27th International symposium: Synthesis in organic chemistry

Stereospecific nucleophilic substitution at quaternary carbon stereocenters Kaushalendra Patel, Dr.Veeranjaneyulu Lanke, Dr. Xu chen, Prof. Ilan Marek Technion - Israel Institute of Technology, Haifa, Israel Nucleophilic substitution reactions are one of the most fundamental transformations in organic chemistry that have found numerous applications in synthesis. All nucleophilic displacements proceed at either primary, secondary, or tertiary carbon stereocenters. What about nucleophilic substitution at a quaternary carbon center? The nucleophilic substitution at a quaternary stereocenter has never been considered since the 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. If the C-C bond is the least reactive functional group, how a C-C bond cleavage could be performed under mild conditions that would allow the presence of more sensitive functional groups such as C-O or C-halogen bond? References

1. Patel, K.; Lanke, V.; Marek, I., J. Am. Chem. Soc . 2022 , 144 , 7066-7071. 2. Chen, X.; # Patel, K.; # Marek, I., Angew. Chem. Int. Ed. 2023 , 62 , e202212425. 3. Chen, X.; Patel, K.; Marek, I., Chem 2023 , 9 , 266-279.

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