Alcohols as electrophiles? Iron catalysis-enabled C-C- and C-N-bond formation through nucleophilic displacement of unactivated alcohols

An emerging area in synthetic chemistry involves the direct use of alcohols; a functional group that is widely available and an economical alternative for C-X species. Unfortunately, alcohols are difficult to employ as electrophiles because of the poor leaving group ability of the hydroxyl group. To overcome this issue, "activated" alcohols are typically employed. Enabling the use of unactivated alcohols would improve synthetic routes and simplify access to numerous biologically important molecules. Here, the development of a novel iron-catalyst for the chemical transformation of two distinct classes will be presented: (1) C--C-bond formation through arene alkylation and addition of alcohols to alkynes and (2) C--N-bond formation through the Ritter reaction, the Beckmann rearrangement and N-alkylation of unactivated alcohols. In some instances, this transformation can be done with transfer of chirality. This body of work will expand the scope and use of unactivated alcohols in many transformations for the synthetic community.