Nucleophilic substitution reactions are one of the most fundamental and common transformations in organic chemistry that have found countless applications in synthesis. Most, if not all, nucleophilic displacements proceed at either a primary, secondary or tertiary carbon stereocenters. What about nucleophilic substitution at a quaternary carbon center? The nucleophilic displacement at a quaternary stereocenter has never been considered since the amount of energy required to break a C-C single bond is too high. Is, nevertheless, the nucleophilic substitution at a quaternary carbon center a feasible process? Could we promote a carbon-carbon bond cleavage at a quaternary center with a pure inversion of configuration? Does this transformation have the potential to become a general principle in stereoselective synthesis and be used for the preparation of regio- diastereo- and even enantiomerically enriched products possessing several adjacent stereocenters despite that the C-C single bond belongs to the least reactive functional groups in chemistry (is a C-C single bond a functional group)? If the C-C bond is the least reactive functional group, how a C-C bond cleavage be performed under mild conditions that would allow the presence of more sensitive functional groups? All these questions are at the heart of this lecture.

Nucleophilic substitution at quaternary carbon stereocenter

ACS Spring 2022

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