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.


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Supplementary material

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