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Synlett 2024; 35(14): 1613-1620
DOI: 10.1055/a-2211-6538
DOI: 10.1055/a-2211-6538
synpacts
Special Section 13th EuCheMS Organic Division Young Investigator Workshop
Defluorinative Asymmetric Allylic Alkylations
This work was supported by the projects PID2020-116859GA-I00 and CNS2022-135457, funded by MCIN/AEI/10.13039/501100011033. P.R. thanks the Ministry of Education (MEFP) for a collaboration fellowship, J.D. thanks the Generalitat de Catalunya for the AGAUR-FI Joan Oró predoctoral fellowship BDNS-657443, and M.G. thanks the Ministry of Science (MICIN) for an FPI predoctoral fellowship PRE2021-097347.
Abstract
The introduction of allyl fluorides as alternative electrophiles in asymmetric allylic alkylation reactions has recently attracted significant interest. Despite the intrinsic thermodynamically demanding C–F bond-cleavage event, the fluorophilic nature of the silicon atom is key in assisting the activation and cleavage of the allylic C–F bond. Thus, the use of silylated compounds as unconventional nucleophiles, together with the Lewis basicity of fluorine when acting as a leaving group, enables the development of innovative chemical transformations within mild and selective catalytic schemes. This Synpacts article summarizes the diverse defluorinative asymmetric allylic alkylations with allyl fluorides reported to date under both chiral Lewis base and transition-metal catalysis.
Key words
C–F bond activation - defluorination - asymmetric catalysis - allylic alkylation - Lewis base catalysis - transition-metal catalysisPublication History
Received: 03 November 2023
Accepted after revision: 15 November 2023
Accepted Manuscript online:
15 November 2023
Article published online:
02 January 2024
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For selected reviews, see:
For selected reviews on transition-metal-catalyzed AAA, see:
For selected reviews on Lewis base catalyzed AAA, see:
For selected examples using stabilized nucleophiles, see:
For selected examples with unconventional nucleophiles, see:
For selected reviews of C–F bond activation, see:
For selected reviews on defluorinative transformations, see: