烯丙基苄基胺的氮原子进行Boc保护,通过攫取苄位的氢原子形成碳负离子,以82%的产率得到重排产物。该反应通过设计合适的链状重排前体,解决了无张力驱动下的[2,3]-aza-Wittig重排反应,极大的推动了该领域的发展。2010年,James C. Anderson课题组 [16] 将底物范围拓展到含羰基化合物的三级胺,以91%的产率和高对映选择性(dr > 20:1)得到α-氨基酸酯衍生物。
图5. 不对成Wittig重排
除了烯丙基三级胺类结构外,氮叶立德也可以进行[2,3]-aza-Wittig重排反应。随之而来的是,如何高效构建氮叶立德成为研究者关注的重点。2007年,Robert E. Gawley课题组 [17] 报道了从环状二级胺出发,与卤代烃制备季铵盐后,在丁基锂作用下形成碳负离子重排。季铵盐需要分离,且分离困难,于是Andrew D. Smith课题组 [18] 随后报道了二级胺和卤代烃的一锅法[2,3]-aza-Wittig重排反应的研究。
此外,Uttam K. Tambar课题组 [19] 于2011年报道了,在钯催化下,实现了烯丙基乙基碳酸酯与二级胺原位构建叶立德,并发生[2,3]-重排。
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