RESUMO
A palladium-catalyzed synthesis of 2-SF5 -indenols has been developed by reacting commercially available boronic acid derivatives and readily accessible SF5 -alkynes. The present methodology is fully regioselective thanks to the intrinsic polarization of SF5 -alkynes. A selection of downstream functionalizations has been performed to highlight the versatility of 2-SF5 -indenols and indenones as platforms for the design of more complex SF5 -containing molecules.
RESUMO
Herein is described a fully regio- and stereoselective hydroelementation reaction of SF5 -alkynes with N, O and S-nucleophiles and further functionalization of the corresponding Z-(hetero)vinyl-SF5 intermediates, a suitable platform to access α-SF5 ketones and esters, ß-SF5 amines and alcohols under mild reaction conditions. Experimental and computational comparative studies between SF5 - and CF3 -alkynes have been performed to highlight and explain the difference of reactivity and selectivity observed between these two fluorinated motifs.
RESUMO
The chloropentafluorosulfanylation of alkynes is a delicate but crucial operation for accessing SF5-alkynes that serve as substrates in numerous transformations. Dolbier's procedure using Et3B/O2 was the most efficient approach, while recent efforts make use of other initiators and light activation. We found that THF, as a single stimulus, is sufficient to trigger the reaction of SF5Cl with alkynes. We determined the configuration of Cl/SF5 products and clarified the structure of side-products.
RESUMO
Pyrazines are reactive 4π partners in intermolecular Diels-Alder cycloaddition with exceptionally activated dienophiles or in an intermolecular version at elevated temperatures. Herein, it is shown that an intramolecular cascade could occur even at room temperature, delivering a collection of 6- or 7-aza-indazoles. An interesting substituent effect of the cycloaddition precursor on the product distribution was uncovered, and in situ NMR studies were conducted to gain insights into this unexpected selectivity.