TY - JOUR
T1 - Generation and spectroscopic properties of syn-1,6:9,14- bismethanodicyclodeca[cd,gh]pentalene dianion
AU - Kuroda, Shigeyasu
AU - Terada, Yoshihiro
AU - Miyatake, Ryuta
AU - Horino, Yoshikazu
AU - Abe, Takako
AU - Fujiwara, Yurie
AU - Oda, Mitsunori
N1 - Funding Information:
This research was carried out in part under financial support from the Kyowa Hakko Chemical Co. Inc (for S.K.). Financial support from the Faculty of Science at Shinshu University (for M.O.) is also acknowledged.
PY - 2011/12/28
Y1 - 2011/12/28
N2 - The hydrocarbon precursor, 8,16-dihydro-syn-1,6;9,14-bismethano[cd,gh] pentalene (5), to the title structure, dianion 4, was synthesized from ethyl 4-bromo-1,6-methano[10]annulene-3-carboxylate (6) in three steps, which included a nickel-catalyzed stereoselective homo-coupling, LiAlH4 reduction of the ester groups, and scandium triflate-catalyzed double intramolecular cyclization of the biarylmethyldiol. Deprotonation of 5 with n-butyllithium in THF-d8 provided 4, whose structure was confirmed by NMR analysis. Aspects of chemical shifts in the 1H NMR spectrum and the calculated structure of 4 establish its diatropic nature.
AB - The hydrocarbon precursor, 8,16-dihydro-syn-1,6;9,14-bismethano[cd,gh] pentalene (5), to the title structure, dianion 4, was synthesized from ethyl 4-bromo-1,6-methano[10]annulene-3-carboxylate (6) in three steps, which included a nickel-catalyzed stereoselective homo-coupling, LiAlH4 reduction of the ester groups, and scandium triflate-catalyzed double intramolecular cyclization of the biarylmethyldiol. Deprotonation of 5 with n-butyllithium in THF-d8 provided 4, whose structure was confirmed by NMR analysis. Aspects of chemical shifts in the 1H NMR spectrum and the calculated structure of 4 establish its diatropic nature.
KW - Carbanions
KW - Methano[10]annulenes
KW - NICS values
KW - Ni-catalyzed coupling
KW - Scandium triflate
UR - http://www.scopus.com/inward/record.url?scp=82255191206&partnerID=8YFLogxK
U2 - 10.1016/j.tetlet.2011.10.077
DO - 10.1016/j.tetlet.2011.10.077
M3 - 学術論文
AN - SCOPUS:82255191206
SN - 0040-4039
VL - 52
SP - 7071
EP - 7074
JO - Tetrahedron Letters
JF - Tetrahedron Letters
IS - 52
ER -