Over the past decade, the effectiveness of i-PrMgCl·LiCl has been constantly highlighted by a number of research groups. Its enhanced nucleophilicity brings prosperity to highly functionalized Grignard reagents, other useful bimetallic (alkali-metal) agents and nucleophilic alkylation products under mild reaction conditions. In this feature article, a comprehensive, systematical and in-depth overview of i-PrMgCl·LiCl is provided in a multidisciplinary idea. It involves the structural and kinetic perspectives of i-PrMgCl·LiCl as well as its unique reactivity and selectivity, with knowledge of the former helping to rationalize trends of the later.

A transition-metal-free method for the B(CF)-promoted hydrogenations of N-heterocycles using ammonia borane under mild reaction conditions has been developed. The reaction affords a broad range of hydrogenated products in moderate to good yields. The enantioselective versions for the corresponding products were also investigated via our approach, showing good feasibility.

An efficient strategy for the deoxygenation of sulfoxides and amine N‐oxides by using B(C6F5)3 and hydrosilanes was developed. This method provided the corresponding aromatic and aliphatic products in good to high yields and showed good functional‐group tolerance under mild conditions.

A highly efficient and enantioselective hydrogenation of diversely substituted C=N‐containing heterocyclic compounds such as 3‐aryl‐1,4‐benzoxazines and 2‐arylquinolines was experimentally explored by using 1,1′‐spirobiindane‐7,7′‐diol‐derived chiral phosphoric acids as the catalyst. This method provides straightforward access to the corresponding tetrahydroquinolines and dihydro‐2H‐1,4‐benzothiazines in high yields (85–99 %) with excellent enantioselectivities (91–99 %). The attractive features of this procedure, which include mild reaction conditions, operational simplicity, relatively low catalyst loading (1 mol‐%), and high levels of enantioselectivities, make it a useful approach for the practical synthesis of optically active nitrogen‐containing aromatic heterocycles.

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