Related Experiment Video
Updated: Mar 12, 2026
Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
Published on: November 30, 2022
Nickel-Catalyzed Boron-Stereogenic Hydroboration
Siqiang Fang1,2, Peiqi Zhang2, Guanwen Hu2
1Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Kowloon 999077, Hong Kong SAR China.
Abstract:
Hydroboration is one of the most widely utilized reactions for olefin functionalization and organoboron synthesis. While asymmetric hydroboration is well established for creating homochiral alkanes with stereogenic carbon centers, catalytic hydroboration to incorporate boron stereocenters remains an unresolved challenge. In this work, through the rational design of a nickel/chiral phosphoramidite catalyst system, we report a boron-stereogenic hydroboration of a wide range of unactivated and activated olefins using a prochiral, four-coordinate vinylborane reagent. This reaction enables the construction of enantioenriched B(sp3)-C(sp3) skeletons containing both boron and carbon stereocenters. Experimental and computational studies reveal a unique ligand-to-ligand hydrogen transfer pathway for the activation and metalation of inert B(sp3)-H bonds, providing mechanistic insights into the observed enantioselectivity. With its broad substrate scope and remarkable functional group compatibility, this protocol offers access to various acyclic chiral organoboranes with structural diversity.
Related Concept Videos
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.
03:08Hydroboration-Oxidation of Alkenes
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
02:15Preparation of Alcohols via Addition Reactions
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
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...
01:25Radical Anti-Markovnikov Addition to Alkenes: Overview