Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings.
Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings.
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DOI：
10.1021/jacs.7b05155
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发表时间：
2017-08-23
影响因子：
15
通讯作者：
Larrosa I
中科院分区：
文献类型：
--
作者：
Perry GJP;Quibell JM;Panigrahi A;Larrosa I
从物美价廉的原料中开发出具有高综合价值的产品具有重要意义。芳基碘化合物是合成功能分子的重要构件，从化学原料合成芳基碘化合物的有效方法备受人们的追捧。在这里，我们报告了一种低成本的脱羧基碘化反应，它简单地发生在现成的苯甲酸和碘中。该反应是可扩展的，反应的范围和稳健性得到了彻底的检验。机理研究表明，该反应不是通过自由基反应进行的，这与经典的Hunsdiecker脱羧型卤化反应不同。此外，DFT研究允许在我们的程序和目前过渡金属催化的脱羧基之间进行比较。这一方法在芳烃氧化交叉偶联反应中的应用证明了它的有效性，这些反应是通过以I2为末端氧化剂的脱羧基/C-H或双脱羧基活化法进行的。这一策略允许制备以前无法通过脱羧基方法获得的联芳基，并且与现有的脱羧基氧化偶联相比具有其他优点，因为避免了化学计量比的过渡金属。
Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C–H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
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DOI：
10.1126/science.1258538
发表时间：
2014-10-24
期刊：
Science (New York, N.Y.)
影响因子：
--
作者：
Chu L;Xiao KJ;Yu JQ
通讯作者：
Yu JQ
影响因子：
2.1
作者：
Camps, P;Lukach, AE;Vázquez, S
通讯作者：
Vázquez, S
影响因子：
16.6
作者：
Cambeiro, Xacobe C.;Boorman, Tanya C.;Larrosa, Igor
通讯作者：
Larrosa, Igor
影响因子：
15
作者：
Chen, Xiao;Hao, Xue-Shi;Yu, Jin-Quan
通讯作者：
Yu, Jin-Quan
影响因子：
4.9
作者：
Cant, Alastair A.;Bhalla, Rajiv;Sutherland, Andrew
通讯作者：
Sutherland, Andrew