Organic Letters
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lactone products were isolated in high to excellent yields (78−
97%). Complete β-regioselectivity was achieved except for
styrene epoxide 1j. As expected, in this case a mixture (86:14) of
the two regioisomers 3ja and 3ja′, deriving from the nucleophilic
attack at the β- and α-position respectively, has been isolated
(Scheme 2).
Our procedure was also tested with two additional KSA 2b and
2c. Despite its higher steric hindrance, 2b reacted with epoxides
1a, 1c, 1f, 1j in short times (2−5 h) giving only cyclized products
3ab, 3cb, 3fb, 3jb/3jb′ (81:19) in good yields (80−91%). KSA
2c behaved differently, and a different outcome was observed. In
fact, after 4 h at 60 °C, the reaction with 1a lead to the formation
of the ring opened product deriving from the attack of 2c to the
epoxide 1a. To obtain the desired lactonization product 3ac, a
thermal treatment of the reaction mixture was needed and the γ-
lactone was prepared in 70% yield after an additional heating at
270 °C for 1.5 h (Scheme 2).
In conclusion, for the first time we have reported a catalytic
approach to the reaction of epoxides 1 with KSA 2. TBAF·3H2O
was found to be the most efficient fluoride catalyst, and the
efficiency of the process could be reached by adopting SolFC.
The general procedure described herein can be applied to both
aryl and alkyl epoxides leading in all cases to the preparation of γ-
lactones 3 in good to excellent yields. Moreover, the use of the
fluoride catalyst with SolFC allowed the final products to be
obtained without any additives (i.e., p-TsOH for the
lactonization of the epoxide ring-opening product).
The chemical efficiency, simple experimental procedure,
absence of metal species, and use of an inexpensive and mild
catalyst make this process particularly attractive. Further studies
will be devoted to the design and synthesis of novel and more
efficient heterogeneous fluoride sources to be used as recoverable
catalysts.
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(9) (a) Angelini, T.; Bonollo, S.; Ballerini, E.; Lanari, D.; Maggi, R.;
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(10) Amberlite IRA900F is a trimethylammonium fluoride on
macroreticular polystyrene resin which is commercially available from
Aldrich as “Fluoride on polymer support” or as “Fluoride on Amberlyst
A-26”.
ASSOCIATED CONTENT
* Supporting Information
Characterization data and copies of the 1H and 13C NMR spectra
for all compounds 3. This material is available free of charge via
■
S
AUTHOR INFORMATION
Corresponding Author
■
(11) Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. J. Org. Chem.
2004, 69, 8780−8785.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research has been developed and partially financed within
the National project “BIT3G” − Italian Green Chemistry
Cluster. We gratefully acknowledge the Universita
̀
degli Studi di
e della
Perugia and the Ministero dell’Istruzione, dell’Universita
̀
Ricerca (MIUR) for the financial support within the program
“Firb-Futuro in Ricerca” ref. N. RBFR08JKHI. We also thank the
“Fondazione Cassa di Risparmio di Terni e Narni” for financial
support.
REFERENCES
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dx.doi.org/10.1021/ol502855q | Org. Lett. XXXX, XXX, XXX−XXX