Enantioselective SOMO Catalysis has enabled the development of a range of valuable transformations that were previously impossible (including the direct α-allylation, -vinylation, and -enolation of aldehydes). These processes, however all utilize olefinic coupling partners that contain fragmentable groups (eg. allyl silanes, enolsilanes, or vinyl trifluoroborates, respectively). We have discovered that simple olefins (lacking fragmentable groups) are competent SOMOphiles and styrenes couple with aldehydes under oxidative organocatalytic conditions to afford a wide variety of benzylic nitrate products in excellent yield and enantioselectivity. To demonstrate the synthetic utility of these compounds, we have developed a series of operationally trivial manipulations that allow for the direct formation of a number of important enantioenriched heterocyclic building blocks.

We also applied mechanistic elements of this technology toward the development of a radical-polar cycloaddition strategy that couples conjugated olefins with bifunctional aldehydes to afford a range of stereochemically complex cyclic products. The development of this formal [4 + 2] reaction was enabled by the use of Kochi’s trisphenanthroline complex of iron(III) as an outer-sphere oxidant. We have shown that this unique cycloaddition strategy is applicable to a range of cascade cycloadditions forming five- and six-membered carbocyclic and heterocyclic products. This strategy has also been applied to the hetero (3 + 2) cycloadditions of β-amino aldehydes and conjugated olefins to afford a range of enantioenriched di- and trisubstituted pyrrolidines.