Highly enantio- and diastereoselective one-pot synthesis of acyclic epoxy alcohols and allylic epoxy alcohols
Highly enantio- and diastereoselective one-pot synthesis of acyclic epoxy alcohols and allylic epoxy alcohols
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DOI：
10.1021/ja051291k
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发表时间：
2005-10-26
影响因子：
15
通讯作者：
Walsh, PJ
中科院分区：
文献类型：
--
作者：
Kelly, AR;Lurain, AE;Walsh, PJ
在这份报告中，我们概述了一种高对映体和非对映选择性的一锅法，以有效地合成合成有用的无环环氧醇和烯丙基环氧醇。我们的方法利用高对映选择性的C-C键形成反应来设定初始手性。然后，在钛四醇盐存在下，用氧气或TBHP原位环氧化得到的烯丙基锌醇盐中间体。具有最多三个连续立体中心的环氧醇在一锅中形成，具有良好的对映和非对映选择性。在醇锌中间体含有两种不同的烯丙基烯烃的情况下，更富电子的双键被化学选择性地环氧化以得到烯丙基环氧醇。这种方法代表了一种高效、立体选择性和化学选择性的方法来合成一系列有用的环氧醇和烯丙基环氧醇产品，这些产品以前很难获得。
In this report, we outline a highly enantio- and diastereoselective one-pot method for the efficient synthesis of synthetically useful acyclic epoxy alcohols and allylic epoxy alcohols. Our method takes advantage of a highly enantioselective C-C bond-forming reaction to set the initial chirality. The resulting allylic zinc alkoxide intermediate is then epoxidized in situ using either dioxygen or TBHP in the presence of a titanium tetraalkoxide. Epoxy alcohols with up to three contiguous stereocenters are formed in one pot with excellent enantio- and diastereoselectivity. In cases where the zinc alkoxide intermediates contain two different allylic olefins, the more electron-rich double bond is chemoselectively epoxidized to afford an allylic epoxy alcohol. This method represents a highly efficient, stereoselective, and chemoselective approach to the synthesis of a wide range of useful epoxy alcohol and allylic epoxy alcohol products that were previously difficult to access.