Related Experiment Video
Updated: Jun 21, 2025
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes via Chain Walking
Noah Wagner-Carlberg1, Tomislav Rovis1
1Department of Chemistry, Columbia University, New York, New York 10027, United States.
Abstract:
Hydroamination of terminal alkenes represents a powerful and well-established way to introduce nitrogenous functionality to feedstock chemicals. Remote hydroamination reactions are far less known, and represent a way to functionalize unactivated C(sp3) centers distal to the site of the alkene. These transformations commonly take place via metal hydride-mediated chain walking, and as such, regioselectivity can be challenging. The remote introduction of amides is of particular interest due to their prevalence in pharmaceuticals. Herein we report a Rh(III)-catalyzed hydroamidation procedure to functionalize the terminal position of internal alkenes, using dioxazolones as amidation reagents and i-PrOH as a hydride source. The reaction proceeds with high yield and regioselectivity, and tolerates a variety of functionality. Regioconvergent synthesis of a single linear amide from a mixture of isomeric alkenes is demonstrated. Key to the development of this reaction was determining that inorganic bases poison the catalyst, and identifying a suitable trialkylamine replacement.
Related Concept Videos
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.
02:24Reduction 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.
01:17Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
02:35Electrophilic Addition to Alkynes: Hydrohalogenation
02:40Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
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...