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Paper | Regular issue | Vol 43, No. 8, 1996, pp.1633-1640
Published online, 1st January, 1970
DOI: 10.3987/COM-96-7462
Synthesis of 2,12-Dithia[3](2,6)pyridino[3](1,4)cycl[3.2.2]azinophane and It's Barrier to Methylene Twist

Yoshiro Matsuda,* Keisuke Katou, Hiroshi Matsumoto, Takanobu Nishiyori, Takashi Uemura, and Maki Urakami

*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan

Abstract

A synthesis of the title compound (11) is completed starting from indolizine (3). Key intermediate, bis(mercaptomethyl)cycl[3.2.2]azine (9) has been synthesized by reduction of bis(acetylthiomethyl)cycl[3.3.2]azine (8) with LiAlH4. 2,12-Dithia[3](2,6)pyridino[3](1,4)cycl[3.2.2]azinophanes (11a,b) have been synthesized by the reaction of 9 with 2,6-bis(bromomethyl)pyridine (10) in the presence of Cs2CO3 by the high dilution method. In the 1H-nmr spectrum of 11a,b, these exist in the syn conformation in their 1H-nmr spectra. With regard to 2,12-dithia[3](2,6)pyridino[3](1,4)cycl[3.2.2]azinophane (11a), the coalescence temperature for the methylene twist yields an activation barrier, δ G, of 79.5 kJ mol-1 for variable temperature (VT) nmr method.