Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon–Carbon Cleavage/Oxime-Release-Coupling Reactions

The exploitation
of C–C activation to facilitate chemical
reactions is well-known in organic chemistry. Traditional strategies
in homogeneous media rely upon catalyst-activated or metal-mediated
C–C bonds leading to the design of new processes for applications
in organic chemistry. However, activation of a C–C bond, compared
with C–H bond activation, is a more challenging process and
an underdeveloped area because thermodynamics does not favor insertion
into a C–C bond in solution. Carbon–carbon bond cleavage
through loss of an oxime moiety has not been reported. In this paper,
a new observation of self-coupling via C–C bond cleavage with
concomitant loss of oxime in the absence of metals (either metal-complex
mediation or catalysis) results in dihydroxylammonium 5,5-bistetrazole-1,10-diolate
(TKX-50) as well as N,N′-([3,3′-bi­(1,2,4-oxadiazole)]-5,5′-diyl)­dinitramine,
a potential candidate for a new generation of energetic materials.