Balhara Reena, Jindal Garima
Department of Organic Chemistry, Indian Institute of Science, Bangalore, Karnataka 560012, India.
Chem Commun (Camb). 2024 Sep 16;60(75):10322-10325. doi: 10.1039/d4cc03498h.
Fe-based catalysts as well as enzymes typically yield low stereoselectivity for carbene insertion into X-H bonds. Here, we have utilized DFT methods to understand the mechanism and unusually high enantioselectivity in an Fe-spiroBox catalyzed carbene insertion reaction into the O-H bond of aliphatic alcohols. Our transition state model shows a unique binding of the reaction intermediates to the chiral catalyst enabled by weak non covalent interactions that is absent in other X-H insertion reactions.
铁基催化剂以及酶在卡宾插入X-H键的反应中通常立体选择性较低。在此，我们利用密度泛函理论（DFT）方法来理解铁-螺环盒催化卡宾插入脂肪醇O-H键反应的机理及异常高的对映选择性。我们的过渡态模型表明，反应中间体通过弱非共价相互作用与手性催化剂形成独特的结合，而这种相互作用在其他X-H插入反应中并不存在。
