The chiral iminopyridine oxazoline (IPO) ligands were designed, synthesized and utilized for the first cobalt-catalyzed highly regio-and enantioselective anti-Markovnikov hydroboration of 1,1-disubstituted aryl alkenes. This novel IPO ligands will likely be of high value for asymmetric transformations with first-row transition metals.

The highly regio- and enantioselective iron-catalyzed anti-Markovnikov hydroboration of 1,1-disubstituted aryl alkenes is reported by using a novel chiral iminopyridine oxazoline (IPO) ligand, in which the iminopyridine group is proposed to stabilize the iron and chiral oxazoline group to control enantioselectivity. This distinct class of reactive IPO ligands will likely be of high value for a large variety of asymmetric transformations using first-row transition metals.

A ligand-controlled cobalt-catalyzed regioselective hydroboration/cyclization of 1,6-enynes with HBPin was developed by switching the size of the coordinated side arm to afford alkenylboronates and alkylboronates, respectively. Gram-scale reactions could be easily conducted, which is beneficial for further derivatizations. A primary mechanism was proposed on the basis of substrate-controlled experiments and deuterium experiments.

An iminopyridine cobalt dichloride complex was synthesized and demonstrated as an effective precatalyst for hydrosilylation/cyclization of 1,6-enynes with silanes. Various functional groups such as amine, free aniline, ester, ether, cyano, halide, trifluoromethyl, and heterocycle were tolerated to afford a variety of silicon-containing compounds. The reaction could be scaled up to afford products on the gram scale which could undergo further derivatizations. A primary mechanism was proposed based on analysis of side products and a deuterated experiment.

A direct, efficient, and practical protocol to install a chiral oxazoline unit onto aryl/heteroaryl rings via palladium-catalyzed C-H functionalization of 2-positions of oxazolines with a variety of halides using dppe as the ligand has been developed. Various chiral oxazoline ligands could be synthesized, even in a 10-g scale process. This protocol is a good supplement to traditional methods and for diverse synthesis of chiral oxazoline ligands.