1. Divalent lanthanide derivatives in organic synthesis. 1. Mild preparation of samarium iodide and ytterbium iodide and their use as reducing or coupling agents
2. For representative reviews, see: (a) Molander, G. A. Chem. Rev. 1992, 92, 29–68; (b) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J. Synlett1992, 943–961; (c) Molander, G. A.; Harris, C. R. Chem Rev. 1996, 96, 307–338; (d) Krief, A.; Laval, A.-M. Chem. Rev.1999, 99, 745–777.
3. Representative intramolecular reactions. Ketone–aldehyde: (a) Molander, G. A.; Kenny, C. J. Org. Chem.1988, 53, 2132–2134; (b) Davey, A. E.; Schaeffer, M. J.; Taylor, R. J. K. J. Chem. Soc., Perkin Trans. 11992, 2657–2666; (c) de Gracia, I. S.; Dietrich, H.; Bodo, S.; Chiara, J. L. J. Org. Chem.1998, 63, 5883–5889; (d) Kan, T.; Hosokawa, S.; Nara, S.; Oikawa, M.; Ito, S.; Matsuda, F.; Shirahama, H. J. Org. Chem.1994, 59, 5532–5534. Ketone–chloro acyl: (e) see p. 50 in Ref. 2a. Ketone–nitrile: (f) Molander, G. A.; Wolfe, C. N. J. Org. Chem.1998, 63, 9031–9036, also see Ref. 3i; (g) Zhou, L.; Zhang, Y.; Shi, D. Tetrahedron Lett.1998, 39, 8491–8494; Zhou, L.; Zhang, Y.; Shi, D. Synthesis2000, 91–98; (h) Kakiuchi, K; Fujioka, Y.; Yamamura, H.; Tsutsumi, K.; Morimoro, T.; Kurosawa, H. Tetrahedron Lett.2001, 42, 7595–7598. Ketone–unactivated olefin: (i) Molander, G. A.; Kenny, C. J. Am. Chem. Soc.1989, 111, 8236–8246. Ketone–haloalkyl: (j) Molander, G. A.; Etter, J. B. J. Org. Chem.1986, 51, 1778–1786.
4. In the reaction of haloalkylated ketones with SmI2, there has been mechanistic controversy regarding whether it is carbonyls or carbonhalogen bonds that are first reduced by SmI2.2b,4b
5. On the mechanism of the intramolecular samarium Barbier reaction. Probes for formation of radical and organosamarium intermediates