Catalytic Addition of Nitroalkanes to Unactivated Alkenes via Directed Carbopalladation



We report a redox-neutral catalytic coupling of nitroalkanes and unactivated alkenes that proceeds by a directed carbopalladation mechanism. The reaction is uniquely enabled by the combination of PdI2 as the precatalyst and HFIP solvent. Structurally complex nitroalkane products, including nitro-containing carbo- and heterocycles, are prepared under operationally convenient conditions without the need for toxic or corrosive reagents. Deuterium labeling experiments and isolation of a catalytically relevant intermediate shed light on the reaction mechanism. By taking advantage of different catalytic activation modes, we demonstrate orthogonal methods for site-selective functionalization of a polyfunctional nitroalkyl ketone.

Version notes

Corrected the spelling of the first name of one of the authors.


Supplementary material

Supporting Information
Experimental Procedures, Copies of NMR Spectra, and Crystallographic Data
Crystallographic Information File for Compound 5a
Crystallographic Information File for Compound Pd-1
Crystallographic Information File for Compound S1
NMR Data
Copies of NMR Data in MNova Format