Palladium(II)‐Catalyzed Intramolecular Hydroamination of 1,3‐Dienes to Give Homoallylic Amines

Pincer complexes are becoming increasingly important for organometallic chemistry and organic synthesis. Since numerous applications for such catalysts have been developed in recent decades, this Minireview covers progress in their use as catalysts for (de)hydrogenation and transfer (de)hydrogenation reactions during the last four years. Aside from noble-metal-based pincer complexes, the corresponding base metal complexes are also highlighted and their applications summarized.

show abstract

Experimental and Computational Mechanistic Studies of the β‐Diketiminatoiron(II)‐Catalysed Hydroamination of Primary Aminoalkenes

Lepori

Bernoud

Guillot

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

A comprehensive mechanistic study by means of complementary experimental and computational approaches of the exo‐cyclohydroamination of primary aminoalkenes mediated by the recently reported β‐diketiminatoiron(II) complex B is presented. Kinetic analysis of the cyclisation of 2,2‐diphenylpent‐4‐en‐1‐amine (1 a) catalysed by B revealed a first‐order dependence of the rate on both aminoalkene and catalyst concentrations and a primary kinetic isotope effect (KIE) (kH/kD) of 2.7 (90 °C). Eyring analysis afforded ΔH≠=22.2 kcal mol−1, ΔS≠=−13.4 cal mol−1 K−1. Plausible mechanistic pathways for competitive avenues of direct intramolecular hydroamination and oxidative amination have been scrutinised computationally. A kinetically challenging proton‐assisted concerted N−C/C−H bond‐forming non‐insertive pathway is seen not to be accessible in the presence of a distinctly faster σ‐insertive pathway. This operative pathway involves 1) rapid and reversible syn‐migratory 1,2‐insertion of the alkene into the Fe−Namido σ bond at the monomer {N^N}FeII amido compound; 2) turnover‐limiting Fe−C σ bond aminolysis at the thus generated transient {N^N}FeII alkyl intermediate and 3) regeneration of the catalytically competent {N^N}FeII amido complex, which favours its dimer, likely representing the catalyst resting state, through rapid cycloamine displacement by substrate. The collectively derived mechanistic picture is consonant with all empirical data obtained from stoichiometric, catalytic and kinetics experiments.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Palladium(II)‐Catalyzed Intramolecular Hydroamination of 1,3‐Dienes to Give Homoallylic Amines

Cited by 6 publications

References 29 publications

Diversification of NH‐Aryl Sulfoximines through Iridium‐Catalyzed ortho‐ and meta‐Selective C−H Borylation

Diversification of NH‐Aryl Sulfoximines through Iridium‐Catalyzed ortho‐ and meta‐Selective C−H Borylation

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Experimental and Computational Mechanistic Studies of the β‐Diketiminatoiron(II)‐Catalysed Hydroamination of Primary Aminoalkenes

Contact Info

Product

Resources

About