The catalytic Sakurai reaction
The catalytic Sakurai reaction
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DOI：
10.1021/jo0105641
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发表时间：
2001-12-14
影响因子：
3.6
通讯作者：
Chang, S
中科院分区：
文献类型：
--
作者：
Lee, PH;Lee, K;Chang, S
Sakurai 反应，即烯丙基三甲基硅烷与共轭烯酮进行路易斯酸加成形成 δ, ε-烯酮, 1 已广泛应用于有机合成、天然产物合成 2 以及一些杂环化合物的制备中。 3 它们现在被认为是形成 CC 键的最有效方法之一，并且分子间和分子内反应的例子4 均已报道。樱井反应对于新形成的 CC 键具有区域特异性。 Sakurai 反应中使用的路易斯酸范围很广，其中 TiCl4、AlCl3 和 BF3:OEt2 通常对烯丙基化最有效。然而，在所有情况下，该过程都需要化学计量量甚至过量的路易斯酸以获得合理的反应速率和可接受的产物产率。尽管已经报道了一些催化Sakurai反应的例子，4j,k本文中我们公开了一种在三甲基氯硅烷(TMSCl)存在下使用催化量的InCl 3 的新型催化Sakurai反应。
Sakurai reactions, Lewis acid additions of allyltrimethylsilane with conjugated enones to form δ, ϵ-enones, 1 have been extensively applied in organic synthesis, in natural product synthesis, 2 and in the preparation of some heterocyclic compounds. 3 They are now considered to be one of the most efficient means of CC bond formation, and examples of both inter-and intramolecular reactions4 have been reported. Sakurai reactions are regiospecific with regard to the newly formed CC bond. The range of Lewis acids employed in Sakurai reactions is extensive, among which TiCl4, AlCl3, and BF3: OEt2 are in general the most effective for the allylations. In all cases, however, the procedures require a stoichiometric amount or even an excess of the Lewis acid to obtain reasonable reaction rates and acceptable yields of products. Although a few examples of catalytic Sakurai reactions have been reported, 4j, k herein we disclose a novel and catalytic Sakurai reaction using catalytic amounts of InCl3 in the presence of trimethylsilyl chloride (TMSCl).