Related Experiment Video
Updated: Aug 6, 2026
Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Unraveling the Regio- and Enantioselective Control in Transition Metal-Catalyzed Reductive Hydrofunctionalization of
Hongyan Chen1, ManZhu Zhao1, Guangfan Zheng1
1Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun130024, China.
Abstract:
Nickel- and cobalt-catalyzed asymmetric reductive hydrofunctionalization of N-heteroalkenes has emerged as a powerful strategy for the construction of enantiopure 2-/3-substituted pyrrolidine derivatives. However, the origin of the regio- and enantioselective control, particularly under the modulation of bisoxazoline (BOX) ligands, remains to be fully elucidated. Herein, our density functional theory (DFT) studies revealed that the chain-walking process governs the regioselectivity, while the hydrogen atom transfer (HAT) step dictates the enantioselectivity. Energy decomposition analysis reveals that orbital interactions, complemented by electrostatic effects, serve as the predominant factors in governing both regio- and stereoselectivity. Furthermore, the noncovalent interactions between the substrate and the BOX ligand serve to further stabilize the preferred transition states, thereby fine-tuning the energetic landscape of the reaction. These insights provide a rational basis for the development of transition-metal-catalyzed precise functionalization of heterocycles.
Related Concept Videos
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
02:13Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.