Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines

The Chemistry Cascade

Sergey Pronin, Christopher Reiher, and Ryan Shenvi
Nature
DOI: 10.1038/nature12472

The bimolecular nucleophilic substitution (S_N2) reaction is a well understood and widely used chemical transformation that allows a chemist to affect useful functional group interconversions or combine two molecules. A significant advantage of the S_N2 reaction over the related (and often competitive) unimolecular nucleophilic substitution (S_N1) reaction is that it provides predictable stereoinversion at the electrophilic carbon centre. S_N2 processes do, however, suffer from a significant limitation: intolerance of tertiary electrophilic carbon atoms, where steric crowding inhibits the approach of the nucleophilic reacting partner. This drawback limits the stereochemical complexity of possible reaction substrates and the utility of nucleophilic substitution in the synthesis of challenging chiral molecules.

Now, a team of researchers from California led by Ryan Shenvi have developed a process that allows the stereochemical inversion of tertiary alcohols with nitrogen-based…

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