Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).
Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).
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DOI：
10.1021/jacs.0c06995
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发表时间：
2020-09-09
影响因子：
15
通讯作者：
Neufeldt SR
中科院分区：
文献类型：
--
作者：
Entz ED;Russell JEA;Hooker LV;Neufeldt SR
非三氟苯酚衍生物的Suzuki-Miyaura偶联的当前方法受到其对包括芳基氯化物在内的卤化物的不耐受性的限制。这是因为Ni(0)和Pd(0)经常以与大多数Ar-O键相似或更快的速度进行有机卤化物的氧化加成。密度泛函和化学计量氧化加成研究表明，在芳基氯化物存在下，小分子膦，特别是PMe3，在促进Ni(0)与芳基对甲苯磺酸盐和其他C-O键的优先反应方面是独一无二的。这种选择性被首次用于镍催化的氯代苯酚衍生物的C-O选择性Suzuki-Miyaura偶联反应，其中含氧离开基团不是氟磺酸盐等氟磺酸盐。计算研究表明，PMe3和其他膦之间的发散选择性的来源不同于先前的配体控制的化学发散交叉偶联的例子。由于电子和空间因素的共同作用，PMe3在对甲苯磺酸盐上发生选择性反应。在氧化加成过程中，镍与对甲苯磺酸盐的磺酰氧之间的紧密相互作用对观察到的选择性是至关重要的。
Current methods for Suzuki-Miyaura couplings of non-triflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar—O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C—O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C—O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe3 and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe3 effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.
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影响因子：
15
作者：
Everson, Daniel A.;Jones, Brittany A.;Weix, Daniel J.
通讯作者：
Weix, Daniel J.
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影响因子：
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作者：
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通讯作者：
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通讯作者：
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