Alcohols as Electrophiles in CC Bond-Forming Reactions: The Hydrogen Autotransfer Process

The hydrogen autotransfer process involves an initial oxidative hydrogen elimination, followed by different types of reactions, and is completed with a reductive hydrogen addition to give the final product. The sequence allows the alkylation of different nucleophilic agents using environmentally benign alcohols as electrophiles, mild conditions, and soft bases, with water produced as the only waste material. Recent examples of modulating the organometallic catalyst have also lent themselves to expansion of the range of available substrates, as described in this Minireview. . ‥ something new, something borrowed: The hydrogen autotransfer (borrowing) process involves a hydrogen ion/CC coupling/hydrogen capture sequence for the alkylation of nucleophiles using primary alcohols as the source of electrophile (see scheme). The sequence proceeds with high chemical yields and atom efficiencies, with water as the only formal waste material produced.