Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block.
Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block.
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DOI：
10.1038/nature22805
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发表时间：
2017-07-13
期刊：
影响因子：
64.8
通讯作者：
Tambar UK
中科院分区：
文献类型：
--
作者：
Bayeh L;Le PQ;Tambar UK
碳氢化合物的立体选择性氧化代表了过去五十年来合成化学最重要的进步之一。受大自然的启发，化学家开发了不饱和烃的对映选择性二羟基化、环氧化和其他氧化反应。最近，烯烃的催化对映选择性烯丙基 C-H 氧化已成为一种强大的化学策略，简化了药物、天然产物、精细化学品和其他功能材料的生产。烯丙基官能化为手性合成子提供了直接途径，该手性合成子具有从石化原料中新形成的立体中心，同时保留了烯烃官能团作为进一步阐述的手柄。人们已经发现了各种金属基催化剂用于具有环状或末端双键的简单烯烃的对映选择性烯丙型C-H氧化。然而，对于更常见的内烯烃，普遍和选择性的烯丙基氧化仍然难以捉摸。在这里，我们报道了通过与硫属氧化剂的催化不对称杂烯反应，未活化的内烯烃的对映选择性、区域选择性和E/Z选择性烯丙基氧化。该方法代表了选择性地将不对称内烯烃转化为具有高立体选择性和区域选择性的烯丙基官能化产物的第一个例子。多功能烯丙基氧化产物的立体定向转化突出了将内部烯烃快速转化为各种对映体富集结构的潜力，这些结构可用于合成复杂的目标分子。
The stereoselective oxidation of hydrocarbons represents one of the most significant advances in synthetic chemistry over the last fifty years. Inspired by nature, chemists have developed enantioselective dihydroxylations, epoxidations, and other oxidations of unsaturated hydrocarbons. More recently, the catalytic enantioselective allylic C–H oxidation of alkenes has emerged as a powerful chemical strategy, streamlining the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral synthons with a newly formed stereocenter from petrochemical feedstocks while preserving the olefin functionality as a handle for further elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic C–H oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation remains elusive with the more common internal alkenes. Here, we report the enantioselective, regioselective, and E/Z selective allylic oxidation of unactivated internal alkenes via a catalytic asymmetric hetero-ene reaction with a chalcogen-based oxidant. This method represents the first example of selectively converting unsymmetrical internal alkenes into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the multifunctional allylic oxidation products highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be utilized in the synthesis of complex target molecules.
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