TY - JOUR
T1 - Synthesis, structure, and chemistry of new, mixed group 14 and 16 heterocycles
T2 - Nucleophile-induced ring contraction of mesocyclic dications
AU - Block, Eric
AU - Dikarev, Evgeny V.
AU - Glass, Richard S.
AU - Jin, Jin
AU - Li, Bo
AU - Li, Xiaojie
AU - Zhang, Shao Zhong
PY - 2006/11/22
Y1 - 2006/11/22
N2 - More than 40 new 4- to 12-membered ring heterocycles containing various combinations of Group 14 and 16 elements Si, Sn, S, Se, and Te have been synthesized and fully characterized. Synthesis of these small-ring as well as medium-ring (mesocyclic) heterocycles from α,ω-dihalides is facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors. Conformations of several of the new ring systems in the solid state have been determined by X-ray crystal structure analysis. Oxidation of mixed S(Se, Te)/Si eight-membered ring mesocycles with NOPF6 or Br2 gives dications or a bicyclic dibromide, respectively, which can be characterized by NMR methods. On treatment with nucleophiles, mesocyclic dications, or the corresponding radical cations undergo ring contraction, giving five- or six-membered ring heterocycles. Photolysis of a S/Se four-membered ring heterocycle gives selenoformaldehyde, trapped in 80% yield with 2,3-dimethyl-1,3-butadiene.
AB - More than 40 new 4- to 12-membered ring heterocycles containing various combinations of Group 14 and 16 elements Si, Sn, S, Se, and Te have been synthesized and fully characterized. Synthesis of these small-ring as well as medium-ring (mesocyclic) heterocycles from α,ω-dihalides is facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors. Conformations of several of the new ring systems in the solid state have been determined by X-ray crystal structure analysis. Oxidation of mixed S(Se, Te)/Si eight-membered ring mesocycles with NOPF6 or Br2 gives dications or a bicyclic dibromide, respectively, which can be characterized by NMR methods. On treatment with nucleophiles, mesocyclic dications, or the corresponding radical cations undergo ring contraction, giving five- or six-membered ring heterocycles. Photolysis of a S/Se four-membered ring heterocycle gives selenoformaldehyde, trapped in 80% yield with 2,3-dimethyl-1,3-butadiene.
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U2 - 10.1021/ja065037j
DO - 10.1021/ja065037j
M3 - Article
C2 - 17105306
AN - SCOPUS:33845198618
VL - 128
SP - 14949
EP - 14961
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 46
ER -