TY - JOUR
T1 - Synthesis and chemistry of 1,3,5,7-tetranitrocubane including measurement of its acidity, formation of o-nitro anions, and the first preparations of pentanitrocubane and hexanitrocubane
AU - Lukin, Kirill A.
AU - Li, Jianchang
AU - Eaton, Philip E.
AU - Kanomata, Nobuhiro
AU - Hain, Jürgen
AU - Punzalan, Eric
AU - Gilardi, Richard
PY - 1997
Y1 - 1997
N2 - Nitro groups on alternate corners of cubane enhance the acidity of cubyl hydrogen (pK(a) ~21) and provide sufficient activation for ready anion formation. The sodium salt of 1,3,5,7-tetranitrocubane reacts easily with electrophiles and leads thereby to yet more highly substituted cubanes, like carbomethoxy- and (trimethylsilyl)tetranitrocubane. Anions from these species are also easily formed and are useful for further substitution on the cubane nucleus. Dinitrogen tetraoxide reacts with the anion of tetranitrocubane to give 1,2,3,5,7-pentanitrocubane, the first cubane to contain vicinal nitro groups. The reaction probably involves oxidation of the anion to the corresponding radical. Similarly, the anion of pentanitrocubane is used to prepare 1,2,3,4,5,7-hexanitrocubane, the most highly nitrated cubane made to date. Single-crystal X-ray structural information is given for both penta- and hexanitrocubane.
AB - Nitro groups on alternate corners of cubane enhance the acidity of cubyl hydrogen (pK(a) ~21) and provide sufficient activation for ready anion formation. The sodium salt of 1,3,5,7-tetranitrocubane reacts easily with electrophiles and leads thereby to yet more highly substituted cubanes, like carbomethoxy- and (trimethylsilyl)tetranitrocubane. Anions from these species are also easily formed and are useful for further substitution on the cubane nucleus. Dinitrogen tetraoxide reacts with the anion of tetranitrocubane to give 1,2,3,5,7-pentanitrocubane, the first cubane to contain vicinal nitro groups. The reaction probably involves oxidation of the anion to the corresponding radical. Similarly, the anion of pentanitrocubane is used to prepare 1,2,3,4,5,7-hexanitrocubane, the most highly nitrated cubane made to date. Single-crystal X-ray structural information is given for both penta- and hexanitrocubane.
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U2 - 10.1021/ja970552q
DO - 10.1021/ja970552q
M3 - Review article
AN - SCOPUS:0030703631
VL - 119
SP - 9591
EP - 9602
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 41
ER -