Chemical Modification of Plant Alkaloids. 8. Stereocontrolled T-Reactions of (1R,5S,12S)-Tetrahydrocytisine Derivatives
- 50 Downloads
New heterocyclic quinolizidine systems were prepared from (1R,5S,12S)-tetrahydrocytisine. The synthetic scheme included arylation of tetrahydrocytisine by 2-fluoro-5-nitrobenzaldehyde and condensation of the resulting aldehyde with 1,3-dimethylbarbituric acid. The Knoevenagel intermediate obtained from the condensation was cyclized by a T-reaction to give two spirocyclic products as a derivative with the lupanine skeleton and its regioisomer with the 11,15-diazapentacyclo[11.7.1.02,11.05,10.015,20]heneicosane skeleton. The cyclization occurred highly stereoselectively. The structures of the products were proven using NMR and X-ray crystal structure analyses.
Keywords(1R,5S,12S)-tetrahydrocytisine 1,3-dimethylbarbituric acid hydride shift T-reaction lupanine derivative stereocontrolled synthesis
We thank the Russian Foundation for Basic Research (Grant RFBR No. 16-29-10782-ofi_m) and PFUR Program 5-100 for financial support. X-ray measurements were made using the unique science facility at the Kurchatov synchrotron light source and were sponsored by the Ministry of Education and Science of the RF (Project Identifier RFMEFI61917X007).
- 1.K. Saito, S. Takamatsu, M. Yamazaki, S. Ohmiya, and I. Murakoshi, Tennen Yuki Kagobutsu Toronkai Koen Yoshishu, 32, 268 (1990); Chem. Abstr., 114, 203603 (1991).Google Scholar
- 4.A. Yu. Platonova, T. V. Glukhareva, O. A. Zimovets, and Yu. Yu. Morzherin, Khim. Geterotsikl. Soedin., 3, 386 (2013).Google Scholar
- 5.K. A. Krasnov and V. G. Kartsev, Zh. Org. Khim., 41 (6), 920 (2005).Google Scholar
- 6.K. A. Krasnov and V. G. Karcev, in: The Chemistry and Biological Activity of Synthetic and Natural Compounds. Nitrogen-Containing Heterocycles, Vol. 1, V. G. Karcev (ed.), ISCPF Press, Moscow, 2006, p. 76.Google Scholar
- 11.K. A. Krasnov, V. G. Kartsev, and V. N. Khrustalev, Izv. Akad. Nauk, Ser. Khim., 52 (3), 675 (2003).Google Scholar
- 12.T. G. G. Battye, L. Kontogiannis, O. Johnson, H. R. Powell, and A. G. W. Leslie, Acta Crystallogr., Sect. D: Biol. Crystallogr., 67, 271 (2011).Google Scholar
- 13.P. Evans, Acta Crystallogr., Sect. D: Biol. Crystallogr., 62, 72 (2006).Google Scholar
- 14.G. M. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem., 71, 3 (2015).Google Scholar