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.

The use of a mixture of dl‐ and meso‐divinylethylene carbonate as an electrophile in palladium‐catalyzed asymmetric allylic alkylation reactions is reported. From the diastereomeric mixture of meso and chiral racemic starting materials, a single product is obtained in high optical purity employing either oxygen or nitrogen nucleophiles. The resulting dienes have proven to be versatile synthetic intermediates as each carbon is functionalized for further transformation and differentiated by virtue of the reaction. A mechanism for this intriguing transformation is proposed and a concise enantioselective total synthesis of (+)‐australine hydrochloride is reported as well as a formal synthesis of isoaltholactone.

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