Loading…

Kinetic investigation of cross-coupling reaction steps by advanced competing reaction methods

[Display omitted] •Mechanistic investigations using differential selectivity have been performed.•The fast steps of Heck and Cu-free Sonogashira reaction have been elucidated.•The reversibility/irreversibility of the catalytic cycles’ steps has been established.•Mechanistic schemes for Heck and Cu-f...

Full description

Saved in:
Bibliographic Details
Published in:Journal of molecular catalysis. A, Chemical Chemical, 2016-12, Vol.425, p.43-54
Main Authors: Kurokhtina, Anna A., Larina, Elizaveta V., Yarosh, Elena V., Schmidt, Alexander F.
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:[Display omitted] •Mechanistic investigations using differential selectivity have been performed.•The fast steps of Heck and Cu-free Sonogashira reaction have been elucidated.•The reversibility/irreversibility of the catalytic cycles’ steps has been established.•Mechanistic schemes for Heck and Cu-free Sonogashira reactions have been proposed. Investigating the mechanism of a complex catalytic reaction is usually quite complicated because many processes, such as active catalyst formation and deactivation, are linked to the main catalytic cycle. Using artificial multi-route reactions with similar competing substrates is a unique way to elucidate the fine details of a reaction mechanism. Applying such multi-route reaction-based methods to the cross-coupling of alkynes with aryl halides (Cu-free Sonogashira reaction) and alkenes with aromatic carboxylic anhydrides (modified Heck reaction) catalysed by ligand-free Pd allowed us to elucidate the fast, reversible, and rate-determining steps involved in the relevant catalytic cycles.
ISSN:1381-1169
1873-314X
DOI:10.1016/j.molcata.2016.09.022