School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
Nat Chem. 2014 Jul;6(7):584-9. doi: 10.1038/nchem.1971. Epub 2014 Jun 8.
The cross-coupling of boronic acids and related derivatives with sp(2) electrophiles (the Suzuki-Miyaura reaction) is one of the most powerful C-C bond formation reactions in synthesis, with applications that span pharmaceuticals, agrochemicals and high-tech materials. Despite the breadth of its utility, the scope of this Nobel prize-winning reaction is rather limited when applied to aliphatic boronic esters. Primary organoboron reagents work well, but secondary and tertiary boronic esters do not (apart from a few specific and isolated examples). Through an alternative strategy, which does not involve using transition metals, we have discovered that enantioenriched secondary and tertiary boronic esters can be coupled to electron-rich aromatics with essentially complete enantiospecificity. As the enantioenriched boronic esters are easily accessible, this reaction should find considerable application, particularly in the pharmaceutical industry where there is growing awareness of the importance of, and greater clinical success in, creating biomolecules with three-dimensional architectures.
硼酸及其相关衍生物与 sp(2) 亲电试剂（铃木-宫浦反应）的交叉偶联是合成中最强的 C-C 键形成反应之一，其应用涵盖了制药、农业化学和高科技材料。尽管该反应具有广泛的用途，但在应用于脂肪族硼酸酯时，这个获得诺贝尔奖的反应的范围相当有限。伯有机硼试剂的效果很好，但仲和叔硼酸酯则不行（除了一些特定的和孤立的例子）。通过一种不涉及使用过渡金属的替代策略，我们发现手性富集的仲和叔硼酸酯可以与富电子芳烃进行交叉偶联，具有几乎完全的对映选择性。由于手性富集的硼酸酯很容易获得，因此该反应应该有相当大的应用，特别是在制药行业，人们越来越意识到构建具有三维结构的生物分子的重要性，并在临床应用上取得了更大的成功。
