Site-Selective Photochemical Fluorination of Ketals: Unanticipated Outcomes in Selectivity and Stability.
J Org Chem
; 85(5): 2855-2864, 2020 03 06.
Article
en En
| MEDLINE
| ID: mdl-32031800
ABSTRACT
We report a method for the regioselective photochemical sp3 C-H fluorination of acetonide ketals that presents interesting problems in chemical reactivity. The question of why certain products of the reaction are stable while others are not is addressed, as is the question of why only select α-ethereal hydrogen atoms are targeted in the reaction. We demonstrate that the method can be employed to synthesize unprecedented fluorinated sugars and steroids, and it can also be applied toward the fluorination of carbamates. Though some substrates contain up to eight discrete α-ethereal C-H bonds, we observed site-selectivity in each case, prompting us to investigate potential transition states for the reaction. Finally, a remarkable regiochemical switch upon minor structural modification of a diketal is also analyzed.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Año:
2020
Tipo del documento:
Article
País de afiliación:
Estados Unidos