Mechanism of C-P bond formation via Pd-catalyzed decarbonylative phosphorylation of amides: insight into the chemistry of the second coordination sphere.

We report on the basis of DFT computations a plausible and detailed reaction mechanism for the first Pd-catalyzed decarbonylative phosphorylation of amides forming C-P bonds, which reveals, among other things, crucial events in the second coordination sphere, including ion pair and hydrogen bonding interactions as well as proton transfer.

Ni-Catalyzed Reductive Coupling of Electron-Rich Aryl Iodides with Tertiary Alkyl Halides.

This work illustrates the reductive coupling of electron-rich aryl halides with tertiary alkyl halides under Ni-catalyzed cross-electrophile coupling conditions, which offers an efficient protocol for the construction of all carbon quaternary stereogenic centers. The mild and easy-to-operate reaction tolerates a wide range of functional groups. The utility of this method is manifested by the preparation of cyclotryptamine derivatives, wherein successful incorporation of 7-indolyl moieties is of particular interest as numerous naturally occurring products are composed of these key scaffolds.