A safe synthesis of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) has been achieved by using 2-methoxyisopropyl-protected diazidoglyoxime (MIP-DAzG) as an insensitive intermediate. The MIP group acted as a protecting group, which was quantitatively introduced into dichloroglyoxime without the need for any additives, and effectively removed during the course of the cyclization reaction used to construct the 5,5'-bistetrazole-1,1'-diol moi-ety under acidic conditions. Notably, the sensitivity results obtained for MIP-DAzG were significantly lower than those of the DAzG intermediate used in the previously reported synthesis of TKX-50. Furthermore, the sensitivity studies on MIP-DAzG indicated that the sensitivity of protected DAzG was affected by the steric hindrance around the hydroxyl group in DAzG caused by the protecting group.

A DABCO-mediated electrophilic α-trifluoromethylthiolation of α,β-unsaturated carbonyl compounds comprising no β-substituents has been achieved using N-trifluoromethylthio-dibenzenesulfonimide as the SCF 3 source. The direct trifluoromethylthiolation provides the corresponding α-trifluoromethylthio-α,β-unsaturated carbonyl products in good yields (up to 88%). Furthermore, the vinyl group in the α-trifluoromethylthioα,β-unsaturated carbonyl product was successfully transformed into diverse functional groups in good to excellent yields (70−95%) by reactions such as epoxidation, aziridination, hydrocyanation, and hydrogenation.

Organocatalytic enantioselective synthesis of acyclic pyrimidine nucleosides was achieved by the aza-Michael reaction of pyrimidines as N-centered nucleophiles to α,β-unsaturated aldehydes.

A cascade diazotization/intramolecular radical C–H heteroarylation of 1-benzyloxy-5-aminotetrazoles and 1-phenethyl-5-aminotetrazoles as substrates using sodium nitrite and acetic acid without any heating, catalysis, irradiation, or electrolysis is reported. This one-pot reaction afforded the desired tricyclic tetrazole products in good yields (up to 94%) without isolation of the diazonium salt intermediate under mild reaction conditions.