Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.
Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.
复制标题
DOI：
10.1021/jacs.5b08452
复制
发表时间：
2015-11-04
影响因子：
15
通讯作者：
Peters JC
中科院分区：
文献类型：
--
作者：
Ratani TS;Bachman S;Fu GC;Peters JC
我们最近报道，在光和铜催化剂的存在下，氮亲核试剂，如咔唑和伯酰胺进行C-N偶合与烷基卤在温和的条件下。在本研究中，我们建立了光诱导，铜催化的烷基化也可以应用于C-C键的形成，具体地说，未活化的仲烷基氯化物的氰化可以在室温下实现，以提供腈，一类重要的目标分子。因此，在廉价的铜催化剂（CuI;无配体共添加剂）和容易获得的光源（UVC紧凑型荧光灯泡）的存在下，多种烷基卤化物以良好的产率进行氰化。我们最初的机理研究与[Cu（CN）2]−的激发态可能通过单电子转移在这一过程中发挥作用的假设一致。这项调查提供了一个罕见的例子，过渡金属催化的卤化烷基的氰化，以及第一个插图的光诱导，铜催化的烷基化与碳亲核试剂或仲烷基氯。
We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C–N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C–C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand co-additive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]− may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.