Ungewöhnliche Alkylierungsreaktionen in der Natur und die Aufklärung ihrer Mechanismen

Glasenapp-Breiling, Martina; Montforts, Franz‐Peter

doi:10.1002/(sici)1521-3757(20000218)112:4<737::aid-ange737>3.0.co;2-#

Angewandte Chemie

2000

DOI: 10.1002/(sici)1521-3757(20000218)112:4<737::aid-ange737>3.0.co;2-#

|View full text |Cite

Ungewöhnliche Alkylierungsreaktionen in der Natur und die Aufklärung ihrer Mechanismen

Martina Glasenapp-Breiling¹,

Franz‐Peter Montforts²

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2018

Publication Types

Select...

Article1

Relationship

Self Cite0

Independent1

Authors

Journals

Cited by 1 publication

References 15 publications

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

Alkyl Radical Generation by an Intramolecular Homolytic Substitution Reaction between Iron(II) and Trialkylsulfonium Groups

Jungen

Chen

2018

Chemistry A European J

View full text Add to dashboard Cite

Intramolecular, homolytic substitution reactions between iron(II) species and various trialkylsulfonium groups were directly observed in the gas phase upon collision-induced dissociation. In spite of the notoriously low reduction potential of trialkylsulfonium species and the mismatched oxidation potential of iron(II), the reactions proceed at moderate collision energies, forming an alkyl radical as well as a thioether coordinated to the iron. In contrast to classical homolytic substitutions, the attacking radical is a "metalloradical", namely iron(II) that is oxidized to iron(III) during the reaction. With this process we demonstrate that the conceptually analogous, putative radical generation step in radical S-adenosyl methionine (SAM) enzymes is possible and plausible. Further, we show that this kind of reaction only occurs in constrained systems with a defined geometry. Combining experimental measurements with DFT studies and NBO analyses allowed us to gain insights into the reactivity and transition states of these systems. Based on our findings, we challenge the notion of a collinear transition state in the radical generation step of radical SAM enzymes and propose it to be bent instead.

show abstract

Alkyl Radical Generation by an Intramolecular Homolytic Substitution Reaction between Iron(II) and Trialkylsulfonium Groups

Jungen

Chen

2018

Chemistry A European J

View full text Add to dashboard Cite

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

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.

Ungewöhnliche Alkylierungsreaktionen in der Natur und die Aufklärung ihrer Mechanismen

Cited by 1 publication

References 15 publications

Alkyl Radical Generation by an Intramolecular Homolytic Substitution Reaction between Iron(II) and Trialkylsulfonium Groups

Alkyl Radical Generation by an Intramolecular Homolytic Substitution Reaction between Iron(II) and Trialkylsulfonium Groups

Contact Info

Product

Resources

About