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We report the development of a well-defined Fe catalyst and its application to the regio- and stereoselective 1,4-hydrosilylation of 1,3-dienes. To the best of our knowledge, this is the first example of accessing a characterized low-valent Fe catalyst by controlled reductive elimination from a readily accessible Fe precatalyst.

Ironing rubber: Iminopyridine‐based FeCl2 catalysts catalyze the polymerization of 1,3‐dienes and provide stereoselective access to elastomers such as polyisoprenes, polymyrcenes, and polyfarnesenes. The choice of ligand determines the double‐bond geometry in the polymer repeating unit, which can be varied from trans/cis >99:1 to <1:99 (see scheme).

A new intermolecular, stereo- and regioselective iron-catalyzed 1,4-addition of alpha-olefins to 1,3-dienes using as low as 1 mol % of an iminopyridine-ferrous chloride complex was developed. Importantly, both double bonds of the linear 1,4-diene addition products are obtained with absolute stereocontrol.

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