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Synthesis of 1,2-fluoroamines

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In situ generation of amine-HF reagents from benzoyl fluoride and a non-nucleophilic alcohol in the presence of a Lewis base catalyst enables the hydrofluorination of aziridines to provide β-fluoroamines. This protocol displays a broad scope with respect to aziridine substitution and N-protecting groups. Regio- and diastereoselective ring opening to access medicinally relevant β-fluoroamine building blocks are presented.
J. A. Kalow, D. E. Schmitt, A. G. Doyle, J. Org. Chem., 2012, 77, 4177-4183.


The charge density of fluoride with a hydrogen-bond donor urea catalyst directly influences the kinetic regioselectivity in the fluorination of dissymmetric aziridinium salts with aryl and ester substituents. These findings offer a route to access enantioenriched fluoroamine regioisomers from a single chloroamine precursor.
M. A. Horwitz, A. B. Dürr, K. Afratis, Z. Chen, J. Soika, K. E. Christensen, M. Fushimi, R. S. Paton, V. Gouverneur, J. Am. Chem. Soc., 2023, 145, 9708-9717.


The charge density of fluoride with a hydrogen-bond donor urea catalyst directly influences the kinetic regioselectivity in the fluorination of dissymmetric aziridinium salts with aryl and ester substituents. These findings offer a route to access enantioenriched fluoroamine regioisomers from a single chloroamine precursor.
M. A. Horwitz, A. B. Dürr, K. Afratis, Z. Chen, J. Soika, K. E. Christensen, M. Fushimi, R. S. Paton, V. Gouverneur, J. Am. Chem. Soc., 2023, 145, 9708-9717.


A dianionic phase-transfer catalyst enables an asymmetric fluorofunctionalization of γ,γ-disubstituted allylamine derivatives. Depending on the substituents on the alkene moiety, the reaction afforded chiral allylic fluorides and fluorinated dihydrooxazines in a highly enantioselective manner.
T. Niwa, K. Nishibashi, H. Sato, K. Ujiie, K. Yamashita, H. Egami, Y. Hamashima, J. Am. Chem. Soc., 2021, 143, 16599-16609.

Related


A nickel-catalyzed enantioselective hydrofluoromethylation of enamides and enol esters with ICH2F as the fluoromethyl source provides chiral α-fluoromethylated amides as well as esters with wide functional group compatibility as well as excellent enantioselectivity.
Y. Du, S. Chen, H. Cao, Y. Zhang, H. Lei, G. Xia, H. Huang, Z. Li, Org. Lett., 2023, 25, 2218-2222.