Abstract
A theoretical study has been carried out on the palladium-catalyzed C(sp3)–H activation/amidation reaction of carbamoyl chloride precursors (Takemoto, Y. Angew. Chem. Int. Ed. 2012, 51, 2763 ). In Takemoto’s reaction, although the C(sp2)–H bond of naphthalene was present in the substrate, the benzylic C(sp3)–H bond was activated exclusively. Mechanistic calculations have been performed on the two possible pathways: the C(sp3)–H activation/amidation pathway (Path-sp3) and the C(sp2)–H activation/amidation pathway (Path-sp2). Calculation results show that both paths include three steps: oxidative addition (via the mono-phosphine mechanism), C–H activation involving the PivNHO– anion (via the CMD mechanism), and final reductive elimination. The calculations indicate that the Path-sp3 mechanism is kinetically favored, and the C(sp3)–H amidated product is predicted to be the main product. This conclusion is consistent with Takemoto’s experimental observations. The rate-determining step of Path-sp3 is the oxida...
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
