Chemo- and regio-divergent access to fluorinated 1-alkyl and 1-acyl triazenes from alkynyl triazenes.

The 1,1,2,2-tetrafluoroethylene unit is prevalent in bioactive molecules and functional materials. Despite being in principle a straightforward strategy to access this motif, the direct tetrafluorination of alkynes involves very hazardous or inconvenient reagents. Therefore, safer and convenient alternatives are sought after. We developed a mild and operationally simple perfluorination method converting 1-alkynyl triazenes into 1,1,2,2-tetrafluoro alkyl triazenes, employing cheap and readily accessible reagents. Moreover, a judicious tuning of the reaction conditions enables access to α-difluoro triazenyl ketones. Complementary, electrophilic fluorination of alkynyl triazenes gives rise to the regioisomeric α-difluoro acyl triazenes. These three chemo- and regio-divergent protocols enable access to elusive fluorinated 1-alkyl and 1-acyl triazenes, thus expanding the chemical space for these unusual entities. Furthermore, several reaction intermediates and side products revealed insights on the reaction pathways that may be useful for further fluorination chemistry of alkynes.

Synthesis of bicyclic vinyl triazenes by Ficini-type reactions.

Cyclic olefins with triazene functions can display interesting reactivity, but synthetic access to these compounds is limited thus far. Herein, we describe the synthesis of cyclobutenyl triazenes fused to cyclopentanone or cyclohexanone rings. The bicyclic compounds are obtained by Lewis acid-catalyzed [2 + 2] cycloaddition reactions of 1-alkynyl triazenes and enones. In the presence of Me2AlCl, bicyclic [4.2.0] triazenes rearrange into [3.2.1] ring systems. The triazene function in the latter can be used for further functionalizations. Notably, we show that vinyl triazenes can serve as substrates for Pd-catalyzed cross-coupling reactions with arylboronic acids.

Alkynyl triazenes enable divergent syntheses of 2-pyrones.

The 2-pyrone motif occurs frequently in bioactive natural products and is appreciated as synthetic intermediates. However, only few methods allow for diversifying functional group modifications on this relevant heterocycle. The distinct properties of 1-alkynyl triazenes promote a smooth addition of propiolic acids across the triple bond. Addition of catalytic amounts of silver salt induces cyclization to 2-pyrones. Depending on the reaction temperature, either 6-triazenyl or 5-triazenyl 2-pyrones are selectively formed. The triazenyl unit is subsequently replaced by a variety of valuable groups in a one-pot process yielding for instance 2-fluoro pyrones. The substitution occurs with an intriguing 1,5-carbonyl transposition. Moreover, the triazenyl group serves as traceless activating group for subsequent Diels-Alder cycloadditions and as a constituting unit for rare fused aminopyrazole pyrone heterocycles.