Directed Hydroxylation of sp2 and sp3 C-H Bonds Using Stoichiometric Amounts of Cu and H2O2
Directed Hydroxylation of sp2 and sp3 C-H Bonds Using Stoichiometric Amounts of Cu and H2O2
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DOI：
10.1021/acs.inorgchem.9b00901
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发表时间：
2019-06-03
影响因子：
4.6
通讯作者：
Garcia-Bosch, Isaac
中科院分区：
文献类型：
--
作者：
Trammell, Rachel;D'Amore, Lorenzo;Garcia-Bosch, Isaac
与其他金属相比，使用铜进行C-H键官能化相对未被探索。在此，我们报告了一种使用定向基团、化学计量的Cu和H2 O2对sp（2）和sp（3）C-H键进行区域选择性羟基化的合成方案。许多芳香酮和醛在羰基γ-位上被氧化，产率非常高。我们还将这种方法扩展到羟基化烷基酮的β-位。光谱表征，动力学，和密度泛函理论计算指向参与单核LCuII（OOH）物种，它氧化的芳香sp（2）C-H键通过协同异裂O-O键裂解伴随亲电攻击的芳烃系统。
The use of copper for C-H bond functionalization, compared to other metals, is relatively unexplored. Herein, we report a synthetic protocol for the regioselective hydroxylation of sp(2) and sp(3) C-H bonds using a directing group, stoichiometric amounts of Cu and H2O2. A wide array of aromatic ketones and aldehydes are oxidized in the carbonyl gamma-position with remarkable yields. We also expanded this methodology to hydroxylate the beta-position of alkylic ketones. Spectroscopic characterization, kinetics, and density functional theory calculations point toward the involvement of a mononuclear LCuII(OOH) species, which oxidizes the aromatic sp(2) C-H bonds via a concerted heterolytic O-O bond cleavage with concomitant electrophilic attack on the arene system.