Copper-Catalyzed Borocarbonylative Coupling of Internal Alkynes with Unactivated Alkyl Halides: Modular Synthesis of Tetrasubstituted β-Borylenones
Copper-Catalyzed Borocarbonylative Coupling of Internal Alkynes with Unactivated Alkyl Halides: Modular Synthesis of Tetrasubstituted β-Borylenones
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DOI：
10.1002/anie.201804883
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发表时间：
2018-08-06
影响因子：
16.6
通讯作者：
Mankad, Neal P.
中科院分区：
文献类型：
--
作者：
Cheng, Li-Jie;Mankad, Neal P.
报道了一种合成四取代烯酮的一般方法，该反应是利用铜催化的四组分偶联反应，以简单的化学原料：内炔、烷基卤化物、双(频那多)二硼(B(2)Pin(2))和CO为原料，在β-位进行硼化反应。使用这种方法可以有效地获得广泛的高度官能化的β-硼化烯酮，这是一类基本上未知的有机化合物。全碳四取代烯酮的合成是在Suzuki-Miyaura偶联反应中通过使用β-硼化烯单元实现的。通过卤化、氧化和原脱基等反应，进一步证明了该方法的有效性。这些转化反应生成了高密度取代的烯丙醇和酮。
Reported is a general procedure to synthesize tetrasubstituted enones, which are borylated in the beta-position, using a copper-catalyzed four-component coupling reaction of simple chemical feedstocks: internal alkynes, alkyl halides, bis(pinacolato)diboron (B(2)pin(2)), and CO. A broad scope of highly functionalized beta-borylated enones, a largely unknown class of organic compounds, can be accessed efficiently using this method. The synthesis of all-carbon tetrasubstituted enones was realized by employing the beta-borylated enone unit, without purification, in a Suzuki-Miyaura coupling. The utility of the method was further demonstrated by various transformations, including halogenation, oxidation, and protodeboration, of the corresponding reduced oxaborole species to provide densely substituted allylic alcohol and ketone products.