Here, we reported for the first time an iron-catalyzed highly enantioselective hydrogenation of minimally functionalized 1,1-disubstituted alkenes to access chiral alkanes with full conversion and excellent ee. A novel chiral 8-oxazoline iminoquinoline ligand and its iron complex have been designed and synthesized. This protocol is operationally simple by using 1 atm of hydrogen gas and shows good functional group tolerance. A primary mechanism has been proposed by the deuterium-labeling experiments.

A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (−)‐preclamol in gram‐scale. The two primary C(sp3)−B bonds in chiral 1,5‐bis(boronates) could be distinguished in iterative Suzuki–Miyaura cross‐coupling reaction, delivering chiral 1,2,5‐triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt‐hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.

A cobalt‐catalyzed asymmetric reduction of β,β‐dialkyl α,β‐unsaturated esters with polymethylhydrosiloxane (PMHS) was reported to deliver the corresponding esters containing a chiral trialkyl carbon center at β‐position with up to 97 % yield and 98 % ee. The chiral tridentate ligand oxazoline iminopyridine (OIP) could perform well for the asymmetric reduction instead of chiral bidentate ligands. This operationally simple protocol shows a broad scope of substrates using one equivalent of readily available PMHS as a cheap and easy‐to‐handle reductive reagent.

Herein, a cobalt-catalyzed hydroboration of vinylcyclopropanes was reported to access the corresponding homoallylic boronates with excellent regio-and stereoselectivity. This reaction features a broad substrate scope and could be carried out on a gram scale. The possible mechanism and models for selectivity have been proposed.

An efficient method for the synthesis of isoquinolinone derivatives via photopromoted carboamination of alkynes is developed. Starting from the readily available propargyl alcohol derivatives, the polycyclic isoquinolinone derivatives could be...