Kumar Rohit, Dutta Sayan, Sharma Vishal, Singh Praval P, Gonnade Rajesh G, Koley Debasis, Sen Sakya S
Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India.
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India.
Chemistry. 2022 Oct 7;28(56):e202201896. doi: 10.1002/chem.202201896. Epub 2022 Aug 17.
In this work, two monomeric magnesium alkyl complexes (1 and 2) were prepared using bis(phosphino)carbazole framework and among them 1 has been used as a catalyst for hydroboration of alkenes and alkynes with pinacolborane (HBpin). A broad variety of aromatic and aliphatic alkenes and alkynes were efficiently reduced. Anti-Markovnikov regioselective hydroboration of alkenes and alkynes was achieved, which was confirmed by deuterium-labelling experiments. The work represents the first example of the use of magnesium in homogeneous catalytic hydroboration of alkene with broad substrate scope. Experimental mechanistic investigations and DFT calculations provided insights into the reaction mechanism. Finally, the hydroboration protocol was extended to terpenes.
在本工作中，使用双（膦基）咔唑骨架制备了两种单体烷基镁配合物（1和2），其中1已被用作催化剂，用于烯丙基和炔烃与频哪醇硼烷（HBpin）的硼氢化反应。多种芳香族和脂肪族烯烃及炔烃被有效还原。实现了烯烃和炔烃的反马氏区域选择性硼氢化反应，这通过氘标记实验得到证实。该工作代表了镁在具有广泛底物范围的烯烃均相催化硼氢化反应中应用的首个实例。实验机理研究和密度泛函理论（DFT）计算为反应机理提供了深入见解。最后，硼氢化反应方案扩展至萜类化合物。
