The synthetic research and development of high energy density compound (HEDC) were reviewed. Diformyltetrahydroxypiperazine (DFTHP) is an important precursor compound for synthesizing the energetic compound and cyclic-nitroamines compound. The synthesis research of DFTHP can be divided into three periods—condensation reaction of piperazine, fused ring reaction of piperazine and cage reaction of piperazine. Both hexanitrohexaazatricyclododecanedione (HHTDD) and hexanitrohexaazatricyclotetradecanedifuroxan (HHTTD) are the typical representatives of fused ring-nitroamine. 4,10-Dinitro-2,6,8,12-tetraoxadiazatetrocyclo［5.5.0.0^5,9.0^3,11］dodecane (TEX) is the typical representative of cage nitroamine.